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# 1 Introduction

## 1 Introduction

Water molecules which are present on the surface of soft, complex systems have been the focus of attention for a long time . Not only are the intrinsic structure and dynamics of such water molecules themselves interesting, but their ability to influence the structure, dynamics and function (in the case of biologically relevant complex systems) has made the study of interfacial water a subject of paramount interest to a wide spectrum of researchers from different areas . A variety of experimental, computational, and theoretical tools have been employed to study its properties. Dielectric relaxation experiments have shown the presence of a distinct relaxation peak that could be related to the dynamics of water bound to the surface of a macromolecule . Evidence for the existence of bound water, and its slow dynamics has also been provided by local probes such as NMR , and solvation dynamics experiments .

Computer simulations have enormously aided our understanding of these complex systems . Employing state of the art molecular dynamics simulations, we have recently established the presence of a slow component, running into hundreds of picoseconds, both in the orientational relaxation of the interfacial water molecules and also in the solvation dynamics of ions that are present near the water-micelle interface , consistent with time resolved fluorescence experiments . A gainful analysis of the solvation time correlation function into its partial components provided us insight into the microscopic origin of this slow dynamics. We found that the major contribution to the slow solvation of ions arose from their interactions with the polar headgroups of the surfactants . The observation of the slow component in the decay of the dipolar reorientational time correlation function of the interfacial water molecules  led us to investigate into the cause of the dramatic slowing down of orientational relaxation. Careful analysis of the results demonstrated that it is caused by the long lived hydrogen bonds that the water molecules form with the hydrophilic, and polar headgroups that constitute the micellar surface . Specifically, we calculated the lifetimes of such hydrogen bonds through appropriate time correlation functions (TCF), and found that they are nearly 5 to 10 times longer lived than the hydrogen bonds that water molecules form between themselves. We showed that this longer lifetime profoundly influences the intrinsic dynamics of water molecules at the interface, in terms of their ability to rotate, to translate, and their capability to solvate free ions.

Furthermore, in a recent communication, we have presented, for the first time, microscopic evidence for the presence of three kinds of water molecules in the interfacial layer . This classification was based on the number of hydrogen bonds that an interfacial water molecule makes with the polar headgroups of the surfactants. We found that about 80% of the water molecules in the interface are singly coordinated to the surfactants, and that the rest of the interfacial water molecules are evenly divided into categories that either form two hydrogen bonds with two different surfactant molecules, or those that do not form hydrogen bonds with the macromolecule at all. The former class of water molecules that form one or two hydrogen bonds with the surfactants can thus be called bound and the latter as free. We introduced a nomenclature to identify such species as IBW2 – for water molecules that form two hydrogen bonds with two different surfactants, IBW1 – for water molecules that form only one such hydrogen bond, and IFW – for water molecules that do not form such water-PHG (w-PHG) hydrogen bonds. The ratio of IBW2:IBW1:IFW was found to be distributed as 1.1:8:0.9. Because of the enhanced strength of the w-PHG bond, IBW2 has a lower potential energy than IBW1. Yet, it is not found in abundance as it is disfavored entropically, due to its requirement of a constrained environment, and due to the rarity of events in which two surfactants need to be present around it at the proper orientation, and geometry. Thus, we had shown that the bound and free classification, has both energetic, and structural basis. Needless to state is the fact, that the water molecules at the interface retain their nearly tetrahedral coordination, similar to bulk water, and that their coordination shell gets completed by the formation of hydrogen bonds with other water molecules in the vicinity.

It should be pointed out at this stage that this classification of bound and free applies to interfacial water and therefore, does not refer to bulk water. Indeed, the existence of such free (or quasi-free, if we need to distinguish from bulk water) species at the interface could have far reaching consequence in the understanding of both macromolecular activity, like molecular recognition, and water dynamics.

In light of our earlier observations on the slow dynamics of interfacial water , it would be interesting to examine if the bound-free paradigm  can have a much more robust dynamical basis as well. This is required because the hydrogen bond lifetime analysis provides a slow down by a factor of 10 at the maximum. Thus, although the slow down of this lifetime is probably the fundamental process, it does not fully explain the reason for the dramatic slow down, to the extent of more than two orders of magnitude that we observed in simulations and others observed in experiments. In this article, we explore this aspect of the interfacial water molecules. Details of their structure and energetics have been reported earlier . Here we focus on their dynamics. We find that the long time slow decay observed in the dipolar reorientational TCF of the interfacial water molecules can be directly attributed to the doubly bonded bound water species. We also discuss results on the lifetimes of these species, and we find surprisingly that the singly bonded water species is the longest lived among the three species of interfacial water molecules.

An additional important aspect of this paper is an analysis of the intermolecular vibrational frequencies of the interfacial water. With the recent advent of nonlinear spectroscopic methods that use lasers in the midinfrared region, the dynamics of hydrogen bonds between water molecules has been studied experimentally. In such a technique, one studies the change in the intramolecular O-H stretching frequency for water molecules in different environments. Such studies have shed considerable light on the dynamics of the hydration layer around alkali and halide ions in aqueous salt solutions . We foresee such experiments to be performed for the bound water molecules described here. Unfortunately, we cannot study the change in the intramolecular O-H frequency of the bound water molecules, as our water model has a rigid geometry. However, we provide details on the vibrational spectrum of the bound water molecules by studying the Fourier transform of the velocity auto correlation function of water molecules. We find that both the librational and bending frequencies undergo a significant blue shift, signalling the enhanced rigidity in the structure of the surface water. This blue shift in libration frequency is in good agreement with recent incoherent, inelastic neutron scattering data on macromolecular solutions . These results are expected to be rather general and should be relevant to the understanding of dynamics of water near any hydrophilic surface.

The organization of the rest of the paper is as follows. In the next section we present the details of the systems and of MD simulations. Section III present results on hydrogen bond lifetime. Section IV contains results of our analysis of the frequencies of intermolecular vibrations. Section V concludes with discussion of the results.

## 2 Details of Simulation

The surfactant in our simulations is cesium perfluorooctanoate (CsPFO), which has a carboxylate head group, and a fluorinated tail. It forms oblate ellipsoidal micelles in water . We have studied one micelle, an aggregate of 62 of these surfactants in a simulation box of 10,562 water molecules. An atomistic molecular dynamics simulation of this system at 300K was performed, whose details have been reported earlier . Here we provide essential information on the methods used for analysis of the data pertaining to dynamics of the bound water molecules. The simulations were performed in the NVT ensemble with an integration timestep of 4 fs, using the RESPA algorithm  and the PINY\_MD package . The model for water is the SPC/E , and the interaction potential used has been described earlier . Coordinates of all the atoms were recorded every 12 fs, and the correlation functions presented here were calculated from such a trajectory. In order to calculate the atomic velocity TCFs, we generated a 15 ps long trajectory, where the coordinates and velocities of all the atoms in the simulation were recorded every timestep, so as to accurately obtain the initial fast decay of the velocity TCFs. The hydrogen bond lifetime correlation functions were obtained from a trajectory of length 50 ps, with a time resolution of 12 fs. The long time behavior of some of these functions were obtained from another trajectory of length 3.3 ns, with a time resolution of 1 ps.

An important determinant of the dynamics of water molecules is the reorientation of its dipole vector that can be probed with NMR measurements. We have calculated the dipole-dipole TCF, defined as,

$$\mathrm{C}_\mu (\mathrm{t})=\frac{\mu _\mathrm{i}(\mathrm{t}+\tau )\mu _\mathrm{i}(\tau )}{\mu _\mathrm{i}(\tau )\mu _\mathrm{i}(\tau )}$$
(1)
where $`\mu _i(t)`$ is the dipole moment vector of $`i`$-th water molecule at time t, and the angular brackets denote averaging over water molecules, as well as over initial configurations, $`\tau `$.

Further, we have calculated the lifetime of the hydrogen bonds that the bound water molecules form with the polar headgroups of the surfactant. These have been characterized in terms of two time correlation functions, SHB(t) and CHB(t). These TCFs can be defined using the functions h(t), and H(t) which signify the presence or absence of the hydrogen bond at any time $`t`$, and are given as ,

$`\mathrm{h}(\mathrm{t})`$ $`=`$ $`1,\mathrm{if}\mathrm{a}\mathrm{pair}\mathrm{of}\mathrm{atoms}\mathrm{are}\mathrm{bonded}\mathrm{at}\mathrm{time}\mathrm{t},`$
$`=`$ $`0,\mathrm{otherwise}`$
$`\mathrm{H}(\mathrm{t})`$ $`=`$ $`1,\mathrm{if}\mathrm{a}\mathrm{pair}\mathrm{of}\mathrm{atoms}\mathrm{are}\mathrm{continuously}\mathrm{bonded}`$
$`\mathrm{between}\mathrm{time}0\mathrm{and}\mathrm{time}\mathrm{t}`$
$`=`$ $`0,\mathrm{otherwise}`$
Using these definitions, the bond lifetime correlation functions are defined as,

$`\mathrm{S}_{\mathrm{HB}}(\mathrm{t})`$ $`=`$ $`{\displaystyle \frac{\mathrm{h}(\tau )\mathrm{H}(\mathrm{t}+\tau )}{\mathrm{h}}}`$
$`\mathrm{C}_{\mathrm{HB}}(\mathrm{t})`$ $`=`$ $`{\displaystyle \frac{\mathrm{h}(\tau )\mathrm{h}(\mathrm{t}+\tau )}{\mathrm{h}}}`$ (2)
SHB(t) probes the continuous existence of a hydrogen bond, while CHB(t) allows for the reformation of a bond that is broken at some intermediate time. The former is thus a strict definition of the hydrogen bond lifetime, while the latter is more permissive. The true lifetime of a hydrogen bond lies somewhere in between the two time constants obtained from these functions.

In defining the presence of a hydrogen bond, we employ two distance conditions and one energy criterion, as advocated earlier . These criteria and their legitimacy with regard to the hydrogen bond formed between water and the polar head group have been discussed earlier . Here we just state the definition. We assume a water molecule to be hydrogen bonded to a polar headgroup, if (a) the distance between the oxygen of the water molecule and the carbon of the headgroup is within 4.35Å, and (b) the distance between the oxygen atom of the water molecule and any of the oxygens of the polar headgroup is within 3.5Å, and (c) the pair interaction energy between the water molecule and the headgroup is less than $`6.25`$ kcal/mole.

We have also calculated the lifetime correlation function of the interfacial water species, denoted as SW(t), and CW(t). Their defnitions are similar to SHB(t) and CHB(t), above. However, they are dependent on functions, $`\mathrm{h}(\mathrm{t})`$ and $`\mathrm{H}(\mathrm{t})`$ that are unity when a particular water molecule is of a certain type, and are zero, if it is not. Thus, these need to be distinguished from the SHB(t) and CHB(t) functions which are descriptions of the lifetime of the hydrogen bond. In making this distinction, we allow for the existence of a water molecule in any of the three states – IFW, IBW1, or IBW2, despite the ephemeral loss of a hydrogen bond with a particular PHG.

In order to study the vibrational spectrum of the intermolecular hydrogen bonds, especially those of the bound water at the interface, we have carried out the Fourier transform of the velocity auto correlation function of water molecules defined as, $`\stackrel{}{v}`$

$$\mathrm{C}_{\mathrm{vv}}(\mathrm{t})=\frac{\stackrel{}{\mathrm{v}}_\mathrm{i}(\mathrm{t}+\tau )\stackrel{}{\mathrm{v}}_\mathrm{i}(\tau )}{\stackrel{}{\mathrm{v}}_\mathrm{i}(\tau )\stackrel{}{\mathrm{v}}_\mathrm{i}(\tau )}$$
(3)
where $`𝐯_i(t)`$ is the velocity vector of atom $`i`$ in a water molecule at time $`t`$, and the angular brackets denote averaging over all atoms of such type in the system, and over initial times, $`\tau `$. The Fourier transform of the velocity correlation function provide a direct measure of the vibrational density of states as a function of the frequency.

## 3 Results : Lifetime of Hydrogen Bond and of Interfacial Species

We have provided a schematic illustration in Figure 1 of the two bound interfacial water species, that describes their bonding pattern with the headgroups. The free water molecules are present in the interfacial region, however they are not oriented properly to form a hydrogen bond with the PHG. As discussed earlier , the concentration of IFW:IBW1:IBW2 is 9:80:11.

### 3.1 Lifetime of water-surfactant hydrogen bond

We had shown earlier that the hydrogen bond formed between the water molecules at the interface and the polar headgroups of the surfactant has a much larger lifetime than the hydrogen bonds that water molecules form between themselves . In Figure 2, we show similar lifetime correlation functions for the individual species in the interfacial region. Consistent with our earlier observations , the SHB(t) functions for both the bound species are much slower than the corresponding function for the water-water hydrogen bond in pure water. The function for IBW1 water is slower than that for the doubly hydrogen bonded IBW2 water species. The latter is in a constrained bonding arrangement , and thus the average lifetime of any one of its hydrogen bond is shorter than that formed by the IBW1 water species. In our earlier work , the condition on the pair energy of the water molecule with the PHGs, to determine the presence of a hydrogen bond was not included. The current results, which include such an energy criterion, confirm our findings on the long lifetime of the bound water-PHG hydrogen bond . In addition, we are also able to clearly distinguish the contributions from the two types of interfacial bound water.

The CHB(t) function, presented in the inset to Figure 2, shows a similar trend as the SHB(t) function. As noted earlier, this function allows for the reformation of the hydrogen bond, and thus would take into account, recrossing of the barrier, as well as long time diffusive behavior. Again, we find a characteristic slow decay in its relaxation. The relatively longer lived CHB(t) function for the IBW2 species could come from the break and reformation of the bond over short distances or angles. The IBW2 species will have a higher propensity to reform hydrogen bonds than the IBW1 species, as the latter is only singly hydrogen bonded to the PHGs. Note that in this formalism, we only track the existence of a particular bond of the interfacial water species, and hence the behavior of the functions for IBW1 and IBW2 may not be very different.

### 3.2 Lifetime of interfacial water species

A bound water species could remain bound (to another PHG) even if the hydrogen bond it had originally formed with a particular PHG is broken. Hence, it is important to obtain information on the lifetime of the species, apart from the lifetime of the w-PHG bond discussed in Figure 2. We present this data on the lifetime correlation function of the species in Figure 3. As discussed in the previous section, these functions are essentially similar to the SHB(t) functions defined above, but instead are defined for the identity of the species involved. We observe that the IFW species is short lived, and that the IBW1 species is the longest lived. In our earlier work, we had concluded that the IBW1 species is the thermodynamically stable species . The current calculations indicate that this species is also dynamically more stable than the IBW2 or the IFW species. The IBW2 species, although preferred on energetic grounds due to the contribution from two strong w-PHG hydrogen bonds, is disfavored entropically. It requires the simultaneous presence of two surfactant headgroups in the proper geometry, which is rare. We present the CW(t) functions in the inset to Figure 3. Again, the function for IBW1 is much slower than that of IBW2 or that of IFW. The slow component presumably arises out of a few water molecules (say, of IBW1 type) that lose their identity and reform a w-PHG hydrogen bond either with the same PHG or with another PHG. These molecules probably have long residence times within the first few hydration layers around the micelle.

Within the interfacial region, there is a constant exchange of water molecules between the three states, IBW2, IBW1, and IFW. The microscopic reactions between IBW2 and IBW1 on the one hand, and IBW1 and IFW on the other, are reversible, and are described by four distinct rate constants, as described below.

$$\mathrm{IBW2}_{\mathrm{k}_{12}}^{\mathrm{k}_{21}}\mathrm{IBW1}_{\mathrm{k}_{\mathrm{F1}}}^{\mathrm{k}_{1\mathrm{F}}}\mathrm{IFW}$$
(4)
Determining these rates in such a complex system that is also open to bulk water, is a challenge to us and to other simulators, although the basic formalism exists . Here, we concentrate on generic features that one can derive based on the concentrations of these species. The reactions delineated here are the elementary events, and hence the condition of detailed balance must be obeyed for each of these reactions. The ratio of IBW1 to IBW2 is approximately 8. Hence the rate of production of the IBW1 species from the IBW2 species ($`\mathrm{k}_{21}`$) must be a factor of eight larger than the rate of the reverse reaction. This rationalizes the shorter lifespan of the IBW2 species. Note that this ratio of eight in the rates of interconversion between IBW1 and IBW2 species will be reduced by the other reaction proceeding in the system, that between IFW and IBW1. This too will add to the attrition in the lifetime of the IBW1 species. Fitting the SHB data of lifetimes presented in Figure 3 to multiexponential forms, we find that the average lifetime of the IBW2 species is 0.62 ps, and that of the IBW1 species is 2.26 ps. Thus the IBW1 species is around 3.6 times longer lived than the IBW2 species, which is not inconsistent with the arguments presented above.

### 3.3 Reorientational dynamics of interfacial water

Having determined the intrinsic lifetimes of these interfacial water species, and of the strong hydrogen bonds that they form with the polar headgroups of the surfactant molecules that constitute the micellar surface, we turn our attention now to their single particle dynamics, namely their ability to reorient. The behavior of the dipolar reorientational TCF of the individual bound water species illuminates our understanding on the important issue of the slow decay observed in our simulations earlier . With this objective, we have calculated the dipole-dipole TCFs of the IFW, IBW1, and IBW2 species, which are compared to the function for water molecules far away from the micelle in Figure 4. These data were obtained with a time resolution of 12 fs. The data for water molecules that are at least 25Å away from the micellar surface shows that they behave just like bulk water molecules. The inset to the figure shows the very fast decay of the curve corresponding to the IFW species, very similar to that of water far from the micelle. This validates our christening this species as free interfacial water, IFW. The plot also displays the corresponding TCF for the IBW1 and IBW2 species. The reorientation of the IBW1 water, possessing a single, strong hydrogen bond with the PHG is slowed down relative to that of the IFW species, while the IBW2 water species, being in a constrained environment is able to rotate only within a narrow cone. This is borne out by the plateauing of the dipolar TCF after a few picoseconds, found in the data for the IBW2 species. The strict definitions of a water-PHG hydrogen bond precludes us from probing the TCFs any further than the durations shown in the figure, as these species themselves cease to survive, a few picoseconds beyond the maximum times for which the TCFs have been displayed. However, a bound water is unlikely to lose its memory of orientation, once it has “broken” its w-PHG hydrogen bond. It is more likely that its orientation is preserved for some longer duration, and that the strict definition of the existence of the bound nature of water prevents one from probing the orientation any further. This indicates that we could continue to probe the dipolar TCFs of these waters for a longer duration, if we relax the conditions on the nature of the bound water species. We describe such a calculation below.

Water molecules within a 10Å hydration layer around the micelle exhibit a pronounced slowing down in their reorientation . The long time behavior of the C$`\mu `$(t) shows a near-constant value, indicating that the molecules are not able to explore fully all possible orientations. In our simulations, the near-constant value of C$`\mu `$(t) extends to a few hundreds of picoseconds and appears to be a general feature to interfacial water near hydrophilic surfaces in complex systems. This observation may seem apparently inconsistent with the data presented in Figure 3 or Figure 4, where the bound water of either the IBW1 or IBW2 type, are seen to lose their identity within few tens of picoseconds. The resolution of this apparent conflict, lies, as we discussed earlier, in the rather strict definition of the lifetime of the bound species. We have calculated the same functions exhibited in Figure 4, with a coarser resolution of 1 ps, and display them for the bound water species in Figure 5. Shown here are the Cμ(t) functions obtained from a trajectory where the coordinates of all the atoms were stored every 1 ps, instead of the 12 fs used in Figure 4. This effectively allows for the consideration of reformation of the w-PHG hydrogen bond, thus extending the lifetime of the bound water species. We are thus able to observe the reorientational TCFs of these species for a much longer duration than what was possible in Figure 4. Such a data, presented in Figure 5 clearly shows the existence of very slow dynamics in the timescales of hundreds of picoseconds. More importantly, the reorientational TCF obtained for all bound water species, irrespective of the IBW1 or the IBW2 type, exhibits a plateau followed by a slow decay. These results shows that exchanges between the IBW1 and the IBW2 states of water molecules artificially prevents one from obtaining the dipolar reorientational TCF of either of these individual species for times longer than their “intrinsic” lifetimes. However, the TCF for all bound water species, irrespective of their type, clearly proves the existence of a long-lived plateau running probably into hundreds of picoseconds. This is the first, direct microscopic evidence for such a slow relaxation arising out of water species bound to a hydrophilic surface. As mentioned earlier, these results should be of relevance to other hydrophilic surfaces as well.

It is thus clear that the long-time slow decay in the dipolar reorientational TCF arises out of
(i) the orientational locking-in of the IBW2 species, due to its two strong w-PHG hydrogen bonds
(ii) the interconversion between the IBW1 and IBW2 species.

The latter, a secondary process, merits further discussion. From the TCFs shown in Figure 5, one can obtain average time constants for the relaxation of the reorientation of the dipole. This is certainly valid if a water molecule, for example, was of the IBW1 type at time zero, and remained so thereafter. However, the average lifetime of the w-PHG hydrogen bond is of the order of 2 to 40 ps (see Figure 2), and hence one can expect a fair number of water molecules to interconvert between the IFW, IBW1, and IBW2 states within the interfacial layer. Hence the said IBW1 water molecule may form an additional w-PHG bond and change its nature to that of a IBW2 type. This would, in effect, set the clock for reorientation of its dipole to the dipolar TCF corresponding to the IBW2 type shown in Figure 5, which is much slower than that for the IBW1 species. Such interconversions between the interfacial water species will add to the slow decay of the intrinsic species shown in Figure 5 and would contribute, specifically, to the intermediate time scales (tens of picoseconds) in the TCF, while the orientational locking-in of the IBW2 species will contribute to the long time slow decay (hundreds of picoseconds). Further, a few members of the IBW2 type can be long lived, and they too would contribute to the long time behavior of the total dipolar reorientational TCF. It is the sum effect of these processes that we had observed earlier in our preliminary investigations of the reorientations of interfacial water molecules. This interpretation of the exchange between the species present at the interface to contribute to the slow dynamics is consistent with the postulates of Nandi and Bagchi .

## 4 Vibrational Spectrum of Interfacial Water and Density of States

Thus far we have provided microscopic evidence for the slowdown in the dynamics of interfacial water due to the presence of the polar, fluctuating micellar surface. The interface influences not only single particle quantities such as the dipolar reorientation of the water molecules, but it also affects the ability of water molecules to librate (hindered rotation), and their ability to alter the hydrogen bond network through bond bending excitations. We probe such molecular motions through calculations of the velocity time correlation function of the water molecules and the density of states of the respective motions.

Low frequency Raman and neutron scattering experiments on aqueous protein solutions have shown the presence of excess density of states, called the boson peak, at around 3 meV (24 cm-1 which has been corroborated by molecular dynamics simulations . This boson peak is due to low frequency collective vibrational mode of the biomolecule. In this work, however, we concentrate on excitations of relatively higher frequencies. Specifically, we study the effect of the interface on the O..O..O bending, O..O stretching, and the librational modes of water, that are observed at around 50 cm-1, 200 cm-1, and at 500 cm-1 , respectively, in bulk water. Note that all the three are inter-molecular vibrational modes and involve hydrogen bonding. All these modes play an important role in the dynamics of chemical processes in water, such as solvation dynamics and charge transfer .

We have obtained the velocity autocorrelation functions of both the oxygen and the hydrogen atoms of interfacial water molecules, and have obtained their power spectra. The results indicate strong effects of the micellar surface.

The computed velocity correlation functions are presented in Figure 6 where we have also compared them with corresponding functions for water molecules far away from the micelle. In Figure 6a, we present the C$`{}_{}{}^{\mathrm{O}}{}_{\mathrm{vv}}{}^{}`$(t) for the oxygen atoms of the interfacial water species. As expected, there is a clear trend in the variation of this function, particularly near the first minimum that corresponds to backscattering of the atoms. The minimum for IBW2 is deeper than that for the rest of the species, a direct consequence of the enhanced rigidity of its environment. The function for water molecules far away from the micellar surface is identical to its behavior in bulk. The function for IFW follows closely that of bulk water, however it exhibit a shallower first minimum than bulk water. We had shown earlier  that the first coordination shell (up to a distance of 3.5Å) around the IFW species contains 4.4 water molecules and 0.3 PHG oxygens, while that around the IBW1 species contains 4.1 water molecules and 1.2 PHG oxygens, and that of the IBW2 species contains 3.0 water molecules and 2.1 PHG oxygens. This marginal decrease in the coordination number around the IFW species could be a prime reason for the shallower first minimum in its C$`{}_{}{}^{\mathrm{O}}{}_{\mathrm{vv}}{}^{}`$(t) than that for bulk water. These broad conclusions are substantiated by an analysis of the C$`{}_{}{}^{\mathrm{H}}{}_{\mathrm{vv}}{}^{}`$(t) function for the hydrogen atoms of the interfacial water species presented in Figure 6b. The enhanced rigidity around IBW2 water manifests itself in a deeper minimum and again, the data for IFW species mirrors closely the behavior for water in bulk. However the value for the IFW species at the first minimum is less negative than that for bulk water. Lee and Rossky  had found a similar behavior for water molecules present near a hydrophobic surface. This indicates that the IFW species might be somewhat buried within the micelle, in proximity to the CF2 groups adjacent to the polar headgroup. The data for IBW1, the abundant species in the interface lies between the functions for IFW and that of IBW2.

The power spectra, obtained by a Fourier cosine transform of these velocity auto time correlation functions, are displayed in Figure 7. In Figure 7a, we provide this data obtained from oxygen atoms, for all interfacial water species, i.e., for water molecules that reside within a distance of 4.5Å from any of the surfactant headgroups. Transforms of individual water species were noisy, and hence are not provided here. Relative to water in the bulk, we observe a clear blue shift in the frequency corresponding to the O..O..O bending mode by about 40 cm-1 for these interfacial water molecules while the stretching mode seems not to be affected by the interface, consistent with earlier observations on aqueous protein solutions . The most significant change in the vibrational spectrum occurs for the librational mode of the water molecules which can be studied from the power spectrum for the hydrogen atoms of the interfacial water species. Again, the trend observed in Figure 6b is seen in their power spectra. The librational mode of IBW2 is most affected, and is shifted considerably, by about 150 cm-1, whereas that of the IBW1 species is blue shifted by about 100 cm-1 relative to water bulk and is observed at 600 cm-1. These data agree well with recent incoherent, inelastic neutron scattering experiments on aqueous DNA and membrane solutions, where the vibrational signature of interfacial water molecules was found to be predominant in the 400-600 cm-1 range . The hydrogen atoms also contribute to the O..O..O bending mode at around 60 cm-1, whose shift to higher frequencies is also observed from the oxygen spectrum. These frequency shifts in the bending and librational modes must arise from the strong, and longer lived w-PHG hydrogen bond. Evidence for the strength, and the lifetime of these bonds have been provided earlier. Therefore, one may conclude that water structure on the surface is more rigid. While this is of course expected on simple arguments, the strong effect on bending and librations, while the negligible effect on stretching were not anticipated, but is in agreement with IINS results. This needs further study.

## 5 Conclusions

The results of the present atomistic MD simulations provide microscopic explanation for several of the observations reported earlier . We find that the hydrogen bonds between the bound water molecules and the polar headgroups are much longer lived, on the average, than the hydrogen bonds that water molecules form among themselves. The lifetime of the w-PHG hydrogen bond of the IBW2 type of water molecule is shorter than that of the IBW1 type. This can be rationalized in terms of the constrained nature of the environment around the IBW2 water molecule. This aspect is also reflected in the lifetimes of the intrinsic species. The IBW1 water is dynamically more stable than the IBW2 species, which is consistent with our observations on its concentration, energetics and environment.

We have also calculated individual dipolar reorientational time correlation functions for the three species of interfacial water molecules, and have compared them to the corresponding function for water molecules in bulk. The IFW water molecule is able to reorient in the same timescale as the bulk water. Thus, the interfacial free water appears to be energetically, structurally, and dynamically rather similar to, albeit a bit slower than, the water in the bulk. The bound water molecules exhibit very different dynamical properties. The IBW1 water molecule exhibits a slow relaxation with the longest component around several tens of picoseconds, while the IBW2 water molecule exhibits a long lived plateau region in the time correlation function. This can be ascribed to the two strong w-PHG hydrogen bonds that this species makes, resulting in a significant loss of orientational freedom. About 10% of the interfacial water molecules are of the IBW2 type, and hence this plateau can be directly implicated in the long-time relaxation of the dipolar TCF of all the interfacial water molecules that we had reported earlier . The current set of results thus explain, comprehensively, the microscopic origin of the slow decay in the reorientational TCF of interfacial water molecules in aqueous macromolecular solutions.

A significant finding of the present work is the modification in the vibrational spectral features of the interfacial water molecules. We observe a blue shift in the O..O..O bending mode of about 40 cm-1. The librational mode of the water molecule at around 500 cm-1 undergoes a blue shift of about 100 $`cm^1`$. Surprisingly, the 200 cm-1 translational, O..O stretching mode is entirely unaffected due to the interface. These results are somewhat surprising and indicate that the the potential surface around the interfacial water molecules is more rigid along the orientational degrees of freedom rather than along the translational degrees. This conclusion is also consistent with observations on the relative effects of the interface on translational diffusion of water molecules and their orientational relaxation . Our results on the vibrational spectra also adds support to recent IINS data on aqueous membrane and DNA solutions, where the interfacial water molecules have an altered vibrational spectrum in the 400-600 cm-1 range . We plan to probe these aspects further by a normal mode analysis of the potential energy hypersurface. This could explain the reason for the lack of change in the 200 cm-1 intermolecular vibrational mode. This point deserves further study.

## 6 Acknowledgements

We thank Dr. Francis Starr for pointing out Ref. . SB and BB acknowledge financial support from the Council of Scientific and Industrial Research, and the Department of Science & Technology, India.

FIGURE CAPTIONS

Figure 1 Schematic representation of IBW1 and IBW2 types of interfacial water molecules. Water molecules at the interface that are not hydrogen bonded to any surfactant, but are instead coordinated fully to other water molecules in the vicinity are denoted as IFW.

Figure 2 Hydrogen bond lifetime correlation function, SHB(t) for IBW1 (continuous line) and for IBW2 (dashed line) types of water molecules. Inset show the decay of CHB(t) for the same.

Figure 3 Species life time correlation function, SW(t) for the different interfacial water molecules. Inset show the CW(t) function for the same. Numerical data points are shown infrequently for clarity.

Figure 4 Dipolar reorientational time correlation function, Cμ(t), for the interfacial water molecules. The inset compares the data for the IFW water species and for water molecules that are at least 25Å away from the micellar surface. The latter behave like water in bulk. The time resolution of the underlying trajectory used in this calculation is 12 fs. Numerical data points are shown infrequently for clarity.

Figure 5 Dipolar reorientational time correlation function, Cμ(t), for bound water molecules. The data denoted by the legend, IBW1-IBW2, corresponds to all bound water molecules irrespective of their being in state IBW1 or IBW2. The time resolution of the underlying trajectory used in this calculation is 1 ps. Numerical data points are shown infrequently for clarity.

Figure 6a Normalized velocity auto correlation function, C$`{}_{}{}^{\mathrm{O}}{}_{\mathrm{vv}}{}^{}`$(t), of the oxygen atoms for various interfacial water molecule types compared with that for water molecules that are at least 25Å away from the micellar surface. The latter behave like water in bulk. Numerical data points are shown infrequently for clarity.

Figure 6b Normalized velocity auto correlation function, C$`{}_{}{}^{\mathrm{H}}{}_{\mathrm{vv}}{}^{}`$(t), of the hydrogen atoms for various interfacial water molecule types compared with that for water molecules that are at least 25Å away from the micellar surface. The latter behave like water in bulk. Numerical data points are shown infrequently for clarity.

Figure 7a Power spectrum of the C$`{}_{}{}^{\mathrm{O}}{}_{\mathrm{vv}}{}^{}`$(t) function, for oxygen atoms of water molecules lying within 4.5Åfrom any polar head group of the micelle compared with that for water molecules that are at least 25Å away from the micellar surface. The latter behave like water in bulk.

Figure 7b Power spectrum of the C$`{}_{}{}^{\mathrm{H}}{}_{\mathrm{vv}}{}^{}`$(t) function, for hydrogen atoms of various interfacial water molecule types compared with that for water molecules that are at least 25Å away from the micellar surface. The latter behave like water in bulk.


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# Charged hadron transverse momentum distributions in Au+Au collisions at √𝑠__{𝑁𝑁}= 200 GeV

## Abstract

We present transverse momentum distributions of charged hadrons produced in Au+Au collisions at $`\sqrt{s_{_{NN}}}=`$ 200 GeV. The spectra were measured for transverse momenta $`p_T`$ from 0.25 to 4.5 GeV/c in a rapidity range of $`0.2<y_\pi <1.4`$. The evolution of the spectra is studied as a function of collision centrality, from 65 to 344 participating nucleons. The results are compared to data from proton-antiproton collisions and Au+Au collisions at lower RHIC energies. We find a significant change of the spectral shape between proton-antiproton and peripheral Au+Au collisions. Comparing peripheral to central Au+Au collisions, we find that the yields at high $`p_T`$ exhibit approximate scaling with the number of participating nucleons, rather than scaling with the number of binary collisions.

The yield of charged hadrons produced in collisions of gold nuclei at an energy of $`\sqrt{s_{_{NN}}}=200`$ GeV has been measured with the PHOBOS detector at the Relativistic Heavy-Ion Collider (RHIC) at Brookhaven National Laboratory. The data are presented as a function of collision centrality and transverse momentum $`p_T`$. The goal of our measurements is to test our understanding of Quantum Chromodynamics (QCD), the fundamental theory of the strong interaction. Using nuclear collisions, QCD can be studied in a regime of high temperature and energy density. Calculations suggest qgp  that under these conditions a new state of matter, the quark-gluon plasma, will be formed.

In the theoretical analysis of particle production in hadronic and nuclear collisions, a distinction is often made between the relative contributions from “hard” parton-parton scattering processes and “soft” processes. The former can be calculated using perturbative QCD, whereas the latter are typically treated by phenomenological models that describe the non-perturbative sector of QCD pythia . The contribution from hard processes is expected to grow with increasing collision energy and to dominate particle production at high transverse momenta. Collisions of heavy nuclei offer ideal conditions to test our understanding of this picture, as “hard” processes are expected to scale with the number of binary nucleon-nucleon collisions $`N_{coll}`$, whereas “soft” particle production is expected to exhibit scaling with the number of participating nucleons $`N_{part}`$. In Glauber-model calculations, $`N_{coll}`$ scales approximately as $`(N_{part})^{4/3}`$. For central collisions of Au nuclei, this leads to an increase of a factor of six in the ratio of $`N_{coll}/N_{part}`$, relative to proton-proton collisions. Collision centrality is therefore a parameter by which the relative contributions of hard and soft processes to particle production can be varied. It was found that a description based on a combination of hard and soft particle production is compatible with the observed centrality dependence of the charged particle multiplicity at mid-rapidity in Au+Au collisions phenix\_cent ; phobos\_cent\_200 , although the result can also be described by models which incorporate initial state parton saturation kharzeev . A simultaneous study of the $`p_T`$ and centrality dependence of particle yields may allow us to better discriminate between these different physical pictures.

For Au+Au collisions at RHIC energies, it has been predicted that the yield and momentum distribution of particles produced by hard scattering processes may be modified by “jet quenching”, i.e. the energy loss of high momentum partons in the dense medium jet\_quench\_theory . This phenomenon has been proposed as a diagnostic tool for characterizing the parton density in the initial stage of high-energy nuclear collisions. First results for central Au+Au collisions at $`\sqrt{s_{_{NN}}}=`$ 130 GeV have shown that particle spectra at large transverse momenta indeed change in comparison to p+p collisions jet\_quench\_phenix . This result has been used to estimate the energy loss in the dense medium gyulassy\_01 . However, calculations have not yet shown a consistent interpretation of the data on spectral shapes and particle multiplicities. The latter seem to be overpredicted phobos200  when the effects of jet quenching are included. Here we probe the scaling of particle production over a wide range of $`N_{coll}`$ and $`N_{part}`$ in different regimes of $`p_T`$ that are traditionally believed to be dominated by soft or hard processes.

The data were collected using the PHOBOS two-arm magnetic spectrometer phobos1 ; phobos2 ; pak . The spectrometer arms are each equipped with 16 layers of Silicon sensors, providing charged particle tracking both outside and inside the 2 T field of the PHOBOS magnet. Particles within the geometrical acceptance region used in this analysis traverse at least 14 of the layers. A two layer silicon vertex detector covering $`|\eta |<0.92`$ and 25% of the azimuthal angle provided additional information on the position of the primary collision vertex. In total, 135168 detector elements were read out, of which less than 2% were non-functional.

The primary event trigger was provided by two sets of 16 scintillator paddle counters covering pseudorapidities $`3<|\eta |<4.5`$. Additional information for event selection was obtained from two zero-degree calorimeters which detect spectator neutrons. Details of the event selection and centrality determination can be found in phobosprl ; phobos\_cent\_200 . Monte Carlo (MC) simulations of the apparatus were based on the HIJING event generator hijing  and the GEANT 3.21 simulation package, folding in the signal response for scintillator counters and silicon sensors.

For this analysis, the events were divided into six centrality classes, based on the observed signal in the paddle counters. Given the monotonic relationship between the multiplicity of produced particles in the paddle acceptance and the number of participating nucleons $`N_{part}`$, the results of a Glauber-model calculation were used phobosprl ; phobos\_cent\_200  to estimate the average number of participating nucleons and the number of binary collisions for each centrality class. The resulting values are shown in Table I.

As the geometrical layout of the PHOBOS detector leads to an asymmetry in the acceptance and detection efficiency for positively and negatively charged particles for a given magnet polarity, data were taken using both polarities. The reproducibility of the absolute field strength was found to be better than 1%, based on Hall probe measurements for each polarity and the comparison of mass distributions for identified particles at the two polarities.

To optimize the precision of the vertex and track finding, only events with a reconstructed primary vertex position between -10 cm $`<z_{vtx}<`$ 10 cm along the beam axis were selected. By requiring a consistent vertex position from the spectrometer and vertex subdetectors, in combination with the known position of the beam orbit, a vertex resolution better than 0.3 mm (RMS) in the longitudinal and vertical directions, $`z`$ and $`y`$, and better than 0.5 mm in the horizontal direction, $`x`$, was achieved.

Details of the reconstruction algorithm for particle tracks can be found in pbarp\_200 . Track candidates were found combining a road-following algorithm in the region outside the magnetic field and a transformation algorithm for pairs of hits inside the field. The distance of closest approach of each reconstructed track with respect to the primary vertex ($`d_{vtx}`$) was used to reject background particles from decays and secondary interactions. The final track selection was based on the $`\chi ^2`$ fit probability of a full track fit, taking into account multiple scattering and energy loss. For further analysis, particles with a rapidity of $`0.2<y_\pi <1.4`$ were used, assuming the pion mass for calculating $`y_\pi `$.

To obtain the invariant yield for charged hadrons, the observed transverse momentum distributions were corrected for the geometrical acceptance of the detector, the efficiency of the tracking algorithm and the distortion due to binning and momentum resolution. For the acceptance and efficiency corrections, the correction factors in $`p_T`$ and $`y`$ vary as a function of vertex position and are different for the two charge signs in a given field polarity. The correction factors were obtained in vertex bins of $`\pm 2.5`$ cm size by embedding the same MC particle tracks into “empty” events and data events. The events were reconstructed with the standard reconstruction chain with and without the additional embedded tracks. From this comparison, a correction factor as a function of $`p_T`$ and multiplicity was extracted. Over the centrality range covered in this analysis, the reconstruction efficiency decreased by approximately 10%.

MC-simulations based on HIJING and GEANT were used to obtain correction factors for the contribution of secondary particles to the charged particle spectra. The acceptance for secondary and feeddown particles is limited to those produced within 10 cm radial distance from the primary collision vertex, as accepted tracks were required to have at least one hit in the first two layers of the spectrometer. The background contamination is further reduced by requiring the particle tracks to have $`d_{vtx}<3.5`$ mm. We found that the contamination varies from less than 4% at $`p_T0.3`$ GeV/c to less than 2% at $`p_T>2.5`$ GeV/c. The corresponding correction was applied independent of collision centrality.

The contamination by wrongly reconstructed (“ghost”) tracks was studied using two methods. The reconstruction of HIJING events showed a rate of ghost tracks after all quality cuts of less than 4% at $`p_T0.5`$ GeV/c and less than 2% at $`p_T2.5`$ GeV/c. At higher $`p_T`$, the available MC statistics did not allow a precise determination of the ratio of ghost tracks to found tracks. However, MC simulations showed that most ghost tracks arise from a wrong match of track segments inside and outside the magnetic field. The rate of accidental matches was tested by swapping straight and curved track segments between the two spectrometer arms. We found a contribution of accidental matches of less than 1% in the $`p_T>3`$ GeV/c region.

Finally, the spectra were corrected for the effects of the finite bin-width and the momentum resolution using an iterative procedure. The resolution was determined using track embedding and the full reconstruction and fitting procedure. For embedded MC tracks we found a momentum resolution of $`\mathrm{\Delta }p/p=19\%`$ for the momentum range of 0.3 to 10 GeV/c. The corresponding correction was performed for each centrality bin separately, taking into account the non-Gaussian tails in the $`p_T`$-resolution function. At $`p_T4`$ GeV/c, the correction varies from a factor of 0.92 for the most peripheral events to 0.89 for the most central events.

In Fig. 1 we show the invariant yield of charged hadrons as a function of transverse momentum, obtained by averaging the yields of positive and negative hadrons. Data are shown for 6 centrality bins, ranging from $`N_{part}=65`$ to $`N_{part}=344`$. The integrated yields, when scaled by $`N_{part}`$, increase by 15% over the centrality range, consistent with the centrality evolution of the mid-rapidity particle density presented in phobos\_cent\_200 .

In Fig. 2 we show the ratios of data for the most peripheral bin ($`N_{part}=65\pm 4)`$ and the most central bin ($`N_{part}=344\pm 11)`$ to a fit of the measured $`p_T`$-distribution in proton-antiproton collisions at the same energy ua1\_pbarp . In both cases, the Au+Au data were divided by the respective value of $`N_{part}/2`$. The brackets indicate the systematic uncertainty in the Au+Au data (90% C.L.). The largest contribution to the systematic uncertainty are the overall tracking efficiency, independent of $`p_T`$, and the $`p_T`$ dependent momentum resolution and binning correction. The small contamination by secondary particles and feeddown particles, due to the proximity of the tracking detectors to the collision vertex, also ensures that the uncertainty in the corresponding correction factors is small. Similarly, the high granularity and resolution of the tracking planes leads to small uncertainty in the rate of ‘ghost’ tracks.

As has been shown previously phobos200 ; phobosprl , the yield per participant pair in Au+Au collisions at these centralities is significantly larger than in proton-antiproton collisions at the same energy. We also observe that in peripheral Au+Au collisions with $`N_{part}=65`$, corresponding to an impact parameter $`b10`$ fm, the spectral shape is already strongly modified from that in $`p+\overline{p}`$ collisions. It is worth noting that the ratio $`\frac{N_{coll}}{N_{part}/2}`$ increases by a factor of almost three from $`p+\overline{p}`$ to the most peripheral Au+Au collisions studied here. For the highest $`p_T`$, the yield for central events is significantly smaller than expectations based on $`N_{coll}`$-scaling.

The detailed evolution of the spectra from peripheral to central events is shown in Fig. 3, for the six centrality bins. Each spectrum has been been divided by $`N_{part}/2`$ and a fit to the data for the most peripheral bin. $`N_{part}`$-scaling would correspond to the ratio being constant at one (solid line), whereas $`N_{coll}`$-scaling, shown by the dashed line, would lead to an increase by a factor of two from peripheral to central events. Again, the brackets show the systematic uncertainty (90% C.L.). It is remarkable that the change in spectral shape over this range of centralities is small compared to that between $`p+\overline{p}`$ collisions and peripheral events shown in the top panel of Fig. 2. In particular at $`p_T>3`$ GeV/c, the data scale with the number of participants to very good approximation.

The scaling behaviour in various regions of $`p_T`$ is further illustrated in Fig. 4. Here we show the yield per participant pair in six bins of $`p_T`$ between 0.45 and 4.25 GeV/c, normalized to the yield per participant pair in the most peripheral bin. The expectation for $`N_{coll}`$-scaling relative to the most peripheral bin is again shown as a dashed line. The observed evolution can be contrasted with the expectation that particle production should be characterized by a change from $`N_{part}`$ scaling at low $`p_T`$ to $`N_{coll}`$ scaling at high $`p_T`$, with $`N_{part}`$ increasing from 65 to 344 and $`N_{coll}`$ from 107 to 1050 between the most peripheral collisions and the most central collisions studied here. No corresponding increase in particle production per participant at $`p_T=3`$ GeV/c and above is observed. Rather, the yields in this region scale approximately with the number of participating nucleons.

The failure of binary collision scaling at intermediate and large $`p_T`$ was previously observed in Au+Au collisions at $`\sqrt{s_{_{NN}}}=`$ 130 GeV jet\_quench\_phenix . This effect has been interpreted as the result of the energy loss of jets in the dense medium, leading to a suppression of leading hadrons relative to the expected scaling. The observed particle spectra are believed to depend on a complex interplay of initial and final state effects in the production and fragmentation of high $`p_T`$ partons, including initial state multiple scattering, nuclear shadowing and parton energy loss. Our observations show that, surprisingly, the combination of all effects leads to an apparently very simple centrality scaling at large $`p_T`$, providing a challenge to theoretical descriptions. That this is not accidental is suggested by the agreement with earlier measurements at $`\sqrt{s_{_{NN}}}=`$ 130 GeV. The lower energy data star\_highpt\_npart ; phenix\_highpt\_npart , when compared over the same centrality range, show very similar centrality scaling, even though the invariant yield at high $`p_T`$ increases much more rapidly with increasing beam energy than the overall particle yield. It has recently been argued that the observed scaling could be naturally explained in a model assuming the dominance of surface emission of high-$`p_T`$ hadrons mueller\_8\_02 . However, the approximate participant scaling has also been explained in the context of initial state saturation models kharzeev\_10\_02 . Experimentally, upcoming studies of d+Au collisions at RHIC will provide further insight into the modification of particle spectra in a nuclear environment.

This work was partially supported by U.S. DOE grants DE-AC02-98CH10886, DE-FG02-93ER40802, DE-FC02-94ER40818, DE-FG02-94ER40865, DE-FG02-99ER41099, and W-31-109-ENG-38 as well as NSF grants 9603486, 9722606 and 0072204. The Polish group was partially supported by KBN grant 2-P03B-10323. The NCU group was partially supported by NSC of Taiwan under contract NSC 89-2112-M-008-024.