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# Relaxed Scheduling in Dynamic Skin Triangulation Research of the two authors is supported by NSF under grant CCR-00-86013.

## 1 Introduction

In this paper, we describe a relaxed scheduling paradigm for operations that maintain the mesh of a deforming surface. We prove the correctness of this paradigm for skin surfaces.

### Background.

In 1999, Edelsbrunner \[Ede99\] showed how a finite collection of spheres or weighted points can be used to construct a $`C^1`$-continuous surface in $`^3`$. It is referred to as the *skin* or the *skin surface* of the collection. If the spheres represent the atoms of a molecule then the appearance of that surface is similar to the molecular surface used in structural biology \[Con83, LeRi71\]. The two differ in a number of details, one being that the former uses hyperboloids to blend between sphere patches while the latter uses tori. The skin surface is not $`C^2`$-continuous, but its maximum normal curvature, $`\kappa `$, is continuous. This property is exploited by Cheng et al. \[CDES01\], who describe an algorithm that constructs a triangular mesh representing the skin surface. In this mesh, the sizes of edges and triangles are inversely proportional to the maximum normal curvature. The main idea of the algorithm is to maintain the mesh while gradually growing the skin surface to the desired shape, as illustrated in Figure 1.

The algorithm thus reduces the construction to a sequence of restructuring operations. There are *edge flips*, which maintain the mesh as the restricted Delaunay triangulation of its vertices, *edge contractions* and *vertex insertions*, which maintain a sampling whose local density is proportional to the maximum normal curvature, and *metamorphoses*, which adjust the mesh connectivity to reflect changes in the surface topology. Some of these operations are easier to schedule than others, and the most difficult ones are the edge contractions and vertex insertions. They depend on how the sampled points move with the surface as it deforms. The quality of the mesh is guaranteed by maintaining size constraints for all edges and triangles. When an edge gets too short we contract it, and when a triangle gets too large we insert a point near its circumcenter. Both events can be recognized by finding roots of fairly involved functions. Scheduling edge contractions and vertex insertions thus becomes a bottleneck, both in terms of the robustness and the running time of the algorithm.

### Result.

In this paper, we study how fast edges and triangles vary their size, and we use that knowledge to schedule these elements in a relaxed fashion. In other words, we do not determine when exactly an element violates its size constraint, but we catch it before the violation happens. Of course, the danger is now that we either update perfectly well-shaped elements or we waste time by checking elements unnecessarily often. To avoid the former, we introduce intervals or gray zones in which the shapes of the elements are neither good nor unacceptably bad. To avoid unnecessarily frequent checking, we prove lower bounds on how long an element stays in the gray zone before its shape becomes unacceptably bad. These bounds are different for edges and for triangles. Consider first an edge $`uv`$. Let $`R=uv/2`$ be its half-length and $`\varrho =1/\mathrm{max}\{\kappa (u),\kappa (v)\}`$ the smaller radius of curvature at its endpoints. We use judiciously chosen constants $`C`$, $`Q_0`$ and $`Q_1`$ and call the edge

$$\begin{array}{c}\text{acceptable}\hfill \\ \text{borderline}\hfill \\ \text{unacceptable}\hfill \end{array}\}\text{ if }\{\begin{array}{c}C/Q_0<R/\varrho ,\hfill \\ C/Q_1<R/\varrho C/Q_0,\hfill \\ R/\varrho C/Q_1.\hfill \end{array}$$

The middle interval is what we called the gray zone above. Assuming $`uv`$ is acceptable, we prove it will not become unacceptable within a time interval of duration $`\mathrm{\Delta }t=(2\theta \theta ^2)\varrho ^2`$, where

$`\theta ={\displaystyle \frac{RQ_1C\varrho }{RQ_1+C\varrho }}.`$
In the worst case, $`R`$ is barely larger than $`C\varrho /Q_0`$, so we have $`\theta >(Q_1Q_0)/(Q_1+Q_0)`$ as a worst case bound. We will see that $`C=0.06`$, $`Q_0=1.6`$ and $`Q_1=2.3`$ are feasible choices for the constants, and that for these we get $`\theta >0.179\mathrm{}`$ and $`\mathrm{\Delta }t/\varrho ^2>0.326\mathrm{}`$. Consider next a triangle $`uvw`$. Let $`R`$ be the radius of its circumcircle, and $`\varrho =1/\mathrm{max}\{\kappa (u),\kappa (v),\kappa (w)\}`$ the smallest radius of curvature at its vertices. We call $`uvw`$

$$\begin{array}{c}\text{acceptable}\hfill \\ \text{borderline}\hfill \\ \text{unacceptable}\hfill \end{array}\}\text{ if }\{\begin{array}{c}R/\varrho <CQ_0,\hfill \\ CQ_0R/\varrho <CQ_1,\hfill \\ CQ_1R/\varrho .\hfill \end{array}$$

Assuming $`uvw`$ is acceptable, we prove it will not become unacceptable within a time interval of duration $`\mathrm{\Delta }t=(2\theta \theta ^2)\varrho ^2`$, where

$`\theta =1\sqrt[4]{R/(CQ_1\varrho )}.`$
In the worst case, $`R`$ is barely smaller than $`CQ_0\varrho `$, so we have $`\theta >1\sqrt[4]{Q_0/Q_1}`$. For the above values of $`C`$, $`Q_0`$ and $`Q_1`$, this gives $`\theta >0.086\mathrm{}`$ and $`\mathrm{\Delta }t/\varrho ^2>0.165\mathrm{}`$. It seems that triangles can get out of shape about twice as fast as edges, but we do not know whether this is really the case because our bounds are not tight.

### Outline.

Section 2 reviews skin surfaces and the dynamic triangulation algorithm. Section 3 introduces relaxed scheduling as a paradigm to keep track of moving or deforming data. Section 4 analyzes the local distortion within the mesh and derives the formulas needed for the relaxed scheduling paradigm. Section LABEL:sec5 concludes the paper.

## 2 Preliminaries

In this section, we introduce the necessary background from \[Ede99\], where skin surfaces were originally defined, and from \[CDES01\], where the meshing algorithm for deforming skin surfaces was described.

### Skin surfaces.

We write $`S_i=(z_i,r_i)`$ for the sphere with center $`z_i^3`$ and radius $`r_i`$ and think of it as the zero-set of the weighted square distance function $`f_i:^3`$ defined by $`f_i(x)=xz_i^2r_i^2`$. The square radius is a real number and the radius is either a non-negative real or a non-negative multiple of the imaginary unit. We know how to add functions and how to multiply them by scalars. For example, if we have a finite collection of spheres $`S_i`$ and scalars $`\gamma _i=1`$ then $`\gamma _if_i`$ is again a weighted square distance function, and we denote by $`S=\gamma _iS_i`$ the sphere that defines it. The *convex hull* of the $`S_i`$ is the set of such spheres obtained using only non-negative scalars:

$`=\{{\displaystyle \gamma _iS_i}{\displaystyle \gamma _i}=1\text{ and }\gamma _i0,i\}.`$
We also shrink spheres and write $`\sqrt{S}=(z,r/\sqrt{2})`$, which is the zero-set of $`2ff(z)`$. The *skin surface* defined by the $`S_i`$ is then the envelope of the spheres in the convex hull, all scaled down by a factor $`1/\sqrt{2}`$, and we write this as $`F=\mathrm{env}\sqrt{}`$. Equivalently, it is the zero-set of the point-wise minimum over all functions $`2ff(z)`$, over all $`S`$, where $`f`$ is the weighted square distance function defined by $`S`$. At first glance, this might seem like an unwieldy surface, but we can completely describe it as a collection of quadratic patches obtained by decomposing the surface with what we call the mixed complex. Its cells are Minkowski sums of Voronoi vertices, edges, polygons and polyhedra with their dually corresponding Delaunay tetrahedra, triangles, edges and vertices, all scaled down by a factor $`1/2`$. Instead of formally describing this construction, we illustrate it with a two-dimensional example in Figure 2.

Depending on the dimension of the contributing Delaunay simplex, we have four types of mixed cells. Because of symmetry, we have only two types of surface patches, namely pieces of spheres and of hyperboloids of revolution, which we frequently put in Standard Form:

$`\xi _1^2+\xi _2^2+\xi _3^2`$ $`=`$ $`R^2,`$ (1)
$`\xi _1^2+\xi _2^2\xi _3^2`$ $`=`$ $`\pm R^2,`$ (2)
where the plus sign gives the one-sheeted hyperboloid and the minus sign gives the two-sheeted hyperboloid.

### Meshing.

The meshing algorithm triangulates the skin surface using edges and triangles whose sizes adapt to the local curvature. Let us be more specific. At any point $`xF`$, let $`\kappa (x)`$ be the maximum normal curvature at $`x`$. In contrast to other notions of curvature, $`\kappa `$ is continuous over the skin surface and thus amenable to controlling the local size of the mesh. Call $`\varrho (x)=1/\kappa (x)`$ the *local length scale* at $`x`$. The vertices of the mesh are points on the surface. For an edge $`uv`$, let $`R_{uv}=uv/2`$ be half its length, and for a triangle $`uvw`$, let $`R_{uvw}`$ be the radius of its circumcircle. The algorithm obeys the Lower and Upper Size Bounds that require edges not be too short and triangles not be too large:

$`R_{uv}/\varrho _{uv}>C/Q`$ for every edge $`uv`$, and

$`R_{uvw}/\varrho _{uvw}<CQ`$ for every triangle $`uvw`$,

where $`\varrho _{uv}`$ is the larger of $`\varrho (u)`$ and $`\varrho (v)`$, $`\varrho _{uvw}`$ is the minimum of $`\varrho (u)`$, $`\varrho (v)`$ and $`\varrho (w)`$, and $`C`$ and $`Q`$ are judiciously chosen positive constants.

The particular algorithm we consider in this paper is dynamic, in the sense that it maintains the mesh while the surface deforms. We can use this algorithm to construct a mesh by starting with the empty surface and growing it into the desired shape. This is precisely the scenario in which our results apply. To model the growth process, we use a time parameter and let $`S_i(t)=(z_i,\sqrt{r_i^2+t})`$ be the $`i`$-th sphere at time $`t`$. We start at $`t=\mathrm{}`$, at which time all radii are imaginary and the surface is empty, and we end at $`t=0`$, at which time the surface has the desired shape. This particular growth model is amenable to efficient computation because it does not affect the mixed complex, which stays the same at all times. Each patch of the surface sweeps out its mixed cell. At any moment, we have a collection of points sampled on the surface, and the mesh is the restricted Delaunay triangulation of these points, as defined in \[Che93, EdSh97\]. Given the surface and the points, this triangulation is unique. As the surface deforms, we move the points with it and update the mesh as required. From global and less frequent to local and more frequent these operations are:

1. topology changes that affect the local and global connectivity of the surface and the mesh,
2. edge contractions and vertex insertions that locally remove or add points to coarsen or refine the mesh, and
3. edge flips that locally adjust the mesh without affecting the point distribution or the surface topology.

For the particular growth model introduced above, the topology changes are easily predicted using the filtration of alpha complexes as described in \[EdMu94\]. To predict where and when we need to coarsen or refine the mesh is more difficult and depends on how the points move to follow the deforming surface. This is the topic of this paper and will be discussed in detail in the subsequent sections. Finally, edge flips are relatively robust operations, which can be performed in a lazy manner, without any sophisticated scheduling mechanism.

### Point motion.

To describe the motion of the points sampled on the skin surface, it is convenient to consider the trajectory of the surface over time. Note that the $`i`$-th sphere at time $`t`$ is $`S_i(t)=f_i^1(t)`$. Similarly, the convex combination defined by coefficients $`\gamma _i`$ at time $`t`$ is $`S(t)=f^1(t)`$, where $`f=\gamma _if_i`$. We can represent the skin surface in the same manner by introducing the function $`g:^3`$ defined as the point-wise minimum of the functions representing the shrunken spheres. More formally, $`g(x)=\mathrm{min}\{2f(x)f(z)\}`$, where the minimum is taken over all spheres $`S`$ and $`z`$ is the center of $`S`$. The skin surface at time $`t`$ is then $`F(t)=g^1(t)`$, so it is appropriate to call the graph of $`g`$ the *trajectory* of the skin surface. We see that growing the surface in time is equivalent to sweeping out its trajectory with a three-dimensional space that moves through time. It is natural to let the points sampled on $`F(t)`$ move normal to the surface. For a point $`x=[\xi _1,\xi _2,\xi _3]^T`$ on a sphere or hyperboloid in Standard Form $`\xi _1^2+\xi _2^2\pm \xi _3^2=\pm R^2`$, the gradient is $`g_x=2[\xi _1,\xi _2,\pm \xi _3]^T`$. The point $`x`$ moves in the direction of the gradient with a speed that is inversely proportional to the length. In other words, the velocity vector at a point $`x`$ is

$`\dot{x}={\displaystyle \frac{\mathrm{d}x}{\mathrm{d}t}}={\displaystyle \frac{g_x}{g_x^2}}={\displaystyle \frac{g_x}{4x^2}}.`$
The speed of $`x`$ is therefore $`\dot{x}=1/(2x)`$. The implementation of the relaxed scheduling paradigm crucially depends on the properties of this motion. We use the remainder of this section to describe a symmetry property of the velocity vectors that is instrumental in the analysis of the motion. Consider two mixed cells that share a common face. The Standard Forms of the two corresponding surface patches differ by a single sign, and so do the gradients. If we reflect points in one cell across the plane of the common face into the other cell then we preserve the velocity vector, as illustrated in Figure 3.

We use this observation about adjacent mixed cells to relate the velocity vectors of points in possibly non-adjacent cells. Consider points $`u`$ and $`v`$ and let $`x_1,x_2,\mathrm{},x_k`$ be the intersection points with faces of mixed cells encountered as we travel along the edge from $`u`$ to $`v`$. Starting at $`i=k`$, we work backward and reflect the portion of the edge beyond $`x_i`$ across the face that contains $`x_i`$. In the general case, this portion is a polygonal path that leads from $`x_i`$ to the possibly multiply reflected image $`\overline{v}`$ of $`v`$. After $`k`$ reflections we have a polygonal path from $`u`$ to the final $`\overline{v}`$. The length of the path is equal to the length of the initial edge, and hence $`u\overline{v}uv`$. We note that $`\overline{v}`$ does not necessarily lie in the mixed cell of $`u`$, but its velocity vector — which is the same as that of $`v`$ — is consistent with the family of spheres or hyperboloids that sweeps out that mixed cell. In other words, the motion of $`u`$ and $`\overline{v}`$ is determined by the same quadratic function.

## 3 Relaxed Scheduling

In this section, we introduce relaxed scheduling as a paradigm for maintaining moving or deforming data. It is designed to cope with situations in which the precise moment for an update is either not known or too expensive to compute.

### Correctness constraints.

In the context of maintaining the triangle mesh of a skin surface, we use relaxed scheduling to determine when to contract an edge and when to insert a new vertex. Since determining when the size of an edge or triangle stops to be acceptable is expensive, we introduce a gray zone between acceptability and unacceptability and update an element when we catch it inside that gray zone. That this course of action is even conceivable is based on the correctness proof of the dynamic skin triangulation algorithm for a range of its controlling parameters. The first three conditions defining that range refer to $`\epsilon `$, $`C`$ and $`Q`$. We have seen the latter two before in the formulation of the two Size Bounds \[L\] and \[U\]: $`C`$ controls how well the mesh approximates the surface, and $`Q`$ controls the quality of the mesh. Both are related to $`\epsilon `$, which quantifies the sampling density.

We require $`0<\epsilon \epsilon _0`$, where $`\epsilon _0=0.279\mathrm{}`$ is a root of $`2\mathrm{cos}(\mathrm{arcsin}\frac{2\epsilon }{1\epsilon }+\mathrm{arcsin}\epsilon )\frac{2\epsilon }{1\epsilon }=0`$.

$`Q^24CQ>2`$.

$`\frac{\delta ^2}{1+\delta ^2}\frac{\delta ^2}{4}>C^2Q^2`$, where $`\delta =\epsilon \frac{2C(\epsilon +1)}{Q+2C}`$.

It is computationally efficient to select the loosest possible bound for the sampling density: $`\epsilon =\epsilon _0`$. Then we get $`\delta =0.166\mathrm{}`$ and, as noted in \[CDES01\], we may choose $`C=0.08`$ and $`Q=1.65`$ to satisfy Conditions (I) to (III). Alternatively, we may lower $`C`$ to $`0.06`$ and are then free to pick $`Q`$ anywhere inside the interval from $`1.6`$ to $`2.3`$. The two choices of parameters are marked by a hollow dot and a white bar in Figure 5. The last two conditions refer to $`h`$, $`\mathrm{}`$ and $`m`$. All three parameters control how metamorphoses that add or remove a handle are implemented. Since the curvature blows up at the point and time of a topology change, we use a special and relatively coarse sampling inside spherical neighborhoods of such points. Assuming a unit radius of such neighborhoods, we turn the special sampling strategy on and off when the skin surface enters and leaves the smaller spherical neighborhood of radius $`h<1.0`$. If the skin enters as a two-sheeted hyperboloid we triangulate it using two $`\mathrm{}`$-sided pyramids inside the unit sphere neighborhood. If it enters as a one-sheeted hyperboloid we triangulate it as an $`m`$-sided drum with a waist.

The conditions are stated in terms of the edges $`ab`$, $`bc`$ and $`wx`$ and the triangles $`abc`$ and $`vwx`$, as defined in Figure 4. Their sizes can all be expressed in terms of $`h`$, $`\mathrm{}`$ and $`m`$, and we refer to \[CDES01, Section 10\] for the formulas.

$`R_{ab},R_{bc},R_{wx}>C/Q`$.

$`R_{abc},R_{vwx}<\mathrm{min}\{Q,2/Q\}Ch`$.

### Quality buffer.

The key technical insight about the dynamic skin triangulation algorithm is that we can find constants $`\epsilon `$, $`C`$, $`h`$, $`\mathrm{}`$, $`m`$ and $`Q_0<Q_1`$ such that Conditions (I) to (V) are satisfied for all $`Q[Q_0,Q_1]`$. This is illustrated in Figure 5, which shows the feasible region of points $`(C,Q)`$ assuming fixed values for $`\epsilon `$, $`h`$, $`\mathrm{}`$ and $`m`$.

Instead of fixing $`Q`$ and contracting an edge when its size-scale ratio reaches $`C/Q`$, we suggest to contract the edge any time its ratio is in the interval $`(C/Q_1,C/Q_0]`$. After the ratio enters this interval at $`C/Q_0`$ it can either leave again at $`C/Q_0`$ or it can get contracted, but it is not allowed to reach $`C/Q_1`$. Vertex insertions are treated symmetrically. Specifically, a triangle is removed by adding a vertex near its circumcenter, and this can happen at any moment its size-scale ratio is in $`[CQ_0,CQ_1)`$. The ratio can enter and leave the interval at $`CQ_0`$, but it is not allowed to reach $`CQ_1`$. We call $`(C/Q_1,C/Q_0]`$ and $`[CQ_0,CQ_1)`$ the *lower* and *upper size buffers*. The quality of the mesh is guaranteed because all edges and triangles satisfy the two Size Bounds \[L\] and \[U\] for $`Q=Q_1`$. Symmetrically, the correctness of the triangulation is guaranteed because edge contractions and vertex insertions are executed only if the same bounds are violated for $`Q=Q_0`$.

### Early warning.

Recall that an edge is borderline iff its size-scale ratio is contained in the lower size buffer, and it becomes unacceptable at the moment it reaches $`C/Q_1`$. Similarly, a triangle is borderline iff its size-scale ratio is contained in the upper size buffer, and it becomes unacceptable at the moment it reaches $`CQ_1`$. The relaxed scheduling paradigm depends on an early warning algorithm that reports an element before it becomes unacceptable. That algorithm might err and produce false positives, but it may not let any element slip by and become unacceptable. False positives cost time but do not cause any harm, while unacceptable elements compromise the correctness of the meshing algorithm. In Figure 6, false positives are marked by hollow dots and deletions are marked by filled black dots.

All false positive tests of edges are represented by dots above the lower size buffer. To get a correct early warning algorithm we just need to test each edge often enough so that its size-scale ratio cannot cross the entire lower size buffer between two contiguous tests. The symmetric rule applies to triangles. Bounds on the amount of time it takes to cross the size buffers will be given in Section 4.

Note that we have selected the parameters to obtain a fairly long interval $`[Q_0,Q_1]`$. It is not clear whether or not this is a good idea or whether a shorter interval would lead to a more efficient algorithm. An argument *for* a long interval is that the implied large size buffers let us get by with less frequent and therefore fewer tests. An argument *against* a long interval is that large size buffers are more likely to cause the deletion of elements that are on their way to better health but did not recover fast enough and get caught before they could leave the buffers. It might be useful to optimize the length of the intervals through experimentations after implementing the relaxed schedule as part of the skin triangulation algorithm.

## 4 Analysis

In this section, we derive lower bounds on the amount of time it takes for an edge or triangle to change its size by more than some threshold value. From these we will derive lower bounds on the time it takes an element to pass through the entire size buffer. We begin by studying the motion of a single point.

### Traveling point.

We recall that the speed of a point $`u`$ on the skin surface is $`\dot{u}=1/(2u)`$, assuming we write the patch that contains it in Standard Form. The distance traveled by $`u`$ in a small time interval is therefore maximized if it heads straight toward the origin, which for example happens if $`u`$ lies on a shrinking sphere. Starting the motion at point $`u_0`$, which is the point $`u`$ at time $`t_0`$, we get

$`u=\sqrt{u_0^2(tt_0)},`$ (3)
for the point $`u`$ at time $`t`$. This implies $`tt_0=u_0^2u^2`$, so we see that $`u`$ reaches the origin at time $`t=t_0+u_0^2`$. More generally, we reach the point $`u_1=(1\theta )u_0`$ between $`u_0`$ and the origin at time $`t_1=t_0+u_0^2u_1^2=t_0+(2\theta \theta ^2)u_0^2`$. Since the above analysis assumes the fastest way $`u`$ can possibly travel, this implies that within an interval of duration $`\mathrm{\Delta }t=t_1t_0`$, the point $`u_0`$ cannot travel further than a distance $`\theta \varrho (u_0)`$. We use $`\theta `$ as a convenient intermediate quantity that gives us indirect access to the important quantity, which is $`\mathrm{\Delta }t`$.

Recall from the Curvature Variation Lemma of \[CDES01\] that the difference in length scale between two points is at most the Euclidean distance. If that distance is $`u_0u_1\theta \varrho (u_0)`$ then the length scale at $`u_1`$ is between $`1\theta `$ and $`1+\theta `$ times the length scale at $`u_0`$. It follows that if we travel for a duration $`\mathrm{\Delta }t=(2\theta \theta ^2)\varrho ^2(u_0)`$, we can change the length scale only by a factor

$`1\theta {\displaystyle \frac{\varrho (u_1)}{\varrho (u_0)}}<1+\theta .`$ (4)
The lower bound is tight, and the upper bound cannot be reached because the distance $`\theta \varrho ^2(u_0)`$ from $`u_0`$ can only be achieved if the length scale shrinks. We will also be interested in the integral of $`1/(2u^2)`$, which is again maximized if $`u`$ moves straight toward the origin:

$`{\displaystyle _{t_0}^{t_1}}{\displaystyle \frac{\mathrm{d}t}{2u^2}}`$ $``$ $`{\displaystyle _{t_0}^{t_1}}{\displaystyle \frac{\mathrm{d}t}{2u_0^2(2t2t_0)}}`$
$`=`$ $`({\displaystyle \frac{1}{2}})\mathrm{ln}{\displaystyle \frac{u_0^2(t_1t_0)}{u_0^2}}`$
$`=`$ $`\mathrm{ln}{\displaystyle \frac{u_0}{u_1}}.`$
Denoting the above integral by $`X`$ and choosing $`t_1t_0=(2\theta \theta ^2)u_0^2`$, as before, we have

$`e^X{\displaystyle \frac{u_0}{u_1}}={\displaystyle \frac{\varrho (u_0)}{\varrho (u_1)}}{\displaystyle \frac{1}{1\theta }}.`$ (5)
### Edge length variation.

Consider two points $`u`$ and $`v`$ on the skin surface during a time interval $`[t_0,t_1]`$. We assume that both points follow their trajectories undisturbed by any mesh maintenance operations. Let $`u_0`$ and $`u_1`$ be the point $`u`$ at times $`t_0`$ and $`t_1`$ and, similarly, let $`v_0`$ and $`v_1`$ be the point $`v`$ at these two moments. We prove that if the time interval is short relative to the length scale of the points then the distance between them cannot shrink or grow by much.

Let $`\varrho _0=\mathrm{min}\{\varrho (u_0),\varrho (v_0)\}`$ and $`\mathrm{\Delta }t=t_1t_0=(2\theta \theta ^2)\varrho _0^2`$, for some $`0\theta 1`$. Then

$`1\theta {\displaystyle \frac{u_1v_1}{u_0v_0}}<{\displaystyle \frac{1}{1\theta }}.`$
###### Proof

The derivative of the distance between points $`u`$ and $`v`$ with respect to time is

$`{\displaystyle \frac{\mathrm{d}uv}{\mathrm{d}t}}`$ $`=`$ $`{\displaystyle \frac{\mathrm{d}uv}{\mathrm{d}u}}{\displaystyle \frac{\mathrm{d}u}{\mathrm{d}t}}+{\displaystyle \frac{\mathrm{d}uv}{\mathrm{d}v}}{\displaystyle \frac{\mathrm{d}v}{\mathrm{d}t}}`$
$`=`$ $`{\displaystyle \frac{(uv)^T}{uv}}(\dot{u}\dot{v}).`$ (6)
For example if $`u`$ and $`v`$ lie on a common sphere patch then $`\varrho =\varrho (u)=\varrho (v)`$, $`\dot{u}=\pm u/(2\varrho ^2)`$ and $`\dot{v}=\pm v/(2\varrho ^2)`$, which implies

$`{\displaystyle \frac{\mathrm{d}uv}{\mathrm{d}t}}=\pm {\displaystyle \frac{(uv)^T}{uv}}{\displaystyle \frac{(uv)}{2\varrho ^2}}=\pm {\displaystyle \frac{uv}{2\varrho ^2}}.`$
We prove below that in the general case, the distance derivative stays between these two extremes:

$`{\displaystyle \frac{uv}{2\varrho ^2}}{\displaystyle \frac{\mathrm{d}uv}{\mathrm{d}t}}{\displaystyle \frac{uv}{2\varrho ^2}},`$ (7)
where $`\varrho =\mathrm{min}\{\varrho (u),\varrho (v)\}`$. To get the final result from (6), we divide by $`uv`$, multiply by $`\mathrm{d}t`$, and use $`\mathrm{d}\mathrm{ln}x=\mathrm{d}x/x`$ to get

$`{\displaystyle \frac{\mathrm{d}t}{2\varrho ^2}}\mathrm{d}(\mathrm{ln}uv){\displaystyle \frac{\mathrm{d}t}{2\varrho ^2}}.`$
Next we integrate over $`[t_0,t_1]`$ and exponentiate to eliminate the natural logarithm:

$`e^X{\displaystyle \frac{u_1v_1}{u_0v_0}}e^X.`$
The claimed pair of inequalities follows from (5) and the observation that the upper bound for $`X`$ cannot be realized when the distance derivative is positive. To prove (7) for general points $`u`$ and $`v`$, it suffices to show that the length of $`\dot{u}\dot{v}`$ is at most $`uv/(2\varrho ^2)`$. We have seen that this is true if $`u`$ and $`v`$ belong to a common sphere patch. It is also true if $`u`$ and $`v`$ belong to a common hyperboloid patch because

$`\dot{u}\dot{v}={\displaystyle \frac{u^{}}{2\varrho ^2(u)}}{\displaystyle \frac{v^{}}{2\varrho ^2(v)}}{\displaystyle \frac{uv}{2\varrho ^2}},`$
where the primed and unprimed vectors are the same, except that they have a different sign in the third coordinate. We need a slightly more elaborate argument if $`u`$ and $`v`$ do not belong to the same mixed cell. We then reflect $`v`$ across the faces of mixed cells that intersect the edge $`uv`$. As described in Section 2, such a sequence of reflections does not affect the velocity vector. The distance between $`u`$ and the image $`\overline{v}`$ of $`v`$ under the composition of reflections is at most that between $`u`$ and $`v`$. Hence,

$`\dot{u}\dot{v}=\dot{u}\dot{\overline{v}}{\displaystyle \frac{uv}{2\varrho ^2}},`$
as required.

The lower bound in the Length Lemma is tight and realized by points $`u`$ and $`v`$ on a common sphere patch.

### Shrinking edge.

Consider an edge $`uv`$, whose half-length at time $`t_0`$ is $`R_0`$. As before, let $`u_0`$ and $`v_0`$ be the points $`u`$ and $`v`$ at time $`t_0`$. Let $`\varrho _0=\mathrm{min}\{\varrho (u_0),\varrho (v_0)\}`$. We follow the two points during the time interval $`[t_0,t_1]`$, whose duration is $`\mathrm{\Delta }t=t_1t_0=(2\theta \theta ^2)\varrho _0^2`$. The Length Lemma implies that at time $`t_1`$, the length of the edge satisfies

$`{\displaystyle \frac{u_1v_1}{u_0v_0}}={\displaystyle \frac{R_1}{R_0}}1\theta .`$ (8)
Our goal is to choose $`\theta `$ such that the edge at time $`t_1`$ is guaranteed to satisfy the Lower Size Bound for $`Q=Q_1`$. Using $`R_1(1\theta )R_0`$ from (8) and $`\varrho _1<(1+\theta )\varrho _0`$ from (4), we note that $`R_1/\varrho _1>C/Q_1`$ is implied by $`(1\theta )R_0/(1+\theta )C\varrho _0/Q_1`$. In other words,

$`\theta ={\displaystyle \frac{R_0Q_1C\varrho _0}{R_0Q_1+C\varrho _0}}`$ (9)
is sufficiently small. The corresponding time interval during which we can be sure that the edge $`uv`$ does not become unacceptably short has duration $`\mathrm{\Delta }t=(2\theta \theta ^2)\varrho _0^2`$. To get a better feeling for what these results mean, let us write the half-length of $`u_0v_0`$ as a multiple of the lower bound in \[L\] for $`Q=Q_0`$: $`R_0=AC\varrho _0/Q_0`$ with $`A>1.0`$. We then get $`\theta =(AQ_1Q_0)/(AQ_1+Q_0)`$ and $`\mathrm{\Delta }t`$ from $`\theta `$ as before. Table 1 shows the values of $`\theta `$ and $`\mathrm{\Delta }t`$ for a few values of $`A`$.

### Height variation.

Consider a triangle $`uvw`$ during a time interval $`[t_0,t_1]`$. We assume that all three points follow their trajectories undisturbed by any mesh maintenance operations. Each vertex has a distance to the line spanned by the other two vertices, and the *height* $`H`$ of $`uvw`$ is the smallest of the three distances. If $`uv`$ is the longest edge then $`H=ww^{}`$, where $`w^{}`$ is the orthogonal projection of $`w`$ onto $`uv`$. We prove if the time interval is short relative to the length scale at the points then the height cannot shrink or grow by much. To state the claim we use indices 0 and 1 for points and heights at times $`t_0`$ and $`t_1`$.

Let $`\varrho _0=\mathrm{min}\{\varrho (u_0),\varrho (v_0),\varrho (w_0)\}`$ and $`\mathrm{\Delta }t=t_1t_0=(2\theta \theta ^2)\varrho _0^2`$, for some $`0\theta 1`$. Then

$`1\theta {\displaystyle \frac{H_1}{H_0}}<{\displaystyle \frac{1}{1\theta }}.`$


format: text

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# Magnetic phase diagram of cubic perovskites SrMn1-xFexO3

## I INTRODUCTION

Perovskite manganites, AMnO3, have been studied in great detail during the past several years because of very interesting magnetic and electronic properties resulting from competing charge, exchange, and phonon interactions.Tokura00  Insulating A-, C-, CE-, and G- type antiferromagnetic (AFM), metallic ferromagnetic, and charge or orbital ordering properties can be tuned over a wide range through the choice of size and charge of the A-site cations which control the degree of structural distortions and the formal valence of Mn. Recently, increased interest has focused on the colossal magnetoresistive effect and the destruction of the charge ordering induced by substitutions on the Mn-site.Hebert02

From the point of view of competing interactions, the stoichiometric SrMn1-xFexO3 system is interesting because it should contain Mn+4 ($`t_{2g}^3`$) and Fe+4 ($`t_{2g}^3e_g^1`$) ions. The G-type AFM ($`T_N=233`$ K) and insulating SrMnO3 can be obtained in a cubic perovskite form through a two-step synthesis procedure,Negas70  although many previous studies focused on the hexagonal phase that is stable in air at $`T<1440^{}`$C. We have recently shown that the G-type AFM phase is preserved for single-valent Mn4+ in Sr1-xCaxMnO3 in the cubic, tetragonal and orthorhombic crystal structures.Chmaissem01  $`T_N`$ is suppressed by the bending of the Mn-O-Mn bond angle from 180 and by the variance of the average size of the A-site ion via changes in the Sr/Ca ratio. The other end member of the series, SrFeO3, is also a cubic perovskite with a helical AFM structure ($`T_N=134`$ K).Takeda72  The low resistivity ($`10^3\mathrm{\Omega }`$ cm) and metallic character when fully oxygenated MacChesney65 ; Yamada02  was considered the reason for the absence of the Jahn-Teller distortion and orbital ordering of Fe4+. Deviations from oxygen stoichiometry in SrFeO3-δ lead to a formation of several different oxygen-vacancy-ordered perovskite structures for $`\delta =1/8,1/4,`$ and $`1/2`$.Hodges00  The substitution of Co for Fe yields a SrFe1-xCoxO3 compound, which is ferromagnetic for $`x0.2`$ with a large negative magnetoresistance for $`0x0.7`$.Abbate02  Several oxygen-deficient SrMn1-xFexO3-δ compositions have recently been studied.Fawcett00  The orthorhombically distorted perovskite CaFeO3 compound was shown to undergo the charge separation to Fe5+ ($`t_{2g}^3`$) and Fe3+ ($`t_{2g}^3e_g^2`$).Takano77  The highly energetically stable high-spin configuration was invoked as a reason for this behavior. This charge disproportionation phenomenon can also be observed in Ca1-xSrxFeO3,Takano83  La1-xSrxFeO3,Dann94  and SrMn1-xFexO3-δ.Fawcett00

In this study, we investigate polycrystalline SrMn1-xFexO3. We have constructed the magnetic phase diagram for fully oxygenated samples. We observe an antiferromagnetic order for Fe content $`x0.5`$ and $`x0.9`$. For intermediate Fe content $`0.3x0.8`$ we observe a spin-glass behavior with features characteristic of “ideal” 3D Ising spin glasses. Increasing the Fe content leads to significant covalency effects, such as a decrease of resistivity and covalent shortening of the lattice parameter. We also observe Fe3+/Fe5+ charge disproportionation in stoichiometric SrMn1-xFexO3.

## II EXPERIMENTAL DETAILS

The samples were prepared using a two-step synthesis method developed for similar kinetically stable perovskites.Hinks88  First, oxygen-deficient samples were prepared in argon at $`T=13001400^{}`$C for $`x0.5`$ and in air at $`1300^{}`$C for $`x>0.5`$. The samples were then annealed in air or O2 at lower temperatures to achieve stoichiometric compositions with respect to the oxygen content. High pressure O2 in the range of 140 - 600 bar was applied for $`x0.1`$. High-pressure annealing is essential to produce fully oxygenated samples. The oxygen content in the $`x=0.5`$ sample was controlled within the range 2.86 - 3.00 by annealing the sample under partial pressure of oxygen between $`10^4`$ and 600 bar on a thermobalance or in a high-pressure furnace. The samples annealed in the furnace were carefully weighed before and after annealing and the oxygen content was determined from the mass difference. The ac susceptibility, dc magnetization and resistivity were measured using a Physical Property Measurement System Model 6000 (Quantum Design). X-ray diffraction patterns were collected using a Rigaku diffractometer. Powder neutron diffraction was performed at the Intense Pulsed Neutron Source at Argonne National Laboratory. Both X-ray and neutron diffraction data were refined using a GSAS software. Typical diffraction patterns are presented in Fig. 1. Mössbauer

measurements were performed in transmission geometry using a 50 mCi 57mCo in Rh source kept at room temperature and a krypton proportional detector. The samples measured at 5 K and 293 K were placed in an exchange gas cryostat cooled with liquid helium. Silicon diode sensors allowed the control and stabilization of temperature to within $`\pm 0.1`$ K.

## III STRUCTURAL DATA

All synthesized samples were single-phase with primitive cubic Pm-3m crystal structure. The structure can be simply described as a three-dimensional stacking of corner-sharing (Mn,Fe)O6 regular octahedra formed by six equivalent randomly distributed Mn-O or Fe-O bonds. Fig. 2 shows the $`a`$-axis lattice parameter for SrMn1-xFexO3. We also

present previously determined values of $`a`$ for SrFeO3 Hodges00  and SrMn1-xFexO3-δ from Ref. Fawcett00 . The $`a`$-axis lattice parameter systematically increases with increasing content of the larger Fe ion substituted for Mn. The slope of the $`a`$ vs. $`x`$ dependence is smaller for larger $`x`$, which indicates the increasing role of the covalency of the Fe-O bond. By studying the structural data for samples with the oxygen content $`3\delta `$ (determined from the thermogravimetric analysis), we also found that the lattice parameter, $`a`$, linearly increases with decreasing oxygen content. For example, for $`x=0.5`$, the rate of this increase is 0.064(2) Å per oxygen atom in the formula unit. Hence, we conclude that the difference of the lattice parameter between our results and those of Ref. 10 is a result of different oxygen contents.

## IV MAGNETIC PROPERTIES

The ac susceptibility for SrMn1-xFexO3 samples is presented in Fig. 3. For $`x0.5`$ and $`x0.9`$, we observe temperature dependencies that are characteristic

of antiferromagnetic materials. For $`0.3x0.8`$ we also observed a cusp, which is a signature of spin-glass behavior. From these results we have determined Néel temperatures (defined as the temperatures for which $`\chi (T)`$ has a maximum slope) and the spin-glass freezing temperatures, $`T_f`$ (defined as the temperatures where the susceptibility cusp reaches its maximum). We also observed additional magnetic properties that substantiate the presence of the spin-glass state in our samples. These properties will be discussed in detail throughout this Section. Inverse susceptibility as a function of temperature is linear above $`T_N`$ for $`x<0.5`$ and its intersection with the horizontal axis is negative, which points to antiferromagnetic interactions. $`\chi ^1(T)`$ for higher Fe contents $`x=0.51`$ is curved and its slope can be extrapolated either to a negative intersection when we analyze the temperature range just above $`T_N`$, or to a positive intersection when we take into account higher temperatures. This behavior has been observed in SrFeO3 Takeda72  and is a result of the presence of both ferromagnetic and antiferromagnetic interactions in these materials.

The values of Néel temperature and spin-glass freezing temperature are collected in the phase diagram in Fig. 4. Four distinct regions in the phase diagram are observed. For $`x0.2`$, only an antiferromagnetic phase is observed with $`T_N`$ decreasing as $`x`$ increases.

A decrease of $`T_N`$ has been explained for isoelectronic Ca- and Ba- lightly substituted in the cubic perovskite SrMnO3 Chmaissem01  to be a result of the $`A`$-site size variance $`\sigma ^2=\mathrm{\Sigma }y_ir_i^2(\mathrm{\Sigma }y_ir_i)^2`$, where $`r_i`$ is the ionic size and $`y_i`$ is the fractional occupancy of the $`A`$ site.RM96  This parameter describes the local variations of the Mn-O-Mn bond angle in the cubic region that exist even when the average Mn-O-Mn bond angle is equal to 180 degrees. In the present case, the increase of the Fe content $`x`$ increases the $`B`$-site size variance. This effect changes the local variation of the Mn-O-Mn bond angle even when the average structure is cubic and hence leads to lower $`T_N`$. Additionally, different magnetic $`B`$-site ions (Fe3+ or Fe5+: see Sec. VI) randomly substituted for Mn4+ change the net exchange integral and introduce disorder, which also lowers $`T_N`$.

For $`x=0.30.5`$, we observed both antiferromagnetic order and spin-glass behavior. Fawcett et al.’s results Fawcett00  are shown in Fig. 4 for comparison. Fawcett et al. also observed both antiferromagnetism and spin glass in the $`x=1/3`$ and $`x=1/2`$ samples. We have seen that for a given Fe content, when the oxygen content is increasing, $`T_N`$ decreases and $`T_f`$ increases. Therefore, the $`x=1/2`$ oxygen deficient sample shows higher $`T_N`$ and lower $`T_f`$.

In the next region of the phase diagram, where $`0.6x0.8`$, only the spin-glass behavior can be observed. The spin-glass freezing temperature is almost constant in this region. This characteristic temperature is also nearly independent of the oxygen content. The magnitude of the ac susceptibility (see Fig. 3) is the largest for the $`x=0.7`$ sample, which indicates the largest effective magnetic moment for this composition. The last region is close to $`x=1`$, where only antiferromagnetic order can be observed.

The “zero-field-cooled” ($`M_{ZFC}`$) and “field-cooled” ($`M_{FC}`$) magnetizations, presented in Fig. 5 for $`x=0.5`$ and $`x=0.8`$, were measured in the magnetic field of 1 kOe. $`M_{ZFC}`$

was measured on warming after cooling in a zero magnetic field and switching the magnetic field on at $`T=5`$ K. $`M_{FC}`$ was subsequently measured on cooling in the magnetic field. We can observe a difference between $`M_{ZFC}`$ and $`M_{FC}`$ below a certain temperature. This difference is typical for spin glass systems. Thermoremanent magnetization ($`M_{trm}`$), which can be observed after field cooling to a temperature below $`T_f`$ and switching off the magnetic field, is also a manifestation of the spin-glass behavior. The $`x=0.8`$ sample shows this difference between $`M_{ZFC}`$ and $`M_{FC}`$ below a certain “irreversibility temperature” ($`T_{irr}`$).deAlmeida78  $`T_{irr}36`$ K and is lower than $`T_f`$. $`M_{trm}`$ decreases to zero at $`T_{irr}`$ with increasing temperature. This sample shows a transition from the spin glass state to the paramagnetic state. The $`x=0.5`$ sample, which undergoes a transition from spin glass to the antiferromagnetic state, shows a significant difference between $`M_{ZFC}`$ and $`M_{FC}`$ above $`T_f`$. In addition, the thermoremanent magnetization can also be observed in the antiferromagnetic state above $`T_f`$ up to $`T_N`$. This observation indicates substantial disorder in the antiferromagnetic state for the $`x=0.5`$ sample. This phase is analogous to the “random antiferromagnetic state” observed in Mn1-xFexTiO3.Ito88  Thermoremanent magnetization exhibits a slow decay in time, which is shown in the inset to Fig. 6 (b).

We have fitted the formula Ogielski85

$$M_{trm}=M_0t^\beta $$
(1)
to our experimental data and determined the parameters $`M_0`$ (the extrapolated to zero time magnetization) and the exponent $`\beta `$, which describe the dynamics of spin glasses. Eq. (1) satisfactorily describes the time dependence of the thermoremanent magnetization in nearly the entire time window we span, except for short times $`t<500`$ s where we can see some negative deviations from this time dependence. This formula, derived by Ogielski in Monte-Carlo simulations, was used to describe the time decay of three-dimensional Ising spin glasses,Ogielski85  and also applied to Mn0.5Fe0.5TiO3 Ito86  considered to be an “ideal” three-dimensional short-range Ising spin glass.Mydosh93  The temperature dependence of $`M_0`$ and $`\beta `$ for $`x=0.5`$ and $`x=0.8`$ samples is presented in Fig. 6. $`M_0`$ systematically decreases with $`T`$ for both samples. It approaches zero at the irreversibility line for the $`x=0.8`$ sample. For the $`x=0.5`$ sample, $`M_0`$ remains substantially nonzero above $`T_f`$ in the “random antiferromagnetic state”. The parameter $`\beta `$, which is a measure of the relaxation rate, for $`x=0.8`$ increases with $`T`$ up to $`T_{irr}=36`$ K and rapidly drops above this temperature. The increase of $`\beta (T)`$ is not exponential as expected for an “ideal” spin glass.Ito86  The $`\beta (T)`$ dependence is different for the $`x=0.5`$ sample, which shows a maximum at $`T0.5T_f`$ and a subsequent decrease. This behavior may be a result of the presence of antiferromagnetic order in the spin-glass state, which inhibits the decay rate of the thermoremanent magnetization.

In Fig. 7, we present the ac susceptibility for SrMn0.2Fe0.8O3 and SrMn0.5Fe0.5O3

samples measured at several frequencies in an ac magnetic field of constant amplitude $`H_{ac}=14`$ Oe. One can observe a decrease of the ac susceptibility below $`T_f`$ with increasing frequency, and a shift of $`T_f`$ towards higher temperatures. This confirms that the observed cusp in the ac susceptibility is related to spin-glass behavior.Mydosh93  For the $`x=0.8`$ sample, the ac susceptibility is independent of frequency above $`T_f`$ (in the paramagnetic state). For the $`x=0.5`$ sample, a significant frequency dependence of $`\chi `$ can still be observed, which again points to a frustration of the antiferromagnetic state above the spin-glass freezing temperature. The inset to Fig. 7 (a) shows the dependence of $`T_f`$ on log frequency. The linear fit to $`T_f(\mathrm{log}\omega )`$ gives relative temperature shift vs. frequency $`\mathrm{\Delta }T_f/[T_f\mathrm{\Delta }(\mathrm{log}\omega )]=0.0147\pm 0.008`$ and $`0.0167\pm 0.017`$ for $`x=0.8`$ and $`x=0.5`$, respectively. These values are similar to those observed for canonical spin glasses such as $`Pd`$Mn and $`Ni`$Mn.Mydosh93

## V RESISTIVITY

The temperature dependence of resistivity for SrMn1-xFexO3 samples is presented in Fig. 8. The resistivity is relatively low ($`1`$ $`\mathrm{\Omega }`$ cm at room temperature) for

SrMnO3 and increases by over four orders of magnitude on substitution of 10% Fe for Mn. It reaches a maximum for $`x=0.1`$ and decreases with further Fe substitution. $`\rho (T)`$ shows mostly semiconducting dependence. We were able to fully oxygenate SrFeO3 only in the powder form under high pressure. This powder was used for magnetic, structural, and Mössbauer measurements, but could not be used for resistivity measurements. Polycrystalline pellets were synthesized, but were slightly oxygen-deficient. Therefore, these pellets of SrFeO3-δ show a small increase of resistivity on decreasing temperature as seen in Fig. 8. Assuming thermally activated resistivity, $`\rho =\rho _0exp(E_a/k_BT)`$, we estimated the activation energy for SrMn1-xFexO3. The inset to Fig. 8(b) shows the calculated derivative $`E_a/k_B=d\mathrm{ln}(\rho )/d(1/T)`$ for $`x=0.10.3`$. We have found that calculated in this way $`E_a/k_B`$ is temperature dependent (not constant with respect to temperature as expected for the simple thermal activation conduction model). The negative kinks, which are marked with arrows, denote $`T_N`$. We also checked other models of conduction by introducing a temperature dependent pre-factor to the formula $`\rho T^sexp((T_0/T)^p)`$.Shafarman89  The best description of our data can be obtained with $`s=`$ 8 - 9 for this formula. The physical meaning of this value is not yet clear because this value is much higher than that proposed in the framework of the existing models (e.g. $`s=1/2`$ in Mott’s variable range hopping model Mott69  or $`s=1`$ in the small polaron model Worledge98 ).

## VI MÖSSBAUER SPECTROSCOPY

Stoichiometric SrMn1-xFexO3 samples were examined by applying Mössbauer spectroscopy on the 57Fe isotope that is 2% abundant in the material. Through a careful analysis of the magnetic hyperfine field and the isomer shift, Mössbauer spectroscopy provides a way of ascertaining whether iron is in different chemical or crystallographical environments, as well as its valence state. High spin Fe3+, Fe4+, and Fe6+ have room temperature isomer shifts in the range 0.1 to 0.6, -0.2 to 0.2, and -0.8 to -0.9 mm/s, respectively (relative to $`\alpha `$Fe).Greenwood71  There are fewer studies of the isomer shift for Fe5+; therefore it is less well understood. The magnetic hyperfine field is dominated by the Fermi contact interaction which gives rise to about 550 kOe for high-spin Fe3+ having a mean spin of 5/2 for the $`3d`$ electrons. Thus, a general rule is that $``$ 110 kOe corresponds to $``$ 1 Bohr magneton (one unpaired electron). These rules can substantially change due to covalency effects. Increasing the covalency between iron and oxygen tends to produce lower isomer shifts, and to reduce the effective number of unpaired electrons which leads to lower magnetic hyperfine fields. In a metallic material polarized conduction electrons also affect the magnitude of the hyperfine field.

The parent compound, SrFeO3, is known to be a metallic conductor that orders into a helical antiferromagnetic structure at low temperatures due to the competition between ferromagnetic nearest neighbors and antiferromagnetic next nearest neighbors.Takeda72  As seen in Fig. 9, SrFeO3 exhibits a set of sharp magnetically split lines (0.24 mm/s linewidth) at 5 K. In the paramagnetic state at 293 K, the spectrum consists only of a slightly broadened single line (0.27 mm/s linewidth). Thus, Fe exists in only one valence state from 5 K to room temperature. Charge balance suggests that SrFeO3 forms with iron in the +4 valence state. This is confirmed by the measured isomer shift of 0.059 mm/s at 293 K (0.154 mm/s at 5 K). The low magnetic field of 327 kOe would also indicate that this material has a magnetic moment of $`3\mu _B`$ rather than the expected $`4\mu _B`$, but the low magnetic field may be due to the nearly delocalized character of the electron in the $`e_g`$ orbital of Fe4+ with comcomitant lowering of the net field by the polarized conduction electrons. The quadrupole splitting for this material is nearly zero ($`0.019`$ mm/sec) at 293 K, agreeing with the values reported in the literature.Gallagher64  This result indicates the absence of any extensive static Jahn-Teller distorted FeO6 octahedra even though high-spin Fe4+ is a likely candidate for a Jahn-Teller ion due to the single electron in the $`e_g`$ orbital.Takano77  However, a dynamic Jahn-Teller effect is not ruled out. Due to the lifetime of the excited nuclear state, the 57Fe nucleus is sensitive to fluctuating environments that fluctuate on a time scale longer than 10-11 seconds. A fast dynamic Jahn-Teller effect where the electronic hopping is enhanced by the delocalized character of the $`e_g`$ electron could result in electric quadrupole fluctuation times that are too short for the Fe nuclei to detect. Thus, the electric quadrupole interaction effectively averages to near zero. Thus, the high pressure synthesis technique appears to be successful in producing highly stoichiometric compounds of metallic SrFeO3 and is a sound technique to produce stoichiometric samples of SrMn1-xFexO3.

Measurements were made on SrMn1-xFexO3 at various temperatures to characterize the charge disproportionation properties of iron in the spin-glass, antiferromagnetic, and paramagnetic phases. Charge disproportionation has been observed in the highly nonstoichiometric form of SrMn1-xFexO3-δ as well as in CaFeO3.Fawcett00 ; Takeda78  Charge balance would dictate that the valence state of Fe should be +4 (since Fe and Mn share the same crystallographic sites for the first material and Mn exists in only the +4 valence state Fawcett00 ). What is usually observed is a 2-site iron Mössbauer spectrum indicating that Fe exists in 2 valence states rather than in a single, pure valence state of +4. The existence of two different Fe valence states provides evidence for a charge disproportionation as follows: 2 Fe$`{}_{}{}^{4+}`$ Fe(4-δ)+ \+ Fe(4+δ)+, where $`\delta `$ varies from 0 to 1 depending on the covalency between iron and oxygen.

We have observed the presence of charge disproportionation in highly stoichiometric forms of SrMn1-xFexO3. Thus, oxygen vacancies are not a factor in the charge disproportionation properties.Fawcett00  As Mn was added to SrFeO3, the spectra revealed the presence of two distinct Fe sites having different magnetic hyperfine fields and isomer shifts. The spectra for one of the samples, SrMn0.5Fe0.5O3, are shown in Fig. 9 and data for it is given in Table I. In this Table, $`\epsilon `$ is the effective

quadrupole splitting, which is defined as $`\epsilon =eQV_{zz}(3\mathrm{cos}^2\theta 1)/4`$ in a magnetically ordered state and $`\epsilon =eQV_{zz}/2`$ in a paramagnetic state where $`eQ`$ is the nuclear quadrupole moment, $`V_{zz}`$ is the z-component of the electric field gradient tensor, and $`\theta `$ is the angle between the $`V_{zz}`$ axis and $`H_{eff}`$. From this data the Fe ions appear to exist, in nearly equal proportions, in two valence states in the paramagnetic, antiferromagnetic, and spin-glass phases (by examining the area under each Mössbauer subspectra). Mn is known to exist in a valence state close to +4 through x-ray absorption spectroscopy chemical shift measurements on nonstoichiometric compounds.Fawcett00  Since Mn does not charge disproportionate, then, because the Fe sites occur in nearly equal proportions, the Fe site having the largest magnetic field (480 kOe at 5 K) was assigned a +3 valence state, and a +5 valence state was assigned to the other Fe site. The Fe site assigned a +3 valence state also has an isomer shift (0.35 mm/sec at 293 K) that lies near that expected for Fe3+ (between 0.1 and 0.6 mm/s for a high-spin state). This is exactly what one would expect for fully oxygenated SrMn0.5Fe0.5O3 – that the average valence state of Fe would be +4.

The actual environment around each Fe atom is rather complicated. Fe3+, Fe5+, and Mn4+ can all occupy the same site in this cubic perovskite. Thus, since each ion has a different ionic size, there must be a disordered array of Fe3+, Fe5+, and Mn4+ oxygen octahedra of differing sizes and distortions throughout the lattice. It is worth noting that for fully oxygenated samples the quadrupole splitting at room temperature is smaller than for nonstoichiometric ones.Fawcett00  This reflects a less distorted local environment, without oxygen vacancies, for the stoichiometric compositions. The distribution of different ions over the crystallographic lattice gives rise to the slight broadening of the Mössbauer lines in the paramagnetic region. In addition, there are competing ferromagnetic and antiferromagnetic interactions in both the spin-glass region and the antiferromagnetic region (since the parent compound, SrFeO3, has a helical antiferromagnetic structure). The much broader Mössbauer lines observed in the magnetically ordered regions for both the antiferromagnetic and spin-glass phases (the outer linewidths were all greater than 1 mm/sec over the whole temperature region in Fig. 10) are likely due to competing magnetic interactions between the transition metal

cations, Fe+3, Fe+5, and Mn+4. Since the materials under study have a random distribution of Fe+3, Fe+5, and Mn+4 ions throughout the lattice, different sizes and magnetic moments of these ions lead to a variation in the structural and magnetic environments around the Fe sites, resulting in the distribution of hyperfine parameters observed in the Mossbauer spectra. Thus, as a function of temperature and as a function of composition, from $`0.1x0.9`$, there is a pronounced broadening of the Mössbauer linewidths in both the antiferromagnetic and spin-glass phases. Fitting the spectra with a distribution of magnetic hyperfine fields, quadrupole splittings, and isomer shifts did not reveal any clearly distinguishable characteristics between the antiferromagnetic and spin-glass phases – there was a significant amount of frustration in both phases arising from the competing magnetic interactions that also occur in both phases. However, since the spectra revealed two easily distinguishable sites, the fits to the spectra were made using a simple Lorentzian model which gives average hyperfine field values. The variation of the average magnetic hyperfine field with temperature for SrMn0.5Fe0.5O3 is given in Fig. 10. Due to the complicated nature of the magnetic interactions, the magnetization curves do not follow the typical $`S=5/2`$ or $`S=3/2`$ Brillouin curves. The equal proportion of Fe3+ to Fe5+ is nearly maintained over all temperatures. However, near the spin-glass/antiferromagnetic transition temperature, there is a deviation from this behavior indicating the presence of more complex behavior. Three-site models have been applied to other materials where Fe charge disproportionates into +3 and +5 valence states, such as in La1-xSrxFeO3.Dann94  However, applying such a model does not eliminate the anomaly near the spin-glass transition temperature. Further investigations are under way to understand the existence of this valence state anomaly near the spin-glass/antiferromagnetic phase boundary.

## VII SUMMARY

In summary, we have studied the cubic perovskite SrMn1-xFexO3 ($`0x1`$) system. By ac susceptibility studies of fully oxygenated samples, we have constructed the magnetic phase diagram. We have found antiferromagnetic ordering for the lightly and heavily substituted material, while intermediate substitution leads to spin-glass behavior. Close to the SrMn0.5Fe0.5O3 composition these two types of ordering coexist and affect one another. By Mössbauer investigations, we have observed the presence of charge disproportionation of iron to nearly equal proportion of Fe3+ to Fe5+ in stoichiometric SrMn0.5Fe0.5O3 and the single-valence state of Fe4+ in SrFeO3. The increase of Fe content, $`x`$, is accompanied by stronger covalency of the Fe-O bond, which leads to the shortening of this bond, a decrease of resistivity, lower isomer shifts and magnetic hyperfine fields.

## ACKNOWLEDGMENTS

This work was supported by the DARPA/ONR and the State of Illinois under HECA.


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# The differential sum rule for the relaxation rate in dirty superconductors

## Abstract

We consider the differential sum rule for the effective scattering rate $`1/\tau (\omega )`$ and optical conductivity $`\sigma _1(\omega )`$ in a dirty BCS superconductor, for arbitrary ratio of the superconducting gap $`\mathrm{\Delta }`$ and the normal state constant damping rate $`1/\tau `$. We show that if $`\tau `$ is independent of $`T`$, the area under $`1/\tau (\omega )`$ does not change between the normal and the superconducting states, i.e., there exists an exact differential sum rule for the scattering rate. For any value of the dimensionless parameter $`\mathrm{\Delta }\tau `$, the sum rule is exhausted at frequencies controlled by $`\mathrm{\Delta }`$. We show that in the dirty limit the convergence of the differential sum rule for the scattering rate is much faster then the convergence of the $`f`$sum rule, but slower then the convergence of the differential sum rule for conductivity.

Optical constants of solids follow a variety of sum rules. pi\_noz  The origins of the sum rules can be traced back to fundamental conservation laws and are intimately connected to the causality of the electromagnetic response leading to Kramers-Kronig relationships between the real and imaginary parts of the optical constants. The analysis of the sum rules is a powerful tool to study the distribution of the spectral weight in correlated electron systems.

The dynamics of conducting carriers is usually described in terms of the effective scattering rate $`1/\tau (\omega )`$ and the effective mass $`m^{}(\omega )`$ tom

$$\tau ^1(\omega )=\frac{\omega _{pl}^2}{4\pi }\mathrm{}[\frac{1}{\sigma (\omega )}],\frac{m^{}}{m_b}=\frac{\omega _{pl}^2}{4\pi }\frac{1}{\omega }\mathrm{}[\frac{1}{\sigma (\omega )}]$$
(1)
where $`\sigma (\omega )=\sigma _1(\omega )+i\sigma _2(\omega )`$ is the complex optical conductivity, $`\omega _{pl}^2=4\pi ne^2/m_b`$ is the plasma frequency, and $`m_b`$ is the band mass tom . Under special circumstances (e.g., when the Eliashberg theory is valid), the spectra of $`1/\tau (\omega )`$ and $`m^{}`$ can be linked to the real and imaginary parts of the electronic self energy.

The conductivity, that characterizes the absorbing power of a solid, obeys the $`f`$sum rule $`_0^{\mathrm{}}𝑑\omega \sigma _1(\omega )=\omega _{pl}^2/8`$. This sum rule reflects the conservation of the number of particles and physically implies that at a given particle density, the total absorbing power does not depend on the details of the interactions, and is determined only by the total number of particles in the system pi\_noz . It is particularly relevant for a superconductor where the conductivity acquires a $`\delta `$-functional piece proportional to the superfluid density $`n_s`$, and the sum rule transforms into $`_{+0}^{\mathrm{}}𝑑\omega \sigma _1(\omega )=\omega _{pl}^2/8(1n_s/n)`$. As $`n_s/n`$ can be measured independently, the sum rule is a valuable tool to study the transformation of the spectral weight associated with the superconductivity.

The issue raised in series of recent works basov ; marsiglio ; ac\_sum ; homes  is whether there exists any similar sum rule for the relaxation rate. At the first glance, the answer is negative as the integral over $`1/\tau (\omega )`$ diverges and hence has no physical meaning. This can be readily illustrated with a simple Drude model where $`\sigma (\omega )=(\omega _{pl}^2/4\pi )/(1/\tau i\omega )`$, i.e., $`\tau (\omega )=\tau `$, and $`_0^{\mathrm{}}𝑑\omega \tau ^1(\omega )`$ is infinite. This implies that there is no sum rule for $`1/\tau (\omega )`$ that could be traced to a conservation law. However, one still can argue that the frequency integral of the scattering rate has some physical meaning. Basov et al. basov  argued, in connection with the cuprates, that for experimentally relevant frequencies $`1/\tau (\omega )`$ is numerically close to an effective scattering rate $`1/\tau _{sr}`$ (defined below) that is related to the dielectric function and obeys a physically motivated sum rule. In this situation, one can argue that there should exist an approximate sum rule if the frequency integral over $`1/\tau (\omega )`$ is taken in finite limits. This approach was thoroughly analyzed by Marsiglio et al. marsiglio .

In this paper, we analyze whether there exists an exact sum rule for the full frequency integral of the difference between $`1/\tau (\omega )`$ at two different temperatures in the normal state, and, what is actualy more relevant, between $`1/tau(\omega )`$ in the normal and superconducting states. For a Drude metal, the frequency integral over the difference of $`1/\tau (\omega )`$ at different $`T`$ in the normal state is either infinite or vanishes depending on whether or not $`1/\tau `$ depends on $`T`$. We argue that zero and infinity are the only two options for the differential integral in any model, and that if $`\tau (\omega )`$ is $`T`$ independent, the differential sum rule for the relaxation rate is exact between the normal state and a BCS superconductor.

We also analyze what controls the rate of convergence of the sum rules for conductivity and $`1/\tau `$. This issue is elevant for experimental applications as when sum rules are applied to the analysis of the experimental data, one always encounters a problem that actual data is available over limited frequency intervals. It is therefore imperative to know rapidly sum rules converge to estimate the accuracy of the experiment-based sum rule analysis.

The analysis in the clean limit $`\mathrm{\Delta }\tau 1`$, where $`\mathrm{\Delta }`$ is the superconducting gap, and $`\tau `$ is independent on $`T`$ was performed earlier ac\_sum , as a byproduct of the modeling for the cuprates. In this limit, $`\mathrm{\Delta }`$ is the largest energy scale in the problem, and the differential sum rule between the normal state and a BCS superconductor is exact and is exhausted at frequencies of order $`\mathrm{\Delta }`$. Here we consider arbitrary $`\mathrm{\Delta }\tau `$. We show that even in the dirty limit $`\mathrm{\Delta }\tau 1`$, the differential sum rule is exact and is furthermore still exhausted at frequencies of order $`\mathrm{\Delta }`$. This result is not intuitively obvious as the conductivity sum rule in the dirty limit is exhausted only at $`\omega 1/\tau \mathrm{\Delta }`$. We also found that the functional form of $`1/\tau _{sc}(\omega )`$ only weakly depends on $`\mathrm{\Delta }\tau `$ at $`\omega >2\mathrm{\Delta }`$. Here and below we use subscripts “$`sc`$” and “$`n`$” for superconducting and normal states, respectively

The fact that the differential sum rule for $`1/\tau `$ is exausted at $`\omega \mathrm{\Delta }`$ in the dirty limit may be relevant for the interpretation of the data from some high $`T_c`$ materials. The frequency below which fermionic excitations become incoherent may arise from the energy scale $`\omega 1/\tau `$ . The convergence of the differential sum rule at $`O(\mathrm{\Delta })`$ and the near independence of $`\tau _{sc}(\omega )`$ on $`\mathrm{\Delta }\tau `$ implies that as long as the system possesses a sharp superconducting gap the differential sum rule for $`1/\tau `$ is not affected by the increased fermionic incoherence. Indeed in high $`T_c`$ superconductors, $`1/\tau `$ is temperature dependent. The issue of whether or not the differential sum rule is exact between the normal and superconducting states could then only be experimentally addressed if measurements could be done in both states at the same T. This is obviously impossible. What can be clearly observed, at least in YBCO, is the re-distribution of the spectral weight between the normal and superconducting states. If this redistribution is over scales of $`O(\mathrm{\Delta })`$ then the frequency integral can be restricted to a few times $`\mathrm{\Delta }`$. The approximate sum rule can then be analyzed in the hope that the T dependence of the relaxation rate is a minor effect compared to the huge change in $`1\tau (\omega )`$ which takes place between the normal and superconducting states Note in this regard that since $`1/\tau `$ is expressed via both $`\mathrm{}\sigma (\omega )`$ and $`\mathrm{}\sigma (\omega )`$, the analysis of the differential sum rule for $`1/\tau `$, even though it is only approximate, still yields information about the spectral weight distribution in a superconductor, which is complimentary to the information from the $`f`$sum rule that involves only $`\mathrm{}\sigma (\omega )`$

The issue whether or not $`1/\tau `$ differential sum rule is satisfied in dirty BCS superconductors was a subject of recent controversy. Basov et al. basov  argued that in both clean and dirty limits, $`1/\tau _{sc}(\omega )`$ vanish below $`2\mathrm{\Delta }`$, but overshoots the normal state $`1/\tau `$ at larger frequencies. In that paper, the profile of $`1/\tau _{sc}(\omega )`$ was visually related to that of the fermionic density of states, for which the sum rule is exact and reflects the conservation of the number of particles. Homes et al. homes  correctly observed that the relaxation rate and conductivity are expressed via a current-current correlator, and therefore scale with the joint density of states of two fermions about which, they conjectured, no rigorous statements can be made. They computed the frequency integral of $`1/\tau _{sc}(\omega )1/\tau _n(\omega )`$ numerically for a BCS superconductor $`\tau _n(\omega )=\tau `$ with $`\tau \mathrm{\Delta }=1/2`$ and found that even at $`\omega `$ as high as $`15\mathrm{\Delta }`$, it is still about $`25\%`$ of its maximum value at $`\omega =2\mathrm{\Delta }`$. They concluded, based on this numerics, that the value of sum rule integral depends on the choice for cutoff frequency, and that if the integral is truncated at $`\omega =O(\mathrm{\Delta })`$, a finite value is expected. Below we demonstrate explicitly that the differential sum rule is in fact exhausted at the energy scale controlled by $`\mathrm{\Delta }`$, however, a rather slow convergence found in homes  is real and is due to a weak $`(\mathrm{log}\omega )/\omega ^2`$ decay of $`1/\tau _{sc}(\omega )`$ at large frequencies.

We begin with the general argument that zero and infinity are the only two options for $`_0^{\mathrm{}}𝑑\omega /\tau (\omega )`$. This conjecture can be verified by applying the Kubo formula that relates $`\sigma (\omega )`$ with the full retarded current-current correlator $`\mathrm{\Pi }(\omega )`$: $`\sigma (\omega )=(\omega _{pl}^2/4\pi )\mathrm{\Pi }(\omega )/(i\omega +\delta )`$. Substituting this relation into $`1/\tau (\omega )`$ we find that $`1/\tau (\omega )=\mathrm{}S(\omega )/\omega `$ where $`S(\omega )=\omega ^2/\mathrm{\Pi }(\omega )`$. Both $`\mathrm{}\mathrm{\Pi }(\omega )`$ and $`S(\omega )`$ are odd functions of frequency. Since $`\mathrm{\Pi }(\omega )`$ is analytic in the upper half-plane of complex $`\omega `$ and does not have zeros (that can be checked explicitly, see below), $`S(\omega )`$ is also an analytic function in the upper half-plane. The analyticity implies that, by Kramers-Kronig relations,

$$_0^{\mathrm{}}\frac{1}{\tau (\omega )}=_0^{\mathrm{}}\frac{S(\omega )}{\omega }𝑑\omega =\frac{\pi }{2}\mathrm{}S(0)+C$$
(2)
where $`C=0`$ if the integral converges, and $`C=\mathrm{}`$ if it is not. It is easy to show that $`\mathrm{}S(0)`$ vanishes both in the normal and in the superconducting state. In the normal state, $`\mathrm{}\mathrm{\Pi }(\omega )\omega ^2,\mathrm{}\mathrm{\Pi }(\omega )\omega `$ at the lowest frequencies, hence $`S(\omega )\omega ^2`$ and $`S(0)=0`$. In the superconducting state $`\mathrm{}\mathrm{\Pi }(0)`$ is finite, while $`\mathrm{}\mathrm{\Pi }(0)=0`$, hence $`S(\omega )`$ again scales as $`\omega ^2`$, and again $`S(0)=0`$. Hence $`𝑑\omega /\tau (\omega )=C`$, i.e., it is either zero or infinite. For non-differential sum rule, $`C=\mathrm{}`$ as at large frequencies, $`\mathrm{\Pi }(\omega )`$ tends to 1, hence $`S(\omega )\omega ^2`$, and the integral in (2) diverges. This confirms that there is no physically motivated sum rule for $`1/\tau (\omega )`$.

There are two ways to improve the situation. First, one can introduce an effective $`S_{eff}(\omega )`$ that converges at high frequencies and is close to $`S(\omega )`$ at experimentally relevant frequencies. Then one can hope to obtain an experimentally meaningful approximate sum rule. For the scattering rate, the natural choice, suggested by Basov et al. basov  is to introduce an effective scattering rate

$$\frac{1}{\tau _{eff}}=\frac{\omega _{pl}^2}{\omega }\mathrm{}\left[1\frac{1}{ϵ(\omega )}\right]$$
(3)
where $`ϵ(\omega )=1+4\pi i\sigma (\omega )/\omega `$ is the dielectric function. For this scattering rate, $`S_{eff}(\omega )=1\omega /(\omega +4\pi i\sigma (\omega ))`$ is an analytic function, and at high frequencies it vanishes as $`S_{eff}(\omega )=O(1/\omega ^2)`$. The Kramers-Kronig relations are then applicable, and

$$_0^{\mathrm{}}\frac{d\omega }{\tau _{eff}(\omega )}=\frac{\pi \omega _{pl}^2}{2}\mathrm{}[1\frac{1}{ϵ(\omega )}]_{\omega =0}=\frac{\pi }{2}\omega _{pl}^2$$
(4)
For a Drude metal,

$$\frac{1}{\tau _{eff}(\omega )}=\frac{1}{\tau }\frac{\omega _{pl}^4}{(\omega ^2\omega _{pl}^2)^2+\omega ^2/\tau ^2}$$
(5)
At frequencies $`\omega \omega _{pl}`$, the correction term in the denominator can be neglected, and $`1/\tau _{eff}(\omega )1/\tau `$. As the plasma frequency can well be larger than the fermionic bandwidth, the actual integration of experimentally measured $`1/\tau (\omega )`$ may not extend to $`\omega \omega _{pl}`$, i.e., in the measured range $`1/\tau _{eff}(\omega )`$ and $`1/\tau (\omega )`$ are nearly the same. Still, however, this does not imply that there is an “approximate” sum rule for $`1/\tau `$ as $`𝑑\omega /\tau (\omega )`$ and $`𝑑\omega /\tau _{eff}(\omega )`$ both diverge when the integration is restricted to $`\omega \omega _{pl}`$. Only when the frequency integration extends to $`\omega >\omega _{pl}`$, $`_0^\omega 𝑑x/\tau _{eff}(x)`$ converges to the sum rule value. In other words, typical frequencies for $`_0^{\mathrm{}}1/\tau _{eff}(\omega )`$ are of order $`\omega _{pl}`$, and at these frequencies $`1/\tau `$ and $`1/\tau _{eff}`$ are very different.

As we pointed out above, in this paper we use another approach and analyze the difference between $`1/\tau (\omega )`$ in the normal and superconducting states. The leading divergent term in $`S(\omega )\omega ^2`$ at high frequencies is the same for both states. It therefore cancels out in $`S_{sc}(\omega )S_n(\omega )`$. If the subleading terms scale as negative powers of frequency at large $`\omega `$, $`S_{sc}(\omega )S_n(\omega )`$ converges and then the sum rule becomes exact. We emphasize that contrary to $`S_{eff}(\omega )`$, the difference of $`S_{sc}(\omega )S_n(\omega )`$, if converges, begins falling off at frequencies that are still much smaller than the fermionic bandwidth and $`\omega _{pl}`$. In other words, the differential sum rule for the scattering rate is exact in a continuous model.

We now check whether the differential sum rule for $`1/\tau `$ is satisfied in a BCS superconductor (we argue that it is exact) and also examine the energy scale at which this sum rule is exhausted. In order to explore the issue of convergence we will analyze the differential frequency sums for both $`1/\tau (\omega )`$ and $`\sigma _1(\omega )`$ defined as

$`I_\tau (\omega )`$ $`=`$ $`{\displaystyle _0^\omega }𝑑\mathrm{\Omega }(\tau _{sc}^1(\mathrm{\Omega })\tau _n^1)`$ (6)
$`I_\sigma (\omega )`$ $`=`$ $`{\displaystyle _0^\omega }𝑑\mathrm{\Omega }(\sigma _{1,sc}(\mathrm{\Omega })\sigma _{1,n}(\mathrm{\Omega }))`$ (7)
where $`\tau _n=\tau `$ and, as we pointed out above, the notations “sc” and “n” refer to superconducting and normal states, respectively.

The expression for the current-current polarization operator in a dirty BCS superconductor has the form

$`\mathrm{\Pi }_{sc}(\omega )={\displaystyle _0^{\mathrm{}}}𝑑\mathrm{\Omega }{\displaystyle \frac{1}{\left(\sqrt{\mathrm{\Omega }_+^2\mathrm{\Delta }^2}+\sqrt{\mathrm{\Omega }_{}^2\mathrm{\Delta }^2}+i/\tau \right)}}`$
$`\times {\displaystyle \frac{\sqrt{\mathrm{\Omega }_+^2\mathrm{\Delta }^2}\sqrt{\mathrm{\Omega }_{}^2\mathrm{\Delta }^2}\mathrm{\Delta }^2\mathrm{\Omega }_+\mathrm{\Omega }_{}}{\sqrt{\mathrm{\Omega }_+^2\mathrm{\Delta }^2}\sqrt{\mathrm{\Omega }_{}^2\mathrm{\Delta }^2}}}`$ (8)
where $`\mathrm{\Omega }_\pm =\mathrm{\Omega }\pm \omega /2`$. In the normal state, this reduces to a conventional Drude form $`\mathrm{\Pi }_n(\omega )=\omega /(\omega +i/\tau )`$. In the superconducting state, one can show quite generally that $`\mathrm{}\mathrm{\Pi }(\omega )`$ vanishes below $`2\mathrm{\Delta }`$. At high frequencies, $`\mathrm{\Pi }(\omega )`$ gradually approaches $`\mathrm{\Pi }(\mathrm{})=1`$.

We first verify whether $`S_{sc}(\omega )S_n(\omega )`$ vanishes at $`\omega =\mathrm{}`$. As typical internal frequencies in Eq. (8) are of the same order as external $`\omega `$, at $`\omega \mathrm{\Delta }`$, one can expand the integrand in (8) in $`\mathrm{\Delta }/\omega `$. The expansion can be straightforwardly carried out for arbitrary $`\mathrm{\Delta }\tau `$, and the result is that at high frequencies

$`\mathrm{}\mathrm{\Pi }_{sc}(\omega )`$ $`=`$ $`\mathrm{}\mathrm{\Pi }_n(\omega )\left(1{\displaystyle \frac{1}{1+(\omega \tau )^2}}{\displaystyle \frac{2\mathrm{\Delta }^2\mathrm{log}\frac{\omega }{\mathrm{\Delta }}}{\omega ^2}}\right)`$
$`\mathrm{}\mathrm{\Pi }_{sc}(\omega )`$ $`=`$ $`\mathrm{}\mathrm{\Pi }_n(\omega )\left(1+{\displaystyle \frac{(\omega \tau )^21}{(\omega \tau )^2+1}}{\displaystyle \frac{2\mathrm{\Delta }^2\mathrm{log}\frac{\omega }{\mathrm{\Delta }}}{\omega ^2}}\right)`$ (9)
where $`\mathrm{}\mathrm{\Pi }_n(\omega )=(\omega \tau )^2/(1+(\omega \tau )^2),\mathrm{}\mathrm{\Pi }_n(\omega )=\omega \tau /(1+(\omega \tau )^2)`$. Substituting these results into $`S(\omega )=\omega ^2/\mathrm{\Pi }(\omega )`$ we find that for large $`\omega 1/\tau `$

$$\mathrm{}[S_{sc}(\omega )S_n(\omega )]\omega ^2\mathrm{}[S_{sc}(\omega )S_n(\omega )]\omega ^1.$$
(10)
We see that both real and imaginary parts of $`S_{sc}(\omega )S_n(\omega )`$ vanish at infinite frequency. This implies that Kramers-Kronig transformation is applicable, and hence the differential sum rule is exact for a dirty BCS superconductor.

We now address the issue of the energy scale over which the sum rule is exhausted. We consider clean and dirty limits separately. In the clean limit, the frequency integral in (8) was evaluated in Ref. ac\_sum . To first order in $`1/\mathrm{\Delta }\tau `$ we have for $`\omega >2\mathrm{\Delta }`$

$$\mathrm{}\mathrm{\Pi }_{sc}(\omega )1,\mathrm{}\mathrm{\Pi }_{sc}(\omega )\frac{1}{\tau \omega }E\left(\sqrt{1\frac{4\mathrm{\Delta }^2}{\omega ^2}}\right),$$
(11)
where $`E(x)=_0^{\pi /2}𝑑\varphi \sqrt{1x^2\mathrm{sin}^2\varphi }`$ is the complete Elliptic integral of the second kind (note that definitions of $`E`$ differ in different handbooks). In the two limits $`E(0)=\pi /2`$ and $`E(1)=1`$. The result for $`\mathrm{}\mathrm{\Pi }_{sc}(\omega )1`$ is valid outside a tiny $`O(1/\mathrm{\Delta }\tau )`$ range near $`2\mathrm{\Delta }`$ where $`\mathrm{}\mathrm{\Pi }_{sc}(\omega )`$ diverges logarithmically. Substituting $`\mathrm{\Pi }_{sc}(\omega )`$ from (11) into $`1/\tau _{sc}(\omega )`$ we obtain for $`\omega >2\mathrm{\Delta }`$

$$\frac{1}{\tau _{sc}(\omega )}=\frac{1}{\tau }E\left(\sqrt{1\frac{4\mathrm{\Delta }^2}{\omega ^2}}\right),\sigma _1(\omega )=\frac{\omega _{pl}^2}{4\pi }\frac{1}{\omega ^2}\frac{1}{\tau _{sc}(\omega )}$$
(12)
and $`1/\tau (\omega )=\sigma (\omega )=0`$ for $`\omega <2\mathrm{\Delta }`$. We plot these functions in Fig. 1. For the differential sum rule we then obtain ($`\omega >2\mathrm{\Delta }`$)

$`I_\tau (\omega )={\displaystyle \frac{2\mathrm{\Delta }}{\tau }}{\displaystyle _0^{\frac{\omega }{2\mathrm{\Delta }}}}𝑑x\left[1+\mathrm{}E\left(\sqrt{1{\displaystyle \frac{1}{x^2}}}\right)\right]`$ (13)
$`I_\sigma (\omega )={\displaystyle \frac{\omega _{pl}^2}{4\pi }}{\displaystyle \frac{1}{2\mathrm{\Delta }\tau }}\left[{\displaystyle \frac{2\mathrm{\Delta }}{\omega }}{\displaystyle \frac{\pi ^2}{8}}+{\displaystyle _{\frac{2\mathrm{\Delta }}{\omega }}^1}𝑑xE\left(\sqrt{1x^2}\right)\right]`$ (14)
We explicitly verified that $`I_\tau (\mathrm{})=0`$, i.e., the differential sum rule is indeed satisfied.

We also see from (13) that at finite $`\omega `$, $`I_\tau (\omega )`$ depends only on $`\omega /\mathrm{\Delta }`$. This implies that in the clean limit, the differential sum rule is exhausted at frequencies $`O(\mathrm{\Delta })`$. An important issue, however, is how rapidly $`I(\omega )`$ converges to zero at $`\omega \mathrm{\Delta }`$. In Fig. 1b we plot $`I_\tau (\omega )`$ and $`I_\sigma (\omega )`$ evaluated numerically from (13) and normalized to their values at the maximum at $`\omega =2\mathrm{\Delta }`$. We see that $`I_\tau (\omega )`$ converges much more slowly that $`I_\sigma (\omega )`$. In particular, at $`\omega =15\mathrm{\Delta }`$, $`|I_\tau (\omega )|`$ is still about 25% of its maximum value in accord with Ref. homes . On the contrary $`I_s(\omega )`$ is vanishingly small at $`\omega =15\mathrm{\Delta }`$.

value. This result fully agrees with Ref. homes . For the same $`\omega `$, $`I_\sigma (\omega )`$ practically vanishes.

A weaker convergence of $`I_\tau (\omega )`$ can be understood analytically. Indeed, at high frequencies, the elliptic function can be expanded in $`1/\omega ^2`$. This yields $`1/\tau _{sc}(\omega )=(1/\tau )(1+2(\mathrm{\Delta }/\omega )^2\mathrm{log}(2\omega /\mathrm{\Delta }))`$. Integrating this expression over frequency, we obtain that at $`\omega \mathrm{\Delta }`$

$$I_\tau (\omega )=\frac{2\mathrm{\Delta }}{\tau }\frac{\mathrm{\Delta }}{\omega }\left[1/2+\mathrm{log}(2\omega /\mathrm{\Delta })\right]$$
(15)
The conductivity integral meanwhile converges to zero as

$$I_\sigma (\omega )=\frac{\omega _{pl}^2}{4\pi }\frac{1}{12\mathrm{\Delta }\tau }\left(\frac{2\mathrm{\Delta }}{\omega }\right)^3\left[1/6+\mathrm{ln}(2\omega /\mathrm{\Delta })\right]$$
(16)
Comparing (15) and (16), we see that $`I_\sigma (\omega )`$ has an extra $`(2\mathrm{\Delta }/\omega )^2`$ that accounts for much faster convergence of $`I_\sigma (\omega )`$ than of $`I_\tau (\omega )`$.

We next proceed to the dirty limit $`\mathrm{\Delta }\tau 1`$. As we said in the introduction, the key issue here is whether the sum rule is still exhausted at frequencies $`O(\mathrm{\Delta })`$, or one needs to extend the integration to frequencies of order $`1/\tau `$, where the $`f`$sum rule for the conductivity is exhausted. At the first glance, in the dirty limit, the frequency integration has to be extended to larger frequencies than in the clean limit, as one can easily show that at $`\mathrm{\Delta }\tau 1`$, the jump of $`1/\tau _{sc}(\omega )`$ at $`2\mathrm{\Delta }`$ is small, of order $`\mathrm{\Delta }\tau `$, and therefore $`1/\tau _{sc}(\omega )`$ in a superconductor does not overshoot the normal state $`1/\tau `$ immediately above $`2\mathrm{\Delta }`$. However, as we now demonstrate, typical frequencies for the differential sum rule still scale with $`\mathrm{\Delta }`$.

The first indication that the physics is still confined to frequencies $`O(\mathrm{\Delta })`$ comes from the analysis of the form of $`1/\tau _{sc}(\omega )`$ at $`\omega \tau ^1\mathrm{\Delta }`$. Using Eqs. (9) for $`\mathrm{\Pi }(\omega )`$ and substituting them into $`1/\tau _{sc}(\omega )`$, we obtain

$$\frac{1}{\tau _{sc}(\omega )}=\frac{1}{\tau }\left(1+\frac{2\mathrm{\Delta }^2}{\omega ^2}\mathrm{log}\frac{2\omega }{\mathrm{\Delta }}\frac{1+(\omega \tau )^4}{(1+\omega \tau )^4}\right)$$
(17)
We see that at frequencies comparable to $`1/\tau `$, $`1/\tau _{sc}(\omega )`$ exceeds $`1/\tau `$, i.e., the overshoot occurs at a lower frequency. Further, integrating $`1/\tau _{sc}(\omega )`$ from $`O(1/\tau )`$ to infinity we find that the contribution to $`I_\tau (\omega )`$ from these frequencies is of order $`\mathrm{\Delta }^2|\mathrm{log}(\mathrm{\Delta }\tau )|`$. Meanwhile, the loss of $`I_\tau `$ in the superconducting state between $`0`$ and $`2\mathrm{\Delta }`$ is $`2\mathrm{\Delta }/\tau `$ that in the dirty limit is much larger that $`\mathrm{\Delta }^2|\mathrm{log}(\mathrm{\Delta }\tau )|`$. This implies that even in the dirty limit, the dominant contribution to the sum rule comes from frequencies well below $`1/\tau `$. At these frequencies, the current-current polarization operator can be evaluated exactly to leading order in $`\mathrm{\Delta }\tau `$ as one can pull $`1/\tau `$ out of denominator of the integral in the r.h.s. of (8). The remaining integral is evaluated easily, and on substituting the result into $`1/\tau _{sc}(\omega )`$ we obtain for $`\omega >2\mathrm{\Delta }`$

$`{\displaystyle \frac{1}{\tau _{sc}(\omega )}}`$ $`=`$ $`{\displaystyle \frac{1}{\tau }}{\displaystyle \frac{\omega }{\sqrt{\omega ^24\mathrm{\Delta }^2}}}\mathrm{}\left[E^1\left({\displaystyle \frac{\omega }{\sqrt{\omega ^24\mathrm{\Delta }^2}}}\right)\right]`$
$`\sigma _1(\omega )`$ $`=`$ $`{\displaystyle \frac{\omega _{pl}^2}{4\pi }}\tau \sqrt{1{\displaystyle \frac{\omega ^2}{4\mathrm{\Delta }^2}}}\mathrm{}\left[E\left({\displaystyle \frac{\omega }{\sqrt{\omega ^24\mathrm{\Delta }^2}}}\right)\right]`$ (18)
and $`1/\tau _{sc}(\omega )=\sigma _1(\omega )=0`$ for $`\omega <2\mathrm{\Delta }`$. We plot these functions in Fig.2. The behavior of $`1/\tau _{sc}(\omega )`$ near $`2\mathrm{\Delta }`$ and at high frequencies can be well understood analytically. Near $`2\mathrm{\Delta }`$, expanding $`E(x)`$ for large value of the argument, we immediately obtain that $`1/\tau _{sc}(\omega )`$ evolves continuously (up to corrections $`O(\mathrm{\Delta }\tau )`$), and very near $`2\mathrm{\Delta }`$ behaves as $`1/\tau _{sc}(\omega )=(1/\tau )[\omega ^24\mathrm{\Delta }^2]/\omega ^2`$. Still, it overshoots $`1/\tau `$ at $`\omega 2.68\mathrm{\Delta }`$ and develops a maximum at $`\omega =3.48\mathrm{\Delta }`$. At larger frequencies, $`1/\tau _{sc}(\omega )`$ approaches $`1/\tau `$ as $`1/\tau _{sc}(\omega )=(1/\tau )(1+2(\mathrm{\Delta }/\omega )^2\mathrm{log}(2\omega /\mathrm{\Delta }))`$, i.e., exactly the same way as in the clean limit. Analyzing the frequency integrals in $`I_\tau (\omega )`$ and $`I_\sigma (\omega )`$ we immediately make sure that they converge at $`\omega `$ comparable to $`2\mathrm{\Delta }`$.

In Fig. 2b we compare the rates of convergence of $`I_\tau (\omega )`$ and $`I_\sigma (\omega )`$ in the dirty limit. We see that, as in the clean limit, $`I_\sigma (\omega )`$ converges better. This time, it is related to the presence of the extra logarithmical term in the high frequency expansion of $`I_\tau (\omega )`$. We also see that the rate of convergence is almost the same in both clean and dirty limits. We recall that this result is not obvious as in the dirty limit, $`1/\tau _{sc}(\omega )`$ and $`\sigma _1(\omega )`$ gradually increases above at $`2\mathrm{\Delta }`$, while in the clean limit, they both jump at $`2\mathrm{\Delta }`$ and immediately overshoot the normal state values of $`1/\tau `$ and $`\sigma _1`$, respectively.

To conclude, in this paper we analyzed the differential sum rule for the scattering rate and optical conductivity in a dirty BCS superconductor. We demonstrated that this sum rule is exact if the normal state $`\tau `$ is independent on temperature. For arbitrary $`\mathrm{\Delta }\tau `$, the sum rule is exhausted at frequencies controlled by $`\mathrm{\Delta }`$, but the convergence is rather weak due to logarithmical terms. We showed that in the dirty limit the convergence of the differential sum rule for the scattering rate is much faster then the convergence of the $`f`$sum rule for the conductivity, but slower than for the differential sum rule for conductivity. The latter has the fastest convergence in both clean and dirty limits.

###### Acknowledgements.

We acknowledge useful discussions with G. Blumberg, C. Homes, D. van der Marel, F. Marsiglio, M. Strongin, and J. Tu. The research was supported by NSF DMR (A. Ch.) , NSF and DOE (D.N.B) and by DR Project 200153 at Los Alamos National Laboratory (Ar. A.).