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# THE VISCOUS SLOWING DOWN OF SUPERCOOLED LIQUIDS AND THE GLASS TRANSITION: PHENOMENOLOGY, CONCEPTS, AND MODELS

## I INTRODUCTION

When cooling a liquid, usually under isobaric P=1atm conditions, one can often bypass crystallization, thereby obtaining a supercooled liquid that is metastable relative to the crystal. When the temperature is further lowered, the viscosity of the liquid, as well as the relaxation times associated with the primary ($`\alpha `$) relaxation of all kinds of structural, dielectric, macro- and micro-scopic observables, increase rapidly, until a temperature is reached at which the liquid can no longer flow and equilibrate in the time scale of the experiment. The system effectively appears as a rigid amorphous material and is then called a glass. Glass formation thus results from the strong viscous slowing down of a liquid with decreasing temperature***Although not as widely used, there are other ways of generating glassy structures, such as vapor deposition, in situ polymerization or chemical reactions. , a slowing down that can be considered as a classical example of a “jamming process”. A characteristic of this process that is unanimously recognized, a unanimity rare in this otherwise quite open and controversial field, is that it is a dynamic effect. The so-called “glass transition” is not a bona fide thermodynamic phase transition, but represents a crossover below which a liquid falls out of equilibrium on the experimental time scale. The transition temperature, $`T_g`$ depends on this time scale, set either by the observation time (corresponding, for instance, to a relaxation time of $`10^2`$ or $`10^3`$ sec or a viscosity of $`10^{13}`$ Poise) and/or by the cooling rate (in a typical differential scanning calorimetry measurement, $`10`$ K per minute). The dependence on cooling rate is, however, weak, a difference of few K in $`T_g`$ for an order-of-magnitude change of the rate; this is so because on further lowering of the temperature the viscosity and $`\alpha `$-relaxation times rapidly become enormous and out of reach of any experimental technique.

In the following, we shall focus on the jamming process occurring in the supercooled liquid state. Both the crystalNote that for several liquids, such as m-fluoroaniline and dibutylphtalate at atmospheric pressure and atactic polymers, crystallization has never been observed., which is the stable phase below the melting point $`T_m`$ but can be ignored in discussing the glass transition, and the glassy state itself will be excluded from the present discussion. By appropriately eliminating the crystal (experimentally as well as theoretically), metastable supercooled liquids can be treated by equilibrium thermodynamics, statistical mechanics, and conventional linear-response formalisms. Glasses on the other hand, although mechanically stable, are out-of-equilibrium states; especially near $`T_g`$, they display nonlinear responses and relaxations known as aging or annealing, and their properties depend on their history of preparation.  These phenomena will not be considered in this review.

## II SALIENT PHENOMENOLOGY

The distinctive feature of glass-forming liquids is the dramatic, continuous increase of viscosity and $`\alpha `$-relaxation times with decreasing temperature. This sort of jamming is observed in a large variety of substances: covalently bonded systems like $`SiO_2`$, hydrogen-bonded liquids, ionic mixtures, polymers, colloidal suspensions, molecular van der Waals liquids, etc. The emphasis will be placed on those liquids (the vast majority) that do not form 2- or 3-dimensional networks of strong bonds because they show the most striking behavior when passing from the high-temperature liquid phase to the deeply supercooled and very viscous regime.

### 1 Strong, super-Arrhenius T-dependence of viscosity and $`\alpha `$-relaxation times

The viscosity $`\eta `$ and $`\alpha `$-relaxation times can change by $`15`$ orders of magnitude for a mere decrease of temperature by a factor twoThe (shear) viscosity $`\eta `$ can be related to a time characteristic of $`\alpha `$-relaxation, the average shear stress relaxation time $`\tau _s`$, by $`\eta =G_{\mathrm{}}\tau _s`$, where $`G_{\mathrm{}}`$ is the infinite-frequency shear modulus; $`G_{\mathrm{}}`$ is typically of the order of $`10^{10}10^{11}`$ erg.cm-3, so that a viscosity of $`10^{13}`$ Poise roughly corresponds to a time of $`10^2`$ or $`10^3`$ sec.. Such a dramatic variation is conveniently represented on a logarithmic plot of $`\eta `$ or $`\tau _\alpha `$ versus $`1/T,`$ i.e., an Arrhenius plot: see Fig. 1a. A system like $`GeO_2`$, an example of a network-forming system, is characterized by an almost linear variation, which indicates an Arrhenius temperature dependence. For all other liquids on the figure there is a marked upward curvature, which represents a faster-than-Arrhenius, or super-Arrhenius, temperature dependence and is often described by an empirical Vogel-Fulcher-Tammann (VFT) formula (also called Williams-Landel-Ferry formula in the context of polymers studies),

$$\tau _\alpha =\tau _0\mathrm{exp}\left(D\frac{T}{TT_0}\right),$$
(1)
where $`\tau _0`$, $`D`$ and $`T_0<T_g`$ are adjustable parameters. On the basis of such Arrhenius plots, with the temperature scaled by $`T_g`$, Angell proposed the now standard classification of glass-forming liquids into strong (Arrhenius-like) and fragile (super-Arrhenius) systems; in Eq. (1), the smaller the value of $`D`$, the more fragile the liquid. There are, of course, alternative fitting formulas that have been used, some which do not imply a singularity at a nonzero temperature as does the expression in Eq. (1).

A different way of representing the phenomenon is to plot the effective activation free energy for $`\alpha `$-relaxation, $`E(T)`$, obtained from

$$\tau _\alpha =\tau _{\alpha ,\mathrm{}}\mathrm{exp}\left(\frac{E(T)}{k_BT}\right),$$
(2)
where $`k_B`$ is the Boltzmann constant and $`\tau _{\alpha ,\mathrm{}}`$ is a high-$`T`$ relaxation time, or from a similar equation for the viscosity. This is illustrated in Fig. 1b, where the temperature has been scaled for each liquid to a temperature T\* above which the dependence is roughly Arrhenius-like. Although the determination of $`T^{}`$ is subject to some uncertainty, the procedure emphasizes the crossover from Arrhenius-like to super-Arrhenius behavior that is typical of and quite distinct in most supercooled liquids. The appreciable size of the effective activation free energies $`E(T)`$, namely, $`40k_BT_g`$ at the glass transition, is indicative of thermally activated dynamics. Such a large effective activation free energy for weakly bonded fragile molecular liquids such as orthoterphenyl is an intriguing feature of the phenomenology. Another peculiar property of $`E(T)`$ for fragile systems is that it increases significantly between $`T^{}`$ and $`T_g`$ (a factor $`3`$, i.e., a factor of $`5`$ or $`6`$ in units of the thermal energy $`k_BT`$, for weakly bonded fragile liquids). Such a variation is not commonly encountered. For instance, in the field of critical phenomena, the slowing down of dynamics that occurs when approaching the critical point is usually characterized by a power law growth of the relaxation time; in terms of effective activation free energy, this corresponds to a logarithmic growth and it is slower than the variation described by the VFT formula, Eq. (1). Unusually strong slowing down, with exponentially growing times similar to Eq. (1), is found in some disordered systems like the random field Ising model and it is known as “activated dynamic scaling”.

### 2 Nonexponential relaxations

In an “ordinary” liquid above the melting point, relaxation functions are usually well described, after some transient time, by a simple exponential decay. Deviations are observed, but they are neither systematic nor very marked. The situation changes at lower temperatures, and the $`\alpha `$-relaxation is no longer characterized by an exponential decay. A better representation is provided by a “stretched exponential” (or Kohlrausch-Williams-Watts function),

$$f_\alpha (t)\mathrm{exp}\left[\left(\frac{t}{\tau _\alpha }\right)^\beta \right],$$
(3)
where $`\beta `$ is the stretching parameter; the smaller $`\beta `$ the more “stretched” the relaxation. Although not unambiguously established, the degree of departure from exponential behavior, or stretching, appears to increase (i.e., $`\beta `$ decreases) with decreasing temperature.

Alternatively, in frequency space, the spectrum of the imaginary part of the susceptibility, which is characterized by a peak at a frequency $`\omega _\alpha 1/\tau _\alpha `$, tends to be broader (when plotted as a function of $`log(\omega )`$ ) than the simple Lorentzian or Debye spectrum that is just the Fourier transform of the time-derivative of an exponential relaxation function (see Fig. 2). Fitting formulas related to Eq. (3), formulas like the Cole-Davidson function for frequency-dependent susceptibilities, $`(1i(\omega /\omega _\alpha ))^\beta ^{}`$, are used to fit the spectroscopic data, but similar trends are observed: the $`\alpha `$ peak, as observed for instance in the imaginary part of the dielectric susceptibility as a function of $`log(\omega )`$, broadens as the temperature is lowered towards $`T_g`$, which indicates increasing departure from Debye/exponential behavior. Except for network-forming systems, the stretching of the $`\alpha `$ relaxation is significant ($`\beta `$ is typically between $`0.3`$ and $`0.6`$ for fragile liquids at $`T_g`$). However, and this point may not have been given enough attention, the stretching, or broadening in frequency space, is relatively small when compared to the extremely rapid variation with temperature of the $`\alpha `$-relaxation time itself. This is to be contrasted for instance with the activated critical slowing discussed above. There, the power law growth of the activation free energy when the temperature is decreased toward the critical point comes with a more striking stretching of the relaxation function that occurs on a logarithmic scale: in this case, in place of a stretched exponential behavior as in Eq. (3), $`\mathrm{ln}(f(t))`$ goes as some power of $`(1/\mathrm{ln}(t))`$.

### 3 No marked changes in structural quantities

It is tempting to associate the huge increase in $`\alpha `$-relaxation times and viscosity with the growth of a structural correlation length. However, no such growth has been detected so far in supercooled liquids. Quite to the contrary, the variation of structure in liquids and glasses, as measured in neutron and X-ray diffraction experiments, appear rather bland (see Fig. 3). The ordinary, high-temperature liquid has only short-range order whose signature in the static structure factor $`S(Q)`$ is a broad peak (or a split peak for some molecular systems as illustrated in Fig. 3) at a wave vector $`Q`$ that roughly corresponds in real space to some typical mean distance between neighboring molecules. As the temperature is lowered and the supercooled regime is entered, there are small, continuous variations of the structure factor that mostly reflect the change in density (typically, a $`5\%`$ change between $`T_m`$ and $`T_g`$) and, possibly, some adjustments in the local arrangements of the molecules. There is no sign, however, of a significantly growing correlation length, nor of the appearance of a super-molecular length.

In network-forming and $`H`$-bonded systems, an additional “pre-peak” is sometimes detectable at wave vectors somewhat lower than that of the main peak, but it is attributed to specific effects induced by the strongly directional intermolecular bonds and not to a length scale that would correlate with the viscous slowing down.

In contrast to this lack of structural signature for the existence of an increasing super-molecular correlation length with decreasing temperature, there is significant evidence, as discussed below, that corresponding “dynamical” correlation length do exist.

### 4 Rapid entropy decrease and Kauzmann paradox

The absence of marked changes in the structure, at least at the level of two-particle density correlations, or of a strong increase in any directly measured static susceptibility is a puzzling feature of the jamming process associated with glass formation. The only static quantity that shows behavior that might be relevant is the entropy. Below the melting point, $`T_m`$, the heat capacity $`C_p(T)`$ of a supercooled liquid is larger than that of the corresponding crystal. (At $`T_g`$, the $`C_p`$ of the liquid drops to a value that is characteristic of the glass and is close to the $`C_p`$ of the crystal, but this is a consequence of the system no longer being properly equilibrated.) As a result of this “excess” heat capacity, the entropy difference between the liquid and the crystal decreases with temperature, typically by a factor of $`3`$ between $`T_m`$ and $`T_g`$ for fragile liquids. The effect is illustrated in Fig. 4 and leads to the famous Kauzmann paradox: if the entropy difference is extrapolated to temperatures below $`T_g`$, its extrapolated value vanishes at some nonzero temperature $`T_K`$, which results in the unpleasant feature that the entropy of the liquid becomes equal to that of the crystal (even more unpleasant: if the extrapolation is carried to still lower temperatures, the entropy of the liquid becomes negative, which violates the third law of thermodynamics). The paradox is that this extrapolated entropy crisis is avoided for a purely dynamic reason, the intervention of the glass transition: what would occur if one were able to keep the supercooled liquid equilibrated down to temperatures below $`T_g`$? There are certainly many ways to answer the question. The paradox could be resolved by the existence between $`T_g`$ and $`T_K`$ of an intrinsic limit of metastability of the liquid or of a second-order phase transition§§§Note that a low-$`T`$ first-order transition does not resolve the paradox because it can be supercooled. (a speculation that gains additional credibility with the observation that the VFT temperature $`T_0`$ at which the extrapolated viscosity and $`\alpha `$-relaxation times diverge (see Eq. (1)) is often found close to $`T_K`$). Even more simply, one might find that the extrapolation breaks down above $`T_K`$ and that the entropy-difference curve levels off and goes smoothly to zero at zero $`K`$, in much the same way as it does in the Debye theory of crystals. These are of course all speculations, but it remains that the rapid decrease of the entropy of the supercooled liquid relative to that of the crystal represents an intriguing aspect of the phenomenology of fragile glass-formers.

### 5 Two-step relaxation and secondary processes

As we stressed before, the salient features related to glass formation concern the long-time (low-frequency) primary or $`\alpha `$ relaxation. As the $`\alpha `$-relaxation time increases with decreasing temperature, so too does the window between this time and typical microscopic, picosecond or sub-picosecond times. When the relaxation function is plotted against the logarithm of the time, one then observes what is sometimes called a “two-step relaxation”. An illustration is given in Fig. 5 by the dynamic structure factor of the fragile ionic glass-former $`Ca_{0.4}K_{0.6}(NO_3)_{1.4}`$ obtained by neutron techniques. At high temperature, the relaxation function is essentially a one-step process. However, as the liquid becomes more viscous, the relaxation proceeds in two steps separated by a plateau. Although the terminology is far from being universally accepted, the approach to the plateau from the short-time side is often referred to as $`\beta `$ or fast-$`\beta `$ relaxation. If one is to fit the long-time part by a stretched exponential (Eq. (3)), there is a large range of “mesoscopic” times that is not adequately described and that widens as the temperature is lowered. Power law functions of time are often used to reproduce the relaxation function in this mesoscopic range.

This two-step relaxation feature is common to all fragile liquids. In addition, there may also appear additional secondary processes, detected first by Johari and Goldstein in dielectric spectroscopy.  Such secondary processes, whose presence and strength strongly vary from one liquid to another, have characteristic frequencies that are intermediate between those of the $`\alpha `$ and fast-$`\beta `$ relaxations. They are denoted Johari-Goldstein-$`\beta `$, slow-$`\beta `$, or simply $`\beta `$ processes.  To make the description more complete, one should also mention the so-called “boson peak” that may be present on the high-frequency side ($`10^210^3Ghz`$) of light and neutron scattering (or absorption) spectra. Here we do not discuss either the slow-$`\beta `$ processes or the boson peak.

## III  A SELECTION OF QUESTIONS

After this brief review of the salient aspects of the phenomenology of supercooled liquids as they get glassy, we discuss in more detail a number of questions, whose answers give justification or put constraints on the theoretical picture one can build to explain the viscous slowing down.

### 1 How universal is the behavior of glass-forming liquids ?

Universality is a key concept in physics and it has proven to be central in the field of critical phenomena. By the standards of critical phenomena studies, the observed behavior of glass-forming liquids is not universal, the main reason being that no singularity is detected experimentally (or approached asymptotically close), as stressed above. However, if one is willing to take a broader view of the notion of universality, one can find considerable generality or “universality” in the properties, those mostly associated with long-time and low-frequency phenomena, that characterize the approach to the glass transition. For instance, the super-Arrhenius $`T`$-dependence of the viscosity and $`\alpha `$-relaxation times and the nonexponential character of the relaxation function are observed for virtually all glass-formers, be they polymeric, $`H`$-bonded, ionic, van der Waals, etc., with the exception of a minority of strong network-forming systems; and, for a given liquid, these properties are found by a large variety of experimental techniques, such as dielectric relaxation, light and neutron scattering, NMR, viscosity measurements, specific heat spectroscopy, volume and enthalpy relaxation, optical probe methods.

The presence of an underlying ”universality” is supported by the fact that experimental data covering a wide range of temperatures and a great diversity of substances can be collapsed onto master curves with only a small number of species-dependent adjustable parameters. A good example is provided by the scaling plot of the frequency-dependent dielectric susceptibility proposed by Nagel and coworkers. As shown in Fig. 6, the data taken over a $`13`$ decade range of frequencies for many different liquids can be placed with good accuracy onto a single curve after scaling with only three parameters associated with the $`\alpha `$-peak position, width and intensity. The master-curve for the temperature dependence of the effective activation free energy for viscosity and $`\alpha `$ relaxation put forward by Kivelson et al.  is another example. It is nonetheless fair to say that the fits resulting from these various scaling procedures are far from perfect, which leaves room for debate and conflicting interpretations. One can also ask the question whether the universality holds only up to the implied high-frequency cut-off of the susceptibility scaling curve of Nagel et al. (i.e., whether one should be focusing on slow behavior) or whether it extends higher in light of the fact that similarities have also been observed in the high-frequency susceptibilities.

### 2  Is the $`\alpha `$-relaxation homogeneous or heterogeneous?

The observation stressed above that the $`\alpha `$-relaxation is nonexponential in the supercooled liquid range and its representation by a stretched exponential as in Eq. (2) can be formally interpreted in terms of a superposition of exponentially decaying functions with a distribution of relaxation times; but, this per se does not guarantee that the dynamics be “heterogeneous”, in the sense that relaxation of the molecules differs from one environment to another with the environment life time being longer than the relaxation time. An alternative explanation can be offered within a “homogeneous” picture in which relaxation of the molecules everywhere in the liquid is intrinsically nonexponential.

In recent years, there has been mounting evidence that heterogeneities, sufficiently long-lived to be relevant to the $`\alpha `$-relaxation and to be at least partly responsible for its nonexponential feature, do exist in supercooled liquids. The heterogeneous character of the slow dynamics has been demonstrated in several experiments: multi-dimensional NMR,  photobleaching probe rotation measurements,  nonresonant dielectric hole burning.  These techniques involve the selection of a sub-ensemble of molecules in the sample that is characterized by a fairly narrow distribution of relaxation times (and in general a relaxation slower than average) and the further monitoring of the gradual return to the equilibrium situation. Additional evidence of the spatially heterogeneous nature of the dynamics in fragile supercooled liquids is provided by the so-called breakdown of the Stokes-Einstein relation between the translational diffusion constant and the viscosity, and the concomitant “decoupling” between rotational and translational time scales: see Fig.7.

The size of the heterogeneities is not directly observable in the above mentioned experiments, but various estimates, obtained, e. g., from optical studies of the rotational relaxation of probes of varying size,  NMR measurements,  the study of excess light scattering,  and the influence of a well-defined $`3`$-dimensional confinement  lead to a typical length of several nanometers in different fragile liquids near $`T_g`$. One should recall that these signatures are all dynamical and that no signature at such a length scale has been detected so far in small-angle neutron and X-ray diffraction data. If the heterogeneous character of the $`\alpha `$-relaxation appear reasonably well established, at least for deeply supercooled fragile liquids, several points concerning the lifetime, the size, and the nature of the heterogeneities need still be settled.

### 3 Is density or temperature the dominant control variable?

The phenomenon of viscous slowing down and glass formation as it is studied most of the time (and described in the preceding sections) takes place under isobaric $`P=1atm`$ conditions. As a consequence, when the temperature is lowered, there is also an increase of the density of the liquid. This increase is small (a typical variation of $`5\%`$ between $`T_m`$ and $`T_g`$), but it could still have a major influence on the dynamics. Actually, there are theoretical models of jamming, such as those based on free volume concepts and hard sphere systems, that attribute the spectacular increase of viscosity and $`\alpha `$-relaxation times of fragile glass-formers (almost) entirely to the density changes. It is thus important to evaluate the role of density and temperature in driving the jamming process that leads to the glass transition at 1 atm.

Basic models and theories are usually formulated in terms of either density or temperature as control variable, but experiments are carried out with pressure and temperature as external control variables. The data must be converted, when enough experimental results are available, in order to analyze the influence of density at constant temperature and that of temperature at constant density, for a range of density and temperature that is characteristic of the phenomenon at 1 atm. Extant analyses are far from exhaustive. However, as illustrated in Fig. 8, the characteristic super-Arrhenius T-dependence of the viscosity, $`\eta `$, and $`\alpha `$-relaxation times, $`\tau _\alpha `$, appears predominantly due to the variation of temperature and not to that of density. This conclusion is confirmed by a comparative study of the contributions induced by density variations (at constant temperature) and by temperature variations (at constant density) to the rate of change of $`\eta `$ and $`\tau _\alpha `$ at constant (low) pressure in the viscous liquid regime of several molecular and polymeric glass-formers.

How general is the above result? Temperature appears to be the dominant variable controlling the viscous super-Arrhenius slowing down of supercooled liquids at low pressure, but this may not be the case at much higher pressure (although not much data are presently available to confirm this point), and it is most likely not true for describing the concentration-driven congestion of dynamics in colloidal suspensions. In the absence of a “super-universal” picture of the jamming associated with glass formation, we shall restrict ourselves, as we have implicitly done above, to the consideration of supercooled liquids at 1 atm.

### 4 What are the relevant characteristic temperatures?

There is no unbiased way of presenting the phenomenology of glass-forming liquids. Choices must be made about the emphasis put on the different aspects, about the best graphic representations, and about the way in which one analyzes experimental data. To make sense out of the wealth of observations and measurements, it is natural to look for characteristic temperatures about which to organize and scale the data. However, since no singularity is directly detected, the selection of one or several relevant temperatures is far from straightforward. The temperatures that can be easily determined experimentally are the boiling point, $`T_b`$, the melting point, $`T_m`$, and the glass transition temperature(s), $`T_g`$. Unfortunately, the former two are generally considered as irrelevant to the jamming phenomenon, and the latter has an operational rather than a fundamental nature (see the introduction).

Several other candidates have been suggested, that can be split into two groups. First, there are “extrapolation temperatures” below $`T_g`$, i.e., temperatures dynamically inaccessible to supercooled liquids, at which extrapolated behavior diverges or becomes singular. This is the case of the VFT temperature $`T_0`$ (see Eq. 1) and the Kauzmann temperature $`T_K`$ (see section II-4 and Fig. 4). In the second group are “crossover temperatures” above $`T_g`$ at which a new phenomenon seems to appear (decoupling of rotations and translations, emergence of a secondary $`\beta `$ process, etc.), a crossover of behavior or a change of $`\alpha `$-relaxation mechanism seems to take place (passage from Arrhenius to super-Arrhenius $`T`$-dependence, arrest of the relaxation mechanisms described by the mode-coupling theory, putative emergence of activated barrier crossing processes, etc.). A variety of such temperatures for the fragile glass-former $`OTP`$ are shown in Fig. 9: the location of the different characteristic temperatures is illustrated on an Arrhenius plot of the viscosity. It is interesting to note that most putative crossover behaviors occur in the region of strong curvature where $`\eta 110^2`$ Poise or $`\tau _\alpha 10^{10}10^8`$ sec, while, on the other hand, the temperatures obtained by extrapolation of data to low T lie fairly close to each other, some 40 K below $`T_g`$.

### 5 What can be learned from computer simulations?

Computer simulation studies,  in particular those based on Molecular Dynamics algorithms, have proven extremely valuable in investigating the structure and dynamics of simple, ordinary liquids. Their contribution to the understanding of the glass transition is unfortunately limited, the main reason being the restricted range of lengths and times that are accessible to Molecular Dynamics simulations: typical simulations on atomistic models consider $`10^310^4`$ atoms and can follow relaxations for less than $`10^8`$ sec (when expressing the elementary time step in terms of parameters characteristic of simple liquids). As a result, the viscous, deeply supercooled regime of real glass-forming liquids, where strong super-Arrhenius behavior, heterogeneous dynamics, and other significant features associated with the jamming process develop, is out of reach, as is the laboratory glass transition that occurs on a time scale of $`10^2`$ or $`10^3`$ sec. Simple liquid models do form “glasses” on the observation, i.e., simulation, time with many of the attributes of the laboratory glass transition: abrupt change in the thermodynamic coefficients, dependence on the cooling rate, aging effects, etc However, these models are effectively high-temperature structures, since they correspond to liquid configurations that are kinetically arrested at a temperature at which the primary relaxation time is of the order only of nanoseconds. Even with systems specially designed to avoid crystallization, such as binary Lennard-Jones mixtures, the cooling rates to prepare glasses ($`10^8`$ to $`10^9`$ K/sec) are orders of magnitude higher than those commonly used in experiments.. However, these supercooled simulation liquids are not truly fragile (the $`T`$-dependence of the $`\alpha `$-relaxation time shows only small departure from Arrhenius behavior) and are not deeply supercooled so that one´s ability to extract insights into the deeply supercooled fragile liquids is questionable.

Computer simulations can be useful in studying the moderately supercooled liquid region, where one can observe the onset of viscous slowing down (see for instance Fig. 9). The major interest of such studies is that static and dynamic quantities that are not experimentally accessible can be investigated, such as multi-body (beyond two-particle) correlations involving a variety of variables and microscopic mechanisms for transport and relaxation. They also allow for testing in detail theoretical predictions made in the relevant window of times and lengths (e. g., those of the mode-coupling theory) and for analyzing properties associated with configurational or phase space (see below).

In addition to the much studied one- or two-component systems of spheres with spherically symmetric interaction potentials, the models investigated in computer simulations can be divided into two main groups: on one hand, more realistic microscopic models for molecular glass-formers that attempt to describe species-specific effects; on the other hand, more schematic systems, coarse-grained representations,  lower-dimensional systems  or toy-models, that bear less detailed resemblance with real glass-formers, but can be studied on much longer time scales and with bigger system sizes.

## IV THEORETICAL APPROACHES.

There is a large number of theories, models, or simply empirical formulae that attempt to reproduce pieces of the phenomenology of supercooled liquids. There are fewer approaches, however, that address the question of why and how the viscous slowing down leading to the glass transition, with its salient characteristics described in the preceding sections, occurs in liquids as they are cooled. In the following, we shall briefly review the main theoretical approaches, with an emphasis on the concepts and methods that may prove useful in other areas of physics where some sort of jamming process is also encounteredModels addressing more specific questions, such as the “coupling model”  or the “continuous time random walk”, approach are discussed in the reviews cited in .. More specifically, we shall discuss phenomenological models based on free volume and configurational entropy, the description of a purely dynamic arrest resulting from mode-coupling approximations, ideas relying on the consideration of the topographic properties of the configurational space (energy and free-energy landscapes) or on the analogy with generalized spin glass models, and approaches centered on the concept of frustration.

### 1 Free volume

Free-volume models rest on the assumption that molecular transport in viscous fluids occurs only when voids having a volume large enough to accommodate a molecule form by the redistribution of some “free volume”, where this latter is loosely defined as some surplus volume that is not taken up by the molecules. In the standard presentation by Cohen and Turnbull, a molecule in a dense fluid is mostly confined to a cage formed by its nearest neighbors. The local free volume, $`v_f`$, is roughly that part of a cage space which exceeds that taken by a molecule. It is assumed that between two events contributing to molecular transport, a reshuffling of free volume among the cages occurs at no cost of energy. Assuming also that the local free volumes are statistically uncorrelated, one derives a probability distribution, $`P(v_f)`$, which is exponential,

$$P(v_f)\mathrm{exp}\left(\gamma \frac{v_f}{\overline{v_f}}\right),$$
(4)
where $`\overline{v_f}`$ is the average free volume per molecule and $`\gamma `$ is a constant of order $`1`$. Since the limiting mechanism for the diffusion of a molecule is the occurrence of a void, i.e., a local free volume $`v_f`$ larger than some critical value, $`v_0`$, that is approximately equal to the molecular volume, the diffusion constant $`D`$ is given by the probability of finding a free volume equal to $`v_0`$; this leads to an expression for $`D`$, and by extension for the viscosity $`\eta `$,

$$\eta 1/D\mathrm{exp}\left(\gamma \frac{v_0}{\overline{v_f}}\right),$$
(5)
which is similar to the formula first proposed by Doolittle.

In the Cohen-Turnbull formulation, the average free volume per molecule is given by $`\overline{v_f}=vv_0`$, where $`v=1/\rho `$ is the average total volume per molecule. The free-volume concept, in zeroth order, relies on a hard-sphere picture in which thermal activation plays no role. For application to real liquids, temperature enters through the fact that molecules, or molecular segments in the case of polymers, are not truly “hard” and that, consequently, the constant-pressure volume is temperature-dependent,

$$\overline{v_f(T)}\alpha _P(TT_0),$$
(6)
where $`\alpha _P`$ is the coefficient of isobaric expansivity and $`T_0`$ is the temperature at which all free volume is consumed, i.e., $`v=v_0`$. Inserting the above equation in the Doolittle formula, Eq. (4), gives the VFT expression, Eq. (1). An unanswered, but fundamental question associated with Eq. (6) is why the free volume should be consumed at a nonzero temperature, $`T_0`$? An extended version of the free-volume approach has been developed by Cohen and Grest, in which the cages or “cells” are divided into two groups, liquid-like and solid-like, and concepts from percolation theory are included to describe the dependence upon the fraction of liquid-like cells.  (See also the model for molecular diffusivity in fluids of long rod molecules by Edwards and Vilgis.)

The main criticisms of the free volume models are (i) that the concept of free volume is ill-defined, which results in a variety of interpretations and difficulty in finding a proper operational procedure even for simple model systems, and (ii) that the pressure dependence of the viscosity (and $`\alpha `$-relaxation times) is not adequately reproduced. This latter feature has been emphasized in many studies,  and it is a consequence of the observation made above (see II-3) that the viscous slowing down of glass-forming liquids at 1 atm and more generally at low pressure is primarily controlled by temperature and not by density or volume. Glass formation in supercooled liquids does not predominantly results from the drainage of free volume, but rather from thermally activated processes.

### 2 Mode-coupling approximations

The theory of glass-forming liquids that has had the highest visibility for more than a decade is the mode coupling theory.  It predicts a dynamic arrest of the liquid structural relaxation without any significant change in the static properties. All structural quantities are assumed to behave smoothly and jamming results from a nonlinear feedback mechanism that affects the relaxation of the density fluctuations. Formally, the theory involves an analysis of a set of nonlinear integro-differential equations describing the evolution of pair correlation functions of wave-vector- and time-dependent fluctuations that characterize the liquid. These equations have the form of generalized Langevin equations, and they can be derived by using the Zwanzig-Mori projection-operator formalism. The equation for the quantity of prime interest in the theory, the (normalized) correlation function of the density fluctuations,

$$\varphi _Q(t)=\frac{<\rho _Q(t)\rho _Q^{}(0)>}{<|\rho _Q(0)|^2>},$$
(7)
where $`\rho _Q(t)=_j\mathrm{exp}(i\mathrm{𝐐𝐫}_j)`$ and $`𝐫_j`$ denotes the position of the $`j`$th particle, can be written as

$$\frac{d^2}{dt^2}\varphi _Q(t)+\mathrm{\Omega }_Q^2\varphi _Q(t)+_0^t𝑑t^{}m_Q(tt^{})\frac{d}{dt^{}}\varphi _Q(t^{})=0,$$
(8)
where $`\mathrm{\Omega }_Q`$ is a microscopic frequency obtainable from the static structure factor, $`S(Q)<|\rho _Q(0)|^2>`$, and $`m_Q(t)`$ is the time-dependent memory function that is formally related to the correlation function of a Q-dependent random force. The above equation being exact, the crux of the mode-coupling approach consists in formulating an approximate expression for $`m_Q(t)`$. The mode-coupling scheme has been implemented for liquids both in the frame of the kinetic theory of fluids  and that of the fluctuating nonlinear hydrodynamics.  It essentially boils down to approximating the memory function $`m_Q(t)`$ as the sum of a bare contribution coming from the fast relaxing variables and a mode-coupling contribution coming from the slowly decaying bilinear density modes,

$$m_Q(t)=\gamma \delta (t)+\underset{𝐐^{}}{}V_{\mathrm{𝐐𝐐}^{}}\varphi _𝐐^{}(t)\varphi _{|𝐐𝐐^{}|}(t),$$
(9)
where the vertices $`V_{\mathrm{𝐐𝐐}^{}}`$ can be expressed in terms of the static structure factor. The self-consistent solution of the resulting set of nonlinear equations predicts a slowing of the relaxation that is attributed, within a purely homogeneous picture (see II-2), to a cage effect and to the feedback mechanism above mentioned. This solution exhibits a dynamic arrest at a critical point, $`T_c`$, which represents a transition from an ergodic to a nonergodic state with no concomitant singularity in the thermodynamics and structure of the system. The main achievements of the mode-coupling approach are the predicted anomalous increase in relaxation time and the appearance of a two-step relaxation process with decreasing temperature, as indeed observed in real fragile glass-formers (compare Fig. 10 to Fig. 7) and in molecular dynamics simulations.  Early on, however, it was realized, both from empirical fits to experimental data and from comparison to simulation data on model systems, that the dynamic arrest at $`T_c`$ did not describe the observed glass transition at $`T_g`$ nor the transition to an “ideal glass” at a temperature below $`T_g`$. This is illustrated in Fig. 11. Thus, the $`T_c`$ was interpreted as a temperature above $`T_g`$. The singularity at $`T_c`$ is avoided because of the breakdown of the simple mode-coupling approximation, Eq. 9, and the $`T_c`$ of what is called the “idealized” mode-coupling theory is taken as a crossover below which additional relaxation mechanisms, such as activated processes, presumably take over. Unfortunately, beyond some empirical introduction,  activated processes are not theoretically described by mode-coupling approaches, and so the theory of $`\alpha `$ relaxation has not been extended to temperatures below $`T_c`$. To draw once again a parallel with critical phenomena (where a singularity occurs at $`T_c`$ in the structure and the thermodynamics of the system), mode-coupling approximations, as formulated for instance by Kawasaki, are known to describe quite well the standard critical slowing down, but not the activated dynamic scaling such as that observed in the random field Ising model (see section I-1). This failure is related to the underlying nature of the approximation that corresponds to a one-loop self-consistent resummation scheme in a perturbative treatment  (see also below in III-4 the parallel with spin glass models).

Mode-coupling approaches can thus describe at best the dynamics of moderately supercooled liquids\**\**\**It is possible that they are also applicable to the fast-$`\beta `$ relaxations even below $`T_c`$. (see Fig. 11). Because of the many detailed predictions it makes in this regime, the mode-coupling theory has stimulated the use and the development of experimental techniques, such as neutron and depolarized light scattering, and molecular dynamics simulations that are able to probe the early stage of the viscous slowing down; but, the very fact that the predicted dynamic singularity is not observed makes it difficult to reach any clear-cut conclusion about the quantitative adequacy of the theory, and this has led to much debate in recent years.

### 3  Configurational entropy and (free) energy landscape

The existence of a crossover temperature in the moderately supercooled liquid region where $`\alpha `$-relaxation times are of the order of $`10^9`$ sec (hence in the same region as the $`T_c`$ predicted by the mode-coupling theory) was advocated 30 years ago by Goldstein. Goldstein argued that below this crossover flow is dominated by potential energy barriers that are high compared to thermal energies and slow relaxation occurs as a result of thermally activated processes taking the system from one minimum of the potential energy hypersurface to another. The idea that molecular transport in viscous liquids approaching the glass transition could be best described by invoking motion of the representative state point of the system on the potential energy hypersurface had also been suggested by Gibbs.  In his view, the slowing down of relaxations with decreasing temperature is related to a decrease of the number of available minima and to the increasing difficulty for the system to find such minima. The viscous slowing down would thus result from the decrease of some “configurational entropy” that is a measure of the number of accessible minima. These two concepts, potential energy hypersurface, also denoted “energy landscape”, and “configurational entropy”, have gained a renewed interest in recent years, boosted by the analogy with the situation encountered in several generalized spin glass models (see below).

The Adam-Gibbs approach  represents a phenomenological attempt to relate the $`\alpha `$-relaxation time of a glass-forming liquid to the “configurational entropy”. In the picture, $`\alpha `$-relaxation takes place by increasingly cooperative rearrangements of groups of molecules. Any such group, called a “cooperatively rearranging region”, is assumed to relax independently of the others. It is a kind of long-lived heterogeneity. Molecular motion is activated and the effective activated free energy is equal to the typical energy barrier per molecule, which is taken as independent of temperature, times the number of molecules that are necessary to form a cooperatively rearranging region whose size permits a transition from one configuration to a new one independently of the environment. This latter number goes as the inverse of the configurational entropy per molecule, $`S_c(T)/N`$, where $`N`$ is the total number of molecules in the sample. Since $`S_c`$ decreases with decreasing temperature, the reasoning leads to an effective activation free energy that grows with decreasing temperature, i. e., to a super-Arrhenius behavior,

$$\tau _\alpha =\tau _0\mathrm{exp}\left(\frac{C}{TS_c(T)}\right),$$
(10)
where $`C`$ is proportional to $`N`$ times the typical energy barrier per molecule. If the configurational entropy vanishes at a nonzero temperature, an assumption somewhat analogous to that in Eq. (6) for the free volume model, but one that is inherent for instance in the Gibbs-di Marzio approximate mean field treatment of a lattice model of linear polymeric chains,  then the $`\alpha `$-relaxation times diverge at this same nonzero temperature. In particular if the configurational entropy is identified as the entropy difference between the supercooled liquid and the crystal††††††This phenomenological choice for the entropy of configuration has been criticized by Goldstein who showed for several glass-formers that only half of the entropy difference between the liquid and the crystal comes from strictly “configurational” sources; the remainder comes mostly from changes in vibrational anharmonicity or differences in the number of molecular groups able to engage in local motions. , the Adam-Gibbs theory allows one to correlate the extrapolated divergence of the $`\alpha `$-relaxation times with the Kauzmann paradox (see I-4): the Kauzmann temperature $`T_K`$ would then signal a singularity both in the dynamics and in the thermodynamics of a supercooled liquid‡‡‡‡‡‡A recent careful, but conjectural analysis of dielectric relaxation data suggests that these data are consistent with the existence of a critical point, both structural and dynamical, at the approximate $`T_0`$ specified by the VTF expression in Eq. (1).. Note also that by using a hyperbolic temperature dependence to fit the experimental data on the heat capacity difference between the liquid and the crystal, $`\mathrm{\Delta }C_P(T)=K/T`$, and using this formula to extrapolate the configurational entropy down to the Kauzmann temperature, one converts Eq. (10) to a VFT formula,

$$\tau _\alpha =\tau _0\mathrm{exp}\left(\frac{CT_K}{K(TT_K)}\right),$$
(11)
with the VFT temperature $`T_0`$ equal to the Kauzmann temperature $`T_K`$. When comparing to experimental data, the configurational-entropy based expressions provide a good description at least over a restricted temperature range, but the resulting estimates for the critical number of molecules composing a cooperatively rearranging region is often found to be unphysically small (only a few molecules at $`T_g`$).

Building upon the early suggestion made by Goldstein,  and others proposed that the apparent passage with decreasing temperature from flow dynamics described by a mode-coupling approach to activated dynamics such as pictured by the configurational-entropy theory of Adam and Gibbs could be rationalized by considering the physics of exploration of the energy landscape: see Fig. 12. The energy landscape is the potential energy in configurational space. It can be envisaged as an incredibly complex, multi-dimensional ($`3N`$ dimensions for a system of $`N`$ particles) set of hills, valleys, basins, saddle-points, and passage-ways around the hills. At constant volume and constant number of particles, this landscape is independent of temperature. However, the fraction of space that is statistically accessible to the representative state point of the system decreases with decreasing temperature, and the system becomes constrained to deeper and deeper wells. (Recall that below the melting point the deepest energy minima corresponding to the crystalline part of configurational space must be excluded when studying the supercooled liquid.) At low enough temperature, when the representative point of the supercooled liquid is mostly found in fairly deep and narrow wells, it seems reasonable to define a “configurational entropy” that is proportional to the logarithm of the number of minima that are accessible at a given temperature. The liquid configurations corresponding to these accessible minima have been called “inherent structures” and Stillinger and coworkers have devised a gradient-descent mapping procedure to find the inherent structures and study their properties in computer simulations.  Interestingly, Stillinger has also shown, with fairly general arguments, that if one is to use the above defined notion of configurational entropy, an “ideal glass transition” of the type commonly associated with the Kauzmann paradox, i. e., one characterized by the vanishing of the configurational entropy at a nonzero temperature, cannot occur for systems of limited molecular weight and short-range interactions.

It may be more fruitful to investigate in place of the potential energy landscape a free-energy landscape. Such a landscape can only be defined if one is able to construct a free-energy functional by a suitable coarse-graining procedure, as can be done for instance in the case of mean-field spin glass models (see below). A free-energy landscape is temperature-dependent, and it is important to note that the “configurational entropy”, also called “complexity”, that one can define from the logarithm of the number of accessible free-energy minima differs from the “configurational entropy” computed from the potential energy landscape. In particular, the behavior of the complexity is not restricted by the Stillinger arguments given above.

The “landscape paradigm” is very appealing in rationalizing many observations on liquids and glasses and, more generally, in establishing a framework to describe qualitatively slow dynamics in complex systems that span a wide range of scientific fields. It has been used to motivate, in addition to the Adam-Gibbs theory and other phenomenological approaches like the soft-potential model,  simple stochastic models of transport based on master equations.  Nevertheless, it has not so far offered a way for elucidating the physical mechanism that is responsible for the distinctive features of the viscous slowing down of supercooled liquids.

### 4 Analogy with generalized spin glass models

If one takes seriously the observation that the extrapolated temperature dependence of both the viscosity (and $`\alpha `$-relaxation times) and the “configurational” entropy (taken as the difference of entropy between the liquid and the crystal) become divergent or singular at essentially the same temperature $`T_0T_K`$(see Fig. 9), one is naturally led to postulate the existence at this temperature of an underlying thermodynamic transition, usually referred to as the “ideal glass transition”. Looking for analogies with phase transitions in spin glasses is then appealing. However, the kind of dynamic activated scaling that would be required to describe the slowing down of relaxations when approaching the ideal glass transition (see I-1) is not found in the most studied Ising spin glasses.  Kirkpatrick, Thirumalai, and Wolynes argued that generalized spin glass models, such as Potts glasses and random p-spin systems, would be better candidates.  The random p-spin model, for instance, is defined by the following hamiltonian:

$$H=\underset{i_1<i_2<\mathrm{}<i_p}{}J_{i_1i_2\mathrm{}i_p}\sigma _{i_1}\sigma _{i_2}\mathrm{}\sigma _{i_p},$$
(12)
where the $`\sigma _i`$’s are Ising variables and the couplings $`J_{i_1i_2\mathrm{}i_p}`$’s are quenched independent random variables that can take positive and negative values according to a given probability distribution. The behavior of these systems, at least when solved in the mean-field limit where the interactions between spins have infinite range, bears many similarities with the theoretical description of glass-forming liquids outlined above. Indeed, mean-field Potts glasses (with a number of states strictly larger than 4) and mean-field p-spin models (with $`p3`$) have essentially the following characteristics:

1. At high temperature, the system is in a fully disordered (paramagnetic) state. At a temperature $`T_D`$, there appears an exponentially large number of metastable “glassy” states whose overall contribution to the partition function is equal to that of the paramagnetic minimum. The free energy and all other static equilibrium quantities are fully regular at $`T_D`$, but the dynamics have a singularity of the exact same type as that found in the mode-coupling theory of liquids. At $`T_D`$, the system is trapped in one of the metastable free-energy minima, and ergocity is broken.
2. Below $`T_D`$ , a peculiar situation occurs. The partition function has contributions from, both, the paramagnetic state and the exponentially large number of “glassy” (free-energy) minima, the logarithm of which defines the configurational entropy or complexity. This latter decreases as the temperature is lowered.
3. At a nonzero temperature $`T_s<T_D`$, the configurational entropy vanishes. The system undergoes a bona fide thermodynamic transition to a spin-glass phase. The transition has been termed “random first order”  because it is second-order in the usual thermodynamic sense (with, e. g., no latent heat), but shows a discontinuous jump in the order parameter. (Technically, within the replica formalism, it corresponds to a one-step replica symmetry breaking with a discontinuous jump of the Edwards-Anderson order parameter.)

These mean-field systems are the simplest, analytically tractable models found so far that display a high-temperature mode-coupling dynamic singularity, a nontrivial free-energy landscape, and a low-temperature ideal (spin) glass transition with an “entropy crisis”\**\**\**They are also aging phenomena, as discussed in Ref .. Analyzing them sheds light on the mode-coupling approximation, whose validity for fluid systems is otherwise hard to assess. The mode-coupling approximation becomes exact in the mean-field limit, because the barriers separating the metastable minima diverge (in the thermodynamic limit) at and below $`T_D`$ as a result of the assumed infinite range of the interactions. One expects that in a finite-range model, provided the same type of free-energy landscape is still encountered, barriers are large but finite and ergodicity is restored by thermally activated processes. Accordingly, the dynamic transition is smeared out, and the activated relaxation mechanisms that take over must be described in a nonperturbative way, as suggested for instance by Kirkpatrick, Thirumalai, and Wolynes  in their dynamic scaling approach based on entropic droplets.

An advantage of an analogy between glass-forming liquids and generalized spin glasses\*†\*†\*†See also the frustrated percolation model. is that the powerful tools that have been developed in the theory of spin-glass models to characterize the order parameter and the properties associated with the existence of a large number of metastable glassy states, among which the replica formalism,  can be used mutatis mutandis tostudy liquids and glasses.  However, to make the analogy really successful, one must still find a short-range model (even more convincing would be a model without quenched disorder) that actually displays activated dynamic scaling and a random first-order transition and make progress in describing the slow relaxation.

### 5 Intrinsic frustration without randomness

Spin glasses, and related systems like orientational glasses, vortex glasses and vulcanized matter,  owe their fascinating behavior to two main ingredients: randomness, namely the presence of an externally imposed quenched disorder, and frustration, which expresses the impossibility of simultaneously minimizing all the interaction terms in the energy function of the system. Liquids and glasses (sometimes called ”structural glasses” to stress the difference with spin glasses) have no quenched randomness, but frustration has been suggested as a key feature to explain the phenomena associated with glass formation.  Frustration in this context is attributed to a competition between a short-range tendency for the extension of a locally preferred order and global constraints that preclude the periodic tiling of the whole space with the local structure.

The best studied example of such an intrinsic frustration concerns single-component systems of spherical particles interacting with simple pair potentials. What is usually called ”geometric” or ”topological” frustration can be more easily understood by comparing the situations encountered in $`2`$ and $`3`$ dimensions  (see Fig. 13). In $`2`$ dimensions, the arrangement of disks that is locally preferred, in the sense that it maximizes the density and minimizes the energy, is a hexagon of 6 disks around a central one, and this hexagonal structure can be extended to the whole space to form a triangular lattice. In $`3`$ dimensions, as was shown long ago by Frank,  the locally preferred cluster of spheres is an icosahedron; however, the $`5`$-fold rotational symmetry characteristic of icosahedral order is incompatible with translational symmetry, and formation of a periodic icosahedral crystal is forbidden. Geometric or topological frustration is thus absent in the $`2`$-dimensional case but present in the $`3`$-dimensional case. A consequence of this, for instance, is that crystallization is continuous, or weakly first-order, in $`2`$ dimensions (with some subtleties related to ordering in $`2`$ dimensions ) whereas it is strongly first-order in $`3`$ dimensions and accompanied by the breaking of the local icosahedral structure to make the face-centered-cubic or hexagonal-close-packed order that allows to tile space periodically. (In contrast, aligned cubes in 3 dimensions have no frustration and undergo a continuous freezing transition to a crystalline state. ). The geometric frustration that affects spheres in $`3`$-dimensional Euclidean space can be relieved in curved space with a specially tuned curvature; the creation of topological defects (disclination lines) can then be viewed as the result of forcing the ideal icosahedral ordering into ”flat” space. This picture of sphere packing disrupted by frustration has been further developed in models for simple atomic systems and metallic glasses,  and the slowing down of relaxations has been tentatively attributed to the topological constraints that hinder the kinetics of the entangled defect lines;  however, the treatment remains only qualitative and incomplete.

A significant difficulty in applying the concept of geometric or topological frustration to supercooled liquids is that real fragile glass-formers are in general either mixtures or single-component systems of nonspherical molecules with a variety of shapes, all of which obscures the detailed mechanisms and constraints that are responsible for the frustration. Attempts have been made to get around this problem by proposing a more coarse-grained description of frustration\*‡\*‡\*‡In addition, several “toy models”possessing frustration, but no quenched disorder have been studied by computer simulation: see for instance Ref...

In Stillinger’s ”tear and repair” mechanism for relaxation and shear flow  and in the more recently introduced ”frustration-limited domain theory”, frustration is described as the source of a strain free energy that opposes the spatial extension of the locally preferred structure and grows super-extensively with system size. It results in the breaking up of the liquid into domains, whose size and growth with decreasing temperature are limited by frustration, the weaker the frustration the larger the domains. The super-Arrhenius temperature dependence of the viscosity and $`\alpha `$-relaxation times and the heterogeneous nature of the dynamics are attributed to these domains (see also Ref.). Progress has been made along these lines, by making use of a scaling approach based on the concept of avoided critical behaviorThis approach differs from both those based upon spin-glass analogies and those in which the slow kinetics are attributed to frustration-induced entangled defect lines in that these others scale about a low-temperature characteristic point signifying ultimate slowing down, whereas in the frustration-limited domain theory the scaling is carried out about a high-temperature characteristic point signifying the initiation of anomalously slow dynamics. For the same reason, it also differs from the domain (or cluster) picture that has been proposed on the basis of an analogy between a supercooled liquid approaching the glass transition and a mean-field model with purely repulsive interactions near its spinodal..  However, the putative order variable characterizing the locally preferred structure of the liquid has not yet been properly identified, and, as in the case of the generalized spin-glass models discussed above, one must still give convincing evidence that the $`3`$-dimensional statistical-mechanical frustrated models that have been suggested as minimal theoretical descriptions do show the expected activated dynamics.

## V CONCLUSION

The viscous slowing down of supercooled liquids that leads to glass formation can be considered as a classical and thoroughly studied example of a ”jamming process”. In this review, we have stressed the distinctive features characterizing the phenomenon: strong, super-Arrhenius temperature dependence of the viscosity and the $`\alpha `$-relaxation times, nonexponential and heterogeneous character of the $`\alpha `$ relaxation, absence of marked changes in the structural (static) quantities, rapid decrease of the liquid entropy relative to that of the crystal, appearance of a sequence of steps (or regimes) in the relaxation functions. These features are common to most glass-forming liquids (with the exception of systems forming $`2`$\- and $`3`$-dimensional networks of strong intermolecular bonds). We have also discussed the main theoretical approaches that have been proposed to describe the origin and the nature of the viscous slowing down and of the glass transition. We have emphasized the concepts, such as free volume, dynamic freezing and mode-coupling approximations, configurational entropy and (free) energy landscape, and frustration, that could be useful in other areas of physics where jamming processes are encountered.


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# Differential Invariants under Gamma Correction

## 1 Introduction

Invariants are a popular concept in object recognition and image retrieval . They aim to provide descriptions that remain constant under certain geometric or radiometric transformations of the scene, thereby reducing the search space. They can be classified into global invariants, typically based either on a set of key points or on moments, and local invariants, typically based on derivatives of the image function which is assumed to be continuous and differentiable.

The geometric transformations of interest often include translation, rotation, and scaling, summarily referred to as similarity transformations. In a previous paper , building on work done by Schmid and Mohr , we have proposed differential invariants for those similarity transformations, plus linear brightness change. Here, we are looking at a non-linear brightness change known as gamma correction.

Gamma correction is a non-linear quantization of the brightness measurements performed by many cameras during the image formation process.111 Historically, the parameter gamma was introduced to describe the non-linearity of photographic film. Today, its main use is to improve the output of cathode ray tube based monitors, but the gamma correction in display devices is of no concern to us here. The idea is to achieve better perceptual results by maintaining an approximately constant ratio between adjacent brightness levels, placing the quantization levels apart by the just noticeable difference. Incidentally, this non-linear quantization also precompensates for the non-linear mapping from voltage to brightness in electronic display devices .

Gamma correction can be expressed by the equation

$$I_\gamma =pI^\gamma $$
(1)
where $`I`$ is the input intensity, $`I_\gamma `$ is the output intensity, and $`p`$ is a normalization factor which is determined by the value of $`\gamma `$. For output devices, the NTSC standard specifies $`\gamma =2.22`$. For input devices like cameras, the parameter value is just inversed, resulting in a typical value of $`\gamma =1/2.22=0.45`$. The camera we used, the Sony 3 CCD color camera DXC 950, exhibited $`\gamma 0.6`$.222 Martin  reports the settings of $`\gamma =0.45,0.50,0.60`$ for the Kodak Megaplus XRC camera Fig. 1 shows the intensity mapping of 8-bit data for different values of $`\gamma `$.

It turns out that an invariant under gamma correction can be designed from first and second order derivatives. Additional invariance under scaling requires third order derivatives. Derivatives are by nature translationally invariant. Rotational invariance in 2-d is achieved by using rotationally symmetric operators.

## 2 The Invariants

The key idea for the design of the proposed invariants is to form suitable ratios of the derivatives of the image function such that the parameters describing the transformation of interest will cancel out. This idea has been used in  to achieve invariance under linear brightness changes, and it can be adjusted to the context of gamma correction by – at least conceptually – considering the logarithm of the image function. For simplicity, we begin with 1-d image functions.

### 2.1 Invariance under Gamma Correction

Let $`f(x)`$ be the image function, i.e. the original signal, assumed to be continuous and differentiable, and $`f_\gamma (x)=pf(x)^\gamma `$ the corresponding gamma corrected function. Note that $`f(x)`$ is a special case of $`f_\gamma (x)`$ where $`\gamma =p=1`$. Taking the logarithm yields

$$\stackrel{~}{f}_\gamma (x)=\mathrm{ln}(pf(x)^\gamma )=\mathrm{ln}p+\gamma \mathrm{ln}f(x)$$
(2)
with the derivatives $`\stackrel{~}{f}_\gamma ^{}(x)=\gamma f^{}(x)/f(x)`$, and $`\stackrel{~}{f}_\gamma ^{\prime \prime }(x)=\gamma (f(x)f^{\prime \prime }(x)f^{}(x)^2)/f(x)^2`$. We can now define the invariant $`\mathrm{\Theta }_{12\gamma }`$ under gamma correction to be

| $`\mathrm{\Theta }_{12\gamma }(f(x))`$ | = $`\frac{\stackrel{~}{f}_\gamma ^{}\left(x\right)}{\stackrel{~}{f}_\gamma ^{\prime \prime }\left(x\right)}`$ |
| --- | --- |
|  | = $`\frac{\gamma \frac{f^{}\left(x\right)}{f\left(x\right)}}{\gamma \frac{f\left(x\right)f^{\prime \prime }\left(x\right)f^{}\left(x\right)^2}{f\left(x\right)^2}}`$ |
|  | = $`\frac{f\left(x\right)f^{}\left(x\right)}{f\left(x\right)f^{\prime \prime }\left(x\right)f^{}\left(x\right)^2}`$ |

(3)
The factor $`p`$ has been eliminated by taking derivatives, and $`\gamma `$ has canceled out. Furthermore, $`\mathrm{\Theta }_{12\gamma }`$ turns out to be completely specified in terms of the original image function and its derivatives, i.e. the logarithm actually doesn’t have to be computed. The notation $`\mathrm{\Theta }_{12\gamma }(f(x))`$ indicates that the invariant depends on the underlying image function $`f(x)`$ and location $`x`$ – the invariance holds under gamma correction, not under spatial changes of the image function.

A shortcoming of $`\mathrm{\Theta }_{12\gamma }`$ is that it is undefined where the denominator is zero. Therefore, we modify $`\mathrm{\Theta }_{12\gamma }`$ to be continuous everywhere:

|  | 0 | if $`ff^{}=0ff^{\prime \prime }f_{}^{}{}_{}{}^{2}=0`$ |
| --- | --- | --- |
| $`\mathrm{\Theta }_{m12\gamma }=`$ | $`\frac{ff^{}}{ff^{\prime \prime }f_{}^{}{}_{}{}^{2}}`$ | if $`|ff^{}|<|ff^{\prime \prime }f_{}^{}{}_{}{}^{2}|`$ |
|  | $`\frac{ff^{\prime \prime }f_{}^{}{}_{}{}^{2}}{ff^{}}`$ | else |

(4)
where, for notational convenience, we have dropped the variable $`x`$. The modification entails $`1\mathrm{\Theta }_{m12\gamma }1`$. Note that the modification is just a heuristic to deal with poles. If all derivatives are zero because the image function is constant, then differentials are certainly not the best way to represent the function.

### 2.2 Invariance under Gamma Correction and Scaling

If scaling is a transformation that has to be considered, then another parameter $`\alpha `$ describing the change of size has to be introduced. That is, scaling is modeled here as variable substitution : the scaled version of $`f(x)`$ is $`g(\alpha x)=g(u)`$. So we are looking at the function

$$\stackrel{~}{f}_\gamma (x)=\mathrm{ln}(pf(x)^\gamma )=\mathrm{ln}p+\gamma \mathrm{ln}g(\alpha x)=\stackrel{~}{g}_\gamma (u)$$

where the derivatives with respect to $`x`$ are $`\stackrel{~}{g}_\gamma ^{}(u)=\gamma \alpha g^{}(u)/g(u)`$, $`\stackrel{~}{g}_\gamma ^{\prime \prime }(u)=\gamma \alpha ^2(g(u)g^{\prime \prime }(u)g^{}(u)^2)/g(u)^2`$, and $`\stackrel{~}{g}_\gamma ^{\prime \prime \prime }(u)=\gamma \alpha ^3\left(g^{\prime \prime \prime }(u)/g(u)3g^{}(u)g^{\prime \prime }(u)/g(u)^2+2g^{}(u)^3/g(u)^3\right)`$. Now the invariant $`\mathrm{\Theta }_{123\gamma }(g(u))`$ is obtained by defining a suitable ratio of the derivatives such that both $`\gamma `$ and $`\alpha `$ cancel out:

| $`\mathrm{\Theta }_{123\gamma }(g(u))`$ | = $`\frac{\stackrel{~}{g}_\gamma ^{}\left(u\right)\stackrel{~}{g}_\gamma ^{\prime \prime \prime }\left(u\right)}{\stackrel{~}{g}_\gamma ^{\prime \prime }\left(u\right)^2}`$ |
| --- | --- |
|  | = $`\frac{g^2g^{}g^{\prime \prime \prime }3gg_{}^{}{}_{}{}^{2}g^{\prime \prime }+2g_{}^{}{}_{}{}^{4}}{g^2g_{}^{\prime \prime }{}_{}{}^{2}2gg_{}^{}{}_{}{}^{2}g^{\prime \prime }+g_{}^{}{}_{}{}^{4}}`$ |

(5)
Analogously to eq. (4), we can define a modified invariant

|  | 0 | if cond1 |
| --- | --- | --- |
| $`\mathrm{\Theta }_{m123\gamma }=`$ | $`\frac{g^2g^{}g^{\prime \prime \prime }3gg_{}^{}{}_{}{}^{2}g^{\prime \prime }+2g_{}^{}{}_{}{}^{4}}{g^2g_{}^{\prime \prime }{}_{}{}^{2}2gg_{}^{}{}_{}{}^{2}g^{\prime \prime }+g_{}^{}{}_{}{}^{4}}`$ | if cond2 |
|  | $`\frac{g^2g_{}^{\prime \prime }{}_{}{}^{2}2gg_{}^{}{}_{}{}^{2}g^{\prime \prime }+g_{}^{}{}_{}{}^{4}}{g^2g^{}g^{\prime \prime \prime }3gg_{}^{}{}_{}{}^{2}g^{\prime \prime }+2g_{}^{}{}_{}{}^{4}}`$ | else |

(6)
where condition cond1 is $`g^2g^{}g^{\prime \prime \prime }3gg_{}^{}{}_{}{}^{2}g^{\prime \prime }+2g_{}^{}{}_{}{}^{4}=0`$ $``$ $`g^2g_{}^{\prime \prime }{}_{}{}^{2}2gg_{}^{}{}_{}{}^{2}g^{\prime \prime }+g_{}^{}{}_{}{}^{4}=0`$, and condition cond2 is $`|g^2g^{}g^{\prime \prime \prime }3gg_{}^{}{}_{}{}^{2}g^{\prime \prime }+2g_{}^{}{}_{}{}^{4}|`$ $`<`$ $`|g^2g_{}^{\prime \prime }{}_{}{}^{2}2gg_{}^{}{}_{}{}^{2}g^{\prime \prime }+g_{}^{}{}_{}{}^{4}|`$. Again, this modification entails $`1\mathrm{\Theta }_{m123\gamma }1`$.

### 2.3 An Analytical Example

It is a straightforward albeit cumbersome exercise to verify the invariants from eqs. (3) and (5) with an analytical, differentiable function. As an arbitrary example, we choose

$$f(x)=3x\mathrm{sin}(2\pi x)+30$$

The first three derivatives are $`f^{}(x)=3\mathrm{sin}(2\pi x)+6\pi x\mathrm{cos}(2\pi x)`$, $`f^{\prime \prime }(x)=12\pi \mathrm{cos}(2\pi x)12\pi ^2x\mathrm{sin}(2\pi x)`$, and $`f^{\prime \prime \prime }(x)=36\pi ^2\mathrm{sin}(2\pi x)24\pi ^3x\mathrm{cos}(2\pi x)`$. Then, according to eq. (3), $`\mathrm{\Theta }_{12\gamma }(f(x))=(3x\mathrm{sin}(2\pi x)+30)(3x\mathrm{sin}(2\pi x)+6\pi x\mathrm{cos}(2\pi x))/\left((3x\mathrm{sin}(2\pi x)+30)(12\pi \mathrm{cos}(2\pi x)12\pi ^2x\mathrm{sin}(2\pi x))(3\mathrm{sin}(2\pi x)+6\pi x\mathrm{cos}(2\pi x))^2\right)`$.

If we now replace $`f(x)`$ with a gamma corrected version, say $`f_{0.45}(x)=255^{10.45}3x\mathrm{sin}(2\pi x)+30)^{0.45}`$, the first derivative becomes $`f_{0.45}^{}(x)=255^{0.55}0.45(3\mathrm{sin}(2\pi x)+30)^{0.55}(3\mathrm{sin}(2\pi x)+6\pi x\mathrm{cos}(2\pi x))`$, the second derivative is $`f_{0.45}^{\prime \prime }(x)=255^{0.55}0.450.55(3\mathrm{sin}(2\pi x)+30)^{1.55}(3\mathrm{sin}(2\pi x)+6\pi x\mathrm{cos}(2\pi x))^2+255^{0.55}0.45(3x\mathrm{sin}(2\pi x)+30)^{0.55}(12\pi \mathrm{cos}(2\pi x)12\pi ^2x\mathrm{sin}(2\pi x))`$, and the third is $`f_{0.45}^{\prime \prime \prime }(x)=255^{0.55}0.45(3\mathrm{sin}(2\pi x)+30)^{0.55}\left(1.550.55(3\mathrm{sin}(2\pi x)+30)^2(3\mathrm{sin}(2\pi x)+6\pi x\mathrm{cos}(2\pi x))^3+(3)0.55(3\mathrm{sin}(2\pi x)+30)^1(3\mathrm{sin}(2\pi x)+6\pi x\mathrm{cos}(2\pi x))(12\pi \mathrm{cos}(2\pi x)12\pi ^2x\mathrm{sin}(2\pi x))+(36\pi ^2\mathrm{sin}(2\pi x)24\pi ^3x\mathrm{cos}(2\pi x))\right)`$. If we plug these derivatives into eq. (3), we obtain an expression for $`\mathrm{\Theta }_{12\gamma }(f_{0.45}(x))`$ which is identical to the one for $`\mathrm{\Theta }_{12\gamma }(f(x))`$ above. The algebraically inclined reader is encouraged to verify the invariant $`\mathrm{\Theta }_{123\gamma }`$ for the same function.

Fig. 2 shows the example function and its gamma corrected counterpart, together with their derivatives and the two modified invariants. As expected, the graphs of the invariants are the same on the right as on the left. Note that the invariants define a many-to-one mapping. That is, the mapping is not information preserving, and it is not possible to reconstruct the original image from its invariant representation.

### 2.4 Extension to 2-d

If $`\mathrm{\Theta }_{m12\gamma }`$ or $`\mathrm{\Theta }_{m123\gamma }`$ are to be computed on images, then eqs. (3) to (6) have to be generalized to two dimensions. This is to be done in a rotationally invariant way in order to achieve invariance under similarity transformations. The standard way is to use rotationally symmetric operators. For the first derivative, we have the well known gradient magnitude, defined as

$$(x,y)=\sqrt{I_x^2+I_y^2}:=I^{}$$
(7)
where $`I(x,y)`$ is the 2-d image function, and $`I_x`$, $`I_y`$ are partial derivatives along the x-axis and the y-axis. For the second order derivative, we can use the linear Laplacian

$$^2(x,y)=I_{xx}+I_{yy}:=I^{\prime \prime }$$
(8)
Horn  also presents an alternative second order derivative operator, the quadratic variation333Actually, unlike Horn, we have taken the square root.

$$\mathrm{QV}(x,y)=\sqrt{I_{xx}^2+2I_{xy}^2+I_{yy}^2}$$
(9)
Since the QV is not a linear operator and more expensive to compute, we use the Laplacian for our implementation. For the third order derivative, we can define, in close analogy with the quadratic variation, a cubic variation as

$$\mathrm{CV}(x,y)=\sqrt{I_{xxx}^2+3I_{xxy}^2+3I_{xyy}^2+I_{yyy}^2}:=I^{\prime \prime \prime }$$
(10)
The invariants from eqs. (3) to (6) remain valid in 2-d if we replace $`f^{}`$ with $`I^{}`$, $`f^{\prime \prime }`$ with $`I^{\prime \prime }`$, and $`f^{\prime \prime \prime }`$ with $`I^{\prime \prime \prime }`$. This can be verified by going through the same argument as for the 1-d functions. Recall that the critical observation in eq. (3) was that $`\gamma `$ cancels out, which is the case when all derivatives return a factor $`\gamma `$. But such is also the case with the rotationally symmetric operators mentioned above. For example, if we apply the gradient magnitude operator to $`\stackrel{~}{I}(x,y)`$, i.e. to the logarithm of a gamma corrected image function, we obtain

$$=\sqrt{\stackrel{~}{I}_x^2+\stackrel{~}{I}_y^2}=\sqrt{\left(\gamma \frac{I_x}{I}\right)^2+\left(\gamma \frac{I_y}{I}\right)^2}=\gamma \frac{\sqrt{I_x^2+I_y^2}}{I}$$

returning a factor $`\gamma `$, and analogously for $`^2`$, QV, and CV. A similar argument holds for eq. (5) where we have to show, in addition, that the first derivative returns a factor $`\alpha `$, the second derivative returns a factor $`\alpha ^2`$, and the third derivative returns a factor $`\alpha ^3`$, which is the case for our 2-d operators.

### 2.5 Differential Operators

While the derivatives of continuous, differentiable functions are uniquely defined, there are many ways to implement derivatives for sampled functions. We follow Schmid and Mohr , ter Haar Romeny , and many other researchers in employing the derivatives of the Gaussian function as filters to compute the derivatives of a sampled image function via convolution. This way, derivation is combined with smoothing. The 2-d zero mean Gaussian is defined as

$$G=\frac{1}{2\pi \sigma ^2}e^{\frac{x^2+y^2}{2\sigma ^2}}$$
(11)
The partial derivatives up to third order are $`G_x=x/\sigma ^2G`$, $`G_y=y/\sigma ^2G`$, $`G_{xx}=(x^2\sigma ^2)/\sigma ^4G`$, $`G_{xy}=xy/\sigma ^4G`$, $`G_{yy}=(y^2\sigma ^2)/\sigma ^4G`$, $`G_{xxx}=(3\sigma ^2xx^3)/\sigma ^6G`$, $`G_{xxy}=(\sigma ^2yx^2y)/\sigma ^6G`$, $`G_{xyy}=(\sigma ^2xxy^2)/\sigma ^6G`$, $`G_{yyy}=(3\sigma ^2yy^3)/\sigma ^6G`$. They are shown in fig. 3. We used the parameter setting $`\sigma =1.0`$ and kernel size $`7\times 7`$. With these kernels, eq. (3), for example, is implemented as

$$\mathrm{\Theta }_{12\gamma }=\frac{I\sqrt{\left(IG_x\right)^2+\left(IG_y\right)^2}}{I\left(IG_{xx}+IG_{yy}\right)\left(\left(IG_x\right)^2+\left(IG_y\right)^2\right)}$$

at each pixel $`(x,y)`$, where $``$ denotes convolution.

## 3 Experimental Data and Results

We evaluate the invariant $`\mathrm{\Theta }_{m12\gamma }`$ from eq. (4) in two different ways. First, we measure how much the invariant computed on an image without gamma correction is different from the invariant computed on the same image but with gamma correction. Theoretical, this difference should be zero, but in practice, it is not. Second, we compare template matching accuracy on intensity images, again without and with gamma correction, to the accuracy achievable if instead the invariant representation is used. We also examine whether the results can be improved by prefiltering.

### 3.1 Absolute and Relative Errors

A straightforward error measure is the absolute error,

$$\mathrm{\Delta }_{GC}(i,j)=|\mathrm{\Theta }_{GC}(i,j)\mathrm{\Theta }_{0GC}(i,j)|$$
(12)
where ”0GC” refers to the image without gamma correction, and GC stands for either ”SGC” if the gamma correction is done synthetically via eq. (1), or for ”CGC” if the gamma correction is done via the camera hardware. Like the invariant itself, the absolute error is computed at each pixel location $`(i,j)`$ of the image, except for the image boundaries where the derivatives and therefore the invariants cannot be computed reliably.

Fig. 4 shows an example image. The SGC image has been computed from the 0GC image, with $`\gamma =0.6`$. Note that the gamma correction is done after the quantization of the 0GC image, since we don’t have access to the 0GC image before quantization.

Fig. 5 shows the invariant representations of the image data from fig. 4 and the corresponding absolute errors. Since $`1\mathrm{\Theta }_{m12\gamma }1`$, we have $`0\mathrm{\Delta }_{GC}2`$. The dark points in fig. 5, (c) and (e), indicate areas of large errors. We observe two error sources:

* The invariant cannot be computed robustly in homogeneous regions. This is hardly surprising, given that it is based on differentials which are by definition only sensitive to spatial changes of the signal.
* There are outliers even in the SGC invariant representation, at points of very high contrast edges. They are a byproduct of the inherent smoothing when the derivatives are computed with differentials of the Gaussian. Note that the latter put a ceiling on the maximum gradient magnitude that is computable on 8-bit images.

In addition to computing the absolute error, we can also compute the relative error, in percent, as

$$\delta _{CGC}(i,j)=100\mathrm{\Delta }_{CGC}(i,j)/\mathrm{\Theta }_{0GC}(i,j)$$
(13)
Then we can define the set $`\mathrm{RP}_ϵ`$ of reliable points, relative to some error threshold $`ϵ`$, as

$$\mathrm{RP}_ϵ=\{(i,j)|\delta (i,j)ϵ\}$$
(14)
and $`\mathrm{PRP}_ϵ`$, the percentage of reliable points, as

$$\mathrm{PRP}_ϵ=100|\mathrm{RP}_ϵ|/n$$
(15)
where $`n`$ is the number of valid, i.e. non-boundary, pixels in the image. Fig. 6 shows, in the first row, the reliable points for three different values of the threshold $`ϵ`$. The second row shows the sets of reliable points for the same thresholds if we gently prefilter the 0GC and CGC images. The corresponding data for the ten test images from fig. 11 is summarized in table 1.

Derivatives are known to be sensitive to noise. Noise can be reduced by smoothing the original data before the invariants are computed. On the other hand, derivatives should be computed as locally as possible. With these conflicting goals to be considered, we experiment with gentle prefiltering, using a Gaussian filter of size $`\sigma _{pre}`$=1.0. The size of the Gaussian to compute the invariant $`\mathrm{\Theta }_{m12\gamma }`$ is set to $`\sigma _{der}`$=1.0. Note that $`\sigma _{pre}`$ and $`\sigma _{der}`$ can not be combined into just one Gaussian because of the non-linearity of the invariant.

With respect to the set of reliable points, we observe that after prefiltering, roughly half the points, on average, have a relative error of less than 20%. Gentle prefiltering consistently reduces both absolute and relative errors, but strong prefiltering does not.

### 3.2 Template Matching

Template matching is a frequently employed technique in computer vision. Here, we will examine how gamma correction affects the spatial accuracy of template matching, and whether that accuracy can be improved by using the invariant $`\mathrm{\Theta }_{m12\gamma }`$.

An overview of the testbed scenario is given in fig. 7. A small template of size $`6\times 8`$, representing the search pattern, is taken from a 0GC intensity image, i.e. without gamma correction. This query template is then correlated with the corresponding CGC intensity image, i.e. the same scene but with gamma correction switched on. If the correlation maximum occurs at exactly the location where the 0GC query template has been cut out, we call this a correct maximum correlation position, or CMCP.

The correlation function $`s(x,y)`$ employed here is based on a normalized mean squared difference $`c(x,y)`$ :

$`s`$ $`=\mathrm{max}(0,1c)`$
$`c`$ $`={\displaystyle \frac{_{i,j}((I(x+i,y+j)\overline{I})(T(i,j)\overline{T}))^2}{\sqrt{_{i,j}(I(x+i,y+j)\overline{I})^2_{i,j}(T(i,j)\overline{T})^2}}}`$
where $`I`$ is an image, $`T`$ is a template positioned at $`(x,y)`$, $`\overline{I}(x,y)`$ is the mean of the subimage of $`I`$ at $`(x,y)`$ of the same size as $`T`$, $`\overline{T}`$ is the mean of the template, and $`0s1`$. The template location problem then is to perform this correlation for the whole image and to determine whether the position of the correlation maximum occurs precisely at $`(x,y)`$.

Fig. 8 demonstrates the template location problem, on the left for an intensity image, and on the right for its invariant representation. The black box marks the position of the original template at (40,15), and the white box marks the position of the matched template, which is incorrectly located at (50,64) in the intensity image. On the right, the matched template (white) has overwritten the original template (black) at the same, correctly identified position. Fig. 9 visualizes the correlation function over the whole image. The white areas are regions of high correlation.

The example from figs. 8 and 9 deals with only one arbitrarily selected template. In order to systematically analyze the template location problem, we repeat the correlation process for all possible template locations. Then we can define the correlation accuracy CA as the percentage of correctly located templates,

$$\mathrm{CA}_{tn\times tm}=100|\mathrm{CMCP}_{tn\times tm}|/n$$
(16)
where $`tn\times tm`$ is the size of the template, $`\mathrm{CMCP}_{tn\times tm}`$ is the set of correct maximum correlation positions, and $`n`$, again, is the number of valid pixels. We compute the correlation accuracy both for unfiltered images and for gently prefiltered images, with $`\sigma _{pre}=1.0`$. Fig. 10 shows the binary correlation accuracy matrices for our example image. The CMCP set is shown in white, its complement and the boundaries in black. We observe a higher correlation accuracy for the invariant representation, which is improved by the prefiltering.

We have computed the correlation accuracy for all the images given in fig. 11. The results are shown in table 2 and visualized in fig. 12. We observe the following:

* The correlation accuracy CA is higher on the invariant representation than on the intensity images.
* The correlation accuracy is higher on the invariant representation with gentle prefiltering, $`\sigma _{pre}=1.0`$, than without prefiltering. We also observed a decrease in correlation accuracy if we increase the prefiltering well beyond $`\sigma _{pre}=1.0`$. By contrast, prefiltering seems to be always detrimental to the intensity images CA.
* The correlation accuracy shows a wide variation, roughly in the range 30%$`\mathrm{}`$90% for the unfiltered intensity images and 50%$`\mathrm{}`$100% for prefiltered invariant representations. Similarly, the gain in correlation accuracy ranges from close to zero up to 45%. For our test images, it turns out that the invariant representation is always superior, but that doesn’t necessarily have to be the case.
* The medians and means of the CAs over all test images confirm the gain in correlation accuracy for the invariant representation.
* The larger the template size, the higher the correlation accuracy, independent of the representation. A larger template size means more structure, and more discriminatory power.

## 4 Conclusion

We have proposed novel invariants that combine invariance under gamma correction with invariance under geometric transformations. In a general sense, the invariants can be seen as trading off derivatives for a power law parameter, which makes them interesting for applications beyond image processing. The error analysis of our implementation on real images has shown that, for sampled data, the invariants cannot be computed robustly everywhere. Nevertheless, the template matching application scenario has demonstrated that a performance gain is achievable by using the proposed invariant.

## 5 Acknowledgements

Bob Woodham suggested to the author to look into invariance under gamma correction. His meticulous comments on this work were much appreciated. Jochen Lang helped with the acquisition of image data through the ACME facility .