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# Acyclic resolutions for arbitrary groups

## 1 Introduction

Spaces denoted by $`X`$ are assumed to be separable metrizable. A compactum is a metrizable compact space.

Let $`G`$ be an abelian group. A space $`X`$ has the cohomological dimension $`dim_GXn`$ if $`\stackrel{ˇ}{H}^{n+1}(X,A;G)=0`$ for every closed subset $`A`$ of $`X`$. The case $`G=`$ is an important special case of cohomological dimension. It was known long ago that $`dimX=dim_{}X`$ if $`X`$ is finite dimensional. Solving an outstanding problem in cohomological dimension theory Dranishnikov constructed in 1987 an infinite dimensional compactum of $`dim_{}=3`$. A few years earlier a deep relation between $`dim_{}`$ and $`dim`$ was established by the Edwards cell-like resolution theorem  saying that a compactum of $`dim_{}n`$ can be obtained as the image of a cell-like map defined on a compactum of $`dimn`$. A compactum $`X`$ is cell-like if any map $`f:XK`$ from $`X`$ to a CW-complex $`K`$ is null homotopic. A map is cell-like if its fibers are cell-like. The reduced $`\stackrel{ˇ}{\mathrm{C}}`$ech cohomology groups of a cell-like compactum are trivial with respect to any group $`G`$.

Acyclic resolutions originated in the Edwards cell-like resolution. A compactum $`X`$ is $`G`$-acyclic if $`\stackrel{~}{\stackrel{ˇ}{H}}{}_{}{}^{}(X;G)=0`$ and a map is $`G`$-acyclic if its fibers are $`G`$-acyclic. Thus a cell-like map is $`G`$-acyclic with respect to any abelian group $`G`$. By the Vietoris-Begle theorem a $`G`$-acyclic map cannot raise the cohomological dimension $`dim_G`$. Dranishnikov proved the following important

###### Theorem 1.1

() Let $`X`$ be a compactum with $`dim_{}Xn`$, $`n2`$. Then there are a compactum $`Z`$ with $`dim_{}Zn`$ and $`dimZn+1`$ and a $``$-acyclic map $`r:ZX`$ from $`Z`$ onto $`X`$.

It has been widely conjectured that Theorem 1.1 holds for any abelian group $`G`$. A substantial progress in solving this conjecture was made by Koyama and Yokoi  who proved it for a large class of groups including $``$ and very recently by Rubin and Schapiro  who settled the case $`G=_p^{\mathrm{}}`$.

The purpose of this note is to finally answer this conjecture affirmatively by proving

###### Theorem 1.2

Let $`G`$ be an abelian group and let $`X`$ be a compactum with $`dim_GXn`$, $`n2`$. Then there are a compactum $`Z`$ with $`dim_GZn`$ and $`dimZn+1`$ and a $`G`$-acyclic map $`r:ZX`$ from $`Z`$ onto $`X`$.

In general the dimension $`n+1`$ of $`Z`$ in Theorem 1.2 is best possible . However, it is unknown if the dimension of $`Z`$ in Theorem 1.1 can be reduced to $`n`$. In this connection let us also mention the following interesting result of Dranishnikov.

###### Theorem 1.3

() Let $`X`$ be a compactum with $`dim__pXn`$. Then there are a compactum $`Z`$ with $`dimZn`$ and a $`_p`$-acyclic map $`r:ZX`$ from $`Z`$ onto $`X`$.

Our proof of Theorem 1.2 essentially uses Dranishnikov’s idea of constructing a $``$-acyclic resolution presented in  and involves some methods of . The proof is self-contained and does not rely on previous results concerning acyclic resolutions. The paper  is an excellent source of basic information on cohomological dimension theory.

## 2 Preliminaries

All groups below are abelian and functions between groups are homomorphisms. $`𝒫`$ stands for the set of primes. For a non-empty subset $`𝒜`$ of $`𝒫`$ let $`S(𝒜)=\{p_1^{n_1}p_2^{n_2}\mathrm{}p_k^{n_k}:p_i𝒜,n_i0\}`$ be the set of positive integers with prime factors from $`𝒜`$ and for the empty set define $`S(\mathrm{})=\{1\}`$. Let $`G`$ be a group and $`gG`$. We say that $`g`$ is $`𝒜`$-torsion if there is $`nS(𝒜)`$ such that $`ng=0`$ and $`g`$ is $`𝒜`$-divisible if for every $`nS(𝒜)`$ there is $`hG`$ such that $`nh=g`$. $`\mathrm{Tor}_𝒜G`$ is the subgroup of the $`𝒜`$-torsion elements of $`G`$. $`G`$ is $`𝒜`$-torsion if $`G=\mathrm{Tor}_𝒜G`$, $`G`$ is $`𝒜`$-torsion free if $`\mathrm{Tor}_𝒜G=0`$ and $`G`$ is $`𝒜`$-divisible if every element of $`G`$ is $`𝒜`$-divisible.

###### Proposition 2.1

(i) If $`G`$ is $`𝒜`$-torsion then $`G`$ is $`(𝒫𝒜)`$-divisible and $`(𝒫𝒜)`$-torsion free.

(ii) A factor group of an $`𝒜`$-divisible group is $`𝒜`$-divisible and a factor group of an $`𝒜`$-torsion group is $`𝒜`$-torsion.

(iii) The direct sum of $`𝒜`$-divisible groups is $`𝒜`$-divisible and the direct sum of $`𝒜`$-torsion groups is $`𝒜`$-torsion.

Let $`f:GH`$ be a homomorphism of groups $`G`$ and $`H`$ and let $`H`$ be $``$-torsion. Then $`G/\mathrm{Tor}_{}G`$ is

(iv) $`𝒜`$-divisible if $`\mathrm{ker}f`$ is $`𝒜`$-divisible and $`𝒜`$;

(v) $`𝒜`$-torsion if $`\mathrm{ker}f`$ is $`𝒜`$-torsion and $`𝒜=\mathrm{}`$;

(vi) $`𝒜`$-torsion and $`𝒜`$-divisible if $`\mathrm{ker}f`$ is $`𝒜`$-torsion and $`𝒜`$-divisible and $`𝒜=\mathrm{}`$.

Proof. The proof of (i), (ii), (iii) is obvious.

Let $`\varphi :GG/\mathrm{Tor}_{}G`$ be the projection and $`\varphi (x)=y`$. Then there is $`nS()`$ such that $`nf(x)=f(nx)=0`$ and hence $`nx\mathrm{ker}f`$.

(iv) Let $`mS(𝒜)`$. Since $`𝒜`$, $`nmS(𝒜)`$. Then there is $`z\mathrm{ker}f`$ such that $`nmz=nx`$. Hence $`n(mzx)=0`$ and therefore $`\varphi (mzx)=0`$. Thus $`m\varphi (z)=\varphi (x)=y`$ and $`G/\mathrm{Tor}_{}G`$ is $`𝒜`$-divisible.

(v) By (i) $`\mathrm{ker}f`$ is $`(𝒫𝒜)`$-divisible and therefore there is $`z\mathrm{ker}f`$ such that $`nz=nx`$. Then $`n(zx)=0`$ and there is $`mS(𝒜)`$ such that $`mz=0`$. Hence $`\varphi (z)=\varphi (x)=y`$ and $`my=\varphi (mz)=0`$ and (v) follows.

(vi) By (v) $`G/\mathrm{Tor}_{}G`$ is $`𝒜`$-torsion. By (i) $`\mathrm{ker}f`$ is $`(𝒫𝒜)`$-divisible and since $`\mathrm{ker}f`$ is $`𝒜`$-divisible, $`\mathrm{ker}f`$ is $`𝒫`$-divisible. Then by (iv) $`G/\mathrm{Tor}_{}G`$ is $`𝒜`$-divisible. $`\mathrm{}`$

The notation $`\mathrm{e}\mathrm{dim}XY`$ is used to indicate the property that every map $`f:AY`$ of a closed subset $`A`$ of $`X`$ into $`Y`$ extends over $`X`$. It is known that $`dim_GXn`$ if and only if $`\mathrm{e}\mathrm{dim}XK(G,n)`$ where $`K(G,n)`$ is the Eilenberg-Mac Lane complex of type $`(G,n)`$. A map between CW-complexes is combinatorial if the preimage of every subcomplex of the range is a subcomplex of the domain.

Let $`M`$ be a simplicial complex and let $`M^{[n]}`$ be the $`n`$-skeleton of $`M`$ (=the union of all simplexes of $`M`$ of $`dimn`$). By a resolution $`EW(M,n)`$ of $`M`$ we mean a CW-complex $`EW(M,n)`$ and a combinatorial map $`\omega :EW(M,n)M`$ such that $`\omega `$ is 1-to-1 over $`M^{[n]}`$. The resolution is said to be suitable for a map $`f:M^{[n]}Y`$ if the map $`f\omega |_{\omega ^1(M^{[n]})}`$ extends to a map from $`EW(M,n)`$ to $`Y`$. The resolution is said to be suitable for a compactum $`X`$ if for every simplex $`\mathrm{\Delta }`$ of $`M`$, $`\mathrm{e}\mathrm{dim}X\omega ^1(\mathrm{\Delta })`$. Note that if $`\omega :EW(M,n)M`$ is a resolution suitable for $`X`$ then for every map $`\varphi :XM`$ there is a map $`\psi :XEW(M,n)`$ such that for every simplex $`\mathrm{\Delta }`$ of $`M`$ , $`(\omega \psi )(\varphi ^1(\mathrm{\Delta }))\mathrm{\Delta }`$. We will call $`\psi `$ a combinatorial lifting of $`\varphi `$.

Following  we will construct a resolution of an $`(n+1)`$-dimensional simplicial complex $`M`$ which is suitable for $`X`$ with $`dim_GXn`$ and a map $`f:M^{[n]}K(G,n)`$. In the sequel we will refer to this resolution as the standard resolution for $`f`$. Fix a CW-structure on $`K(G,n)`$ and assume that $`f`$ is cellular. We will obtain a CW-complex $`EW(M,n)`$ from $`M^{[n]}`$ by attaching the mapping cylinder of $`f|_\mathrm{\Delta }`$ to $`\mathrm{\Delta }`$ for every $`(n+1)`$-simplex $`\mathrm{\Delta }`$ of $`M`$. Let $`\omega :EW(M,n)M`$ be the projection sending each mapping cylinder to the corresponding $`(n+1)`$-simplex $`\mathrm{\Delta }`$ such that $`\omega `$ is the identity map on $`\mathrm{\Delta }`$, the $`K(G,n)`$-part of the cylinder is sent to the barycenter of $`\mathrm{\Delta }`$ and $`\omega `$ is 1-to-1 on the rest of the cylinder. Clearly $`f|_\mathrm{\Delta }`$ extends over its mapping cylinder and therefore $`f\omega |_{\omega ^1(M^{[n]})}`$ extends over $`EW(M,n)`$. For each simplex $`\mathrm{\Delta }`$ of $`M`$, $`\omega ^1(\mathrm{\Delta })`$ is either contractible or homotopy equivalent to $`K(G,n)`$. Define a CW-structure on $`EW(M,n)`$ turning $`\omega `$ into a combinatorial map. Thus we get that the standard resolution is indeed a resolution suitable for both $`X`$ and $`f`$. Note that from the construction of the standard resolution $`\omega :EW(M,n)M`$ it follows that for every subcomplex $`T`$ of $`M`$, $`\omega ^1(T)`$ is the standard resolution of $`T`$ for $`f|_{T^{[n]}}`$ and $`\omega ^1(T)`$ is $`(n1)`$-connected if $`T`$ is $`(n1)`$-connected.

###### Proposition 2.2

Let $`M`$ be an $`(n+1)`$-dimensional finite simplicial complex and let $`\omega :EW(M,n)M`$ be the standard resolution for $`f:M^{[n]}K(G,n)`$, $`n2`$. Then for $`\omega _{}:H_n(EW(M,n))H_n(M)`$, $`\mathrm{ker}\omega _{}`$ is a factor group of the direct sum $`G`$ of finitely many $`G`$.

Proof. Inside each $`(n+1)`$-simplex of $`M`$ cut a small closed ball around the barycenter and not touching the boundary and split $`M`$ into two subspaces $`M=M_1M_2`$ where $`M_1`$= the closure of the complement to the union of the balls and $`M_2`$=the union of the balls. Then $`\omega `$ is 1-to-1 over $`M_1`$, $`H_{n1}(M_1M_2)=0`$, $`H_n(M_2)=0`$ and the preimage under $`\omega `$ of each ball is homotopy equivalent to $`K(G,n)`$ and hence $`H_n(\omega ^1(M_2))`$ is the direct sum $`G`$ of finitely many $`G`$. Consider the Mayer-Vietoris sequences for the pairs $`(M_1,M_2)`$ and $`(\omega ^1(M_1),\omega ^1(M_2))`$, in which we identify $`M_1`$ and $`M_1M_2`$ with $`\omega ^1M_1`$ and $`\omega ^1(M_1M_2)`$ respectively.

From the Mayer-Vietoris sequences it follows that $`j_{}(H_n(\omega ^1(M_1)H_n(\omega ^1(M_2)))=H_n(\omega ^1(M_1M_2))`$ and $`j_{}(0H_n(\omega ^1(M_2)))\mathrm{ker}\omega _{}`$. Let us show that $`j_{}(0H_n(\omega ^1(M_2)))\mathrm{ker}\omega _{}`$. Let $`j_{}(ab)\mathrm{ker}\omega _{}`$. Then in the Mayer-Vietoris sequence for the pair $`(M_1,M_2)`$, $`j_{}(a0)=0`$ and therefore there is $`cH_n(M_1M_2))`$ such that $`i_{}(c)=a0`$. Then in the Mayer-Vietoris sequence for the pair $`(\omega ^1(M_1),\omega ^1(M_2))`$, $`i_{}(c)=ad`$ and $`j_{}(ad)=0`$. Thus $`j_{}(ab)=j_{}(0(bd))`$ and therefore $`j_{}(0H_n(\omega ^1(M_2)))=\mathrm{ker}\omega _{}`$. Recall that $`H_n(\omega ^1(M_2))=G`$ and the proposition follows. $`\mathrm{}`$

###### Proposition 2.3

Let $`M=M_1M_2`$ be a CW-complex with subcomplexes $`M_1`$ and $`M_2`$ such that $`M_1,M_2`$ and $`M_1M_2`$ are $`(n1)`$-connected, $`n2`$ . Then $`M`$ is $`(n1)`$-connected and

(i) $`H_n(M)`$ is $`𝒜`$-divisible if $`H_n(M_1)`$ and $`H_n(M_2)`$ are $`𝒜`$-divisible;

(ii) $`H_n(M)`$ is $`𝒜`$-torsion if $`H_n(M_1)`$ and $`H_n(M_2)`$ are $`𝒜`$-torsion.

Proof. The connectedness of $`M`$ follows from van Kampen and Hurewicz’s theorems and the Mayer-Vietoris sequence. (i) and (ii) follow from the Mayer-Vietoris sequence and (ii) and (iii) of Proposition 2.1. $`\mathrm{}`$

Let $`X`$ be a compactum and let $`\sigma (G)`$ be the Bockstein basis of a group $`G`$. By Bockstein’s theory $`dim_GXn`$ if and only if $`dim_EXn`$ for every $`E\sigma (G)`$. Denote :

$`𝒯(G)=\{p𝒫:_p\sigma (G)\}`$ ;

$`𝒯_{\mathrm{}}(G)=\{p𝒫:_p^{\mathrm{}}\sigma (G)\}`$ ;

$`𝒟(G)=𝒫`$ if $`\sigma (G)`$ and $`𝒟(G)=𝒫\{p𝒫:_{(p)}\sigma (G)\}`$ otherwise ;

$`(G)=𝒟(G)(𝒯(G)𝒯_{\mathrm{}}(G))`$.

Note that $`𝒯(G)`$, $`𝒯_{\mathrm{}}(G)`$ and $`(G)`$ are disjoint and $`G`$ is $`(G)`$-torsion free.

###### Proposition 2.4

Let $`X`$ be a compactum and let $`G`$ be a group such that $`G/\mathrm{Tor}G0`$ and $`dim_GXn`$. Then $`dim_EXn`$ for every group $`E`$ such that $`E`$ is $`𝒟(G)`$-divisible and $`(G)`$-torsion free.

Proof. The proof is based on Bockstein’s theorem and inequalities.

If $`_p\sigma (E)`$ then $`\mathrm{Tor}_pE`$ is not divisible by $`p`$ and hence $`E`$ is not divisible by $`p`$. Thus $`p𝒫𝒟(G)`$ and therefore $`_{(p)}\sigma (G)`$ and $`dim__pXdim_{_{(p)}}Xn`$.

If $`_p^{\mathrm{}}\sigma (E)`$ then $`p`$ is not in $`(G)`$. Then either $`p𝒫𝒟(G)`$ and $`dim__p^{\mathrm{}}Xdim_{_{(p)}}Xn`$ or $`p𝒟(G)(G)`$ and then either $`p𝒯(G)`$ and $`dim__p^{\mathrm{}}Xdim__pXn`$ or $`p𝒯_{\mathrm{}}(G)`$ and $`dim__p^{\mathrm{}}Xn`$.

If $`_{(p)}\sigma (E)`$ then $`E/\mathrm{Tor}E`$ is not divisible by $`p`$ and hence $`E`$ is not divisible by $`p`$. Thus $`p𝒫𝒟(G)`$ and therefore $`dim_{_{(p)}}Xn`$.

If $`\sigma (E)`$ then consider the following cases:

(i) $`𝒟(G)=𝒫`$. Then since $`G/\mathrm{Tor}G0`$, $`\sigma (G)`$ and therefore $`dim_{}Xn`$ (this is the only place where we use that $`G/\mathrm{Tor}G0`$);

(ii) there is $`p𝒫𝒟(G)`$. Then $`dim_{}Xdim_{_{(p)}}Xn`$. $`\mathrm{}`$

## 3 Proof of Theorem 1.2

Represent $`X`$ as the inverse limit $`X=\stackrel{\text{lim}}{}(K_i,h_i)`$ of finite simplicial complexes $`K_i`$ with combinatorial bonding maps $`h_{i+1}:K_{i+1}K_i`$ onto and the projections $`p_i:XK_i`$ such that for every simplex $`\mathrm{\Delta }`$ of $`K_i`$, diam$`(p_i^1(\mathrm{\Delta }))1/i`$. Following A. Dranishnikov  we construct by induction finite CW-complexes $`L_i`$ and maps $`g_{i+1}:L_{i+1}L_i`$, $`\alpha _i:L_iK_i`$ such that

(a) $`L_i`$ is $`(n+1)`$-dimensional and obtained from $`K_i^{[n+1]}`$ by replacing some $`(n+1)`$-simplexes by $`(n+1)`$-cells attached to the boundary of the replaced simplexes by a map of degree $`S((G))`$. Then $`\alpha _i`$ is a projection of $`L_i`$ taking the new cells to the original ones such that $`\alpha _i`$ is 1-to-1 over $`K_i^{[n]}`$. We define a simplicial structure on $`L_i`$ for which $`\alpha _i`$ is a combinatorial map and refer to this simplicial structure while constructing resolutions of $`L_i`$. Note that for $`(G)=\mathrm{}`$ we don’t replace simplexes of $`K_i^{[n+1]}`$ at all;

(b) the maps $`h_i`$, $`g_i`$ and $`\alpha _i`$ combinatorially commute. By this we mean that for every simplex $`\mathrm{\Delta }`$ of $`K_i`$, $`(\alpha _ig_{i+1})((h_{i+1}\alpha _{i+1})^1(\mathrm{\Delta }))\mathrm{\Delta }`$.

We will construct $`L_i`$ in such a way that $`Z=\stackrel{\text{lim}}{}(L_i,g_i)`$ will be of $`dim_Gn`$ and $`Z`$ will admit a $`G`$-acyclic map onto $`X`$.

Set $`L_1=K_1^{[n+1]}`$ with $`\alpha _1:L_1K_1`$ the embedding and assume that the construction is completed for $`i`$. Let $`E\sigma (G)`$ and let $`f:L_i^{[n]}K(E,n)`$ be a cellular map. Let $`\omega _L:EW(L_i,n)L_i`$ be the standard resolution of $`L_i`$ for $`f`$. We are going to construct from $`EW(L_i,n)`$ a resolution of $`K_i`$ suitable for $`X`$. On the first step of the construction we will obtain from $`EW(L_i,n)`$ a resolution $`\omega _{n+1}:EW(K_i^{[n+1]},n)K_i^{[n+1]}`$ such that $`EW(L_i,n)`$ is a subcomplex of $`EW(K_i^{[n+1]},n)`$ and $`\omega _{n+1}`$ extends $`\alpha _i\omega _L`$. On the second step we will construct resolutions $`\omega _j:EW(K_i^{[j]},n)K_i^{[j]}`$, $`n+2jdimK_i`$ such that $`EW(K_i^{[j]},n)`$ is a subcomplex of $`EW(K_i^{[j+1]},n)`$ and $`\omega _{j+1}`$ extends $`\omega _j`$. The construction is carried out as follows.

Step 1. For every simplex $`\mathrm{\Delta }`$ of $`K_i`$ of $`dim=n+1`$ consider separately the subcomplex $`(\alpha _i\omega _L)^1(\mathrm{\Delta })`$ of $`EW(L_i,n)`$. Note that from (a) and the properties of the standard resolution it follows that the preimage under $`\alpha _i\omega _L`$ of an $`(n1)`$-connected subcomplex of $`K_i`$ is $`(n1)`$-connected. Then $`(\alpha _i\omega _L)^1(\mathrm{\Delta })`$ is $`(n1)`$-connected. Enlarge $`(\alpha _i\omega _L)^1(\mathrm{\Delta })`$ by attaching cells of $`dim=n+1`$ in order to kill $`\mathrm{Tor}_{(G)}H_n((\alpha _i\omega _L)^1(\mathrm{\Delta }))`$ and attaching cells of $`dim>n+1`$ in order to kill all homotopy groups of the enlarged subcomplex in $`dim>n`$. Define $`EW(K_i^{[n+1]},n)`$ as $`EW(L_i,n)`$ with all the cells attached for all $`(n+1)`$-dimensional simplexes $`\mathrm{\Delta }`$ of $`K_i`$ and let a map $`\omega _{n+1}:EW(K_i^{[n+1]},n)K_i^{[n+1]}`$ extend $`\alpha _i\omega _L`$ by sending the interior points of the attached cells to the interior of the corresponding $`\mathrm{\Delta }`$.

Step 2. Assume that a resolution $`\omega _j:EW(K_i^{[j]},n)K_i^{[j]}`$, $`n+1j<dimK_i`$ is constructed such that the $`n`$-skeleton of $`EW(K_i^{[j]},n)`$ coincides with the $`n`$-skeleton of $`EW(L_i,n)`$. For every simplex $`\mathrm{\Delta }`$ of $`K_i`$ of $`dim=j+1`$ consider separately the subcomplex $`\omega _{j}^{}{}_{}{}^{1}(\mathrm{\Delta })`$ of $`EW(K_i^{[j]},n)`$. Then the $`n`$-skeleton of $`\omega _{j}^{}{}_{}{}^{1}(\mathrm{\Delta })`$ coincides with the $`n`$-skeleton of $`(\alpha _i\omega _L)^1(\mathrm{\Delta })`$ and therefore $`\omega _{j}^{}{}_{}{}^{1}(\mathrm{\Delta })`$ is $`(n1)`$-connected. Enlarge $`\omega _{j}^{}{}_{}{}^{1}(\mathrm{\Delta })`$ by attaching cells of $`dim=n+1`$ to in order to kill $`\mathrm{Tor}_{(G)}H_n(\omega _j^1(\mathrm{\Delta }))`$ and attaching cells of $`dim>n+1`$ in order to kill all homotopy groups of the enlarged subcomplex in $`dim>n`$. Define $`EW(K_i^{[j+1]},n)`$ as $`EW(K_i^{[j]},n)`$ with all the cells attached for all $`(j+1)`$-simplexes of $`K_i`$ and let a map $`\omega _{j+1}:EW(K_i^{[j+1]},n)K_i^{[j+1]}`$ extend $`\omega _j`$ by sending the interior points of the attached cells to the interior of the corresponding $`\mathrm{\Delta }`$.

Finally denote $`EW(K_i,n)=EW(K_i^{[m]},n)`$ and $`\omega =\omega _m:EW(K_i,n)K_i`$ where $`m=dimK_i`$. From the construction it follows that the $`n`$-skeleton of $`EW(K_i,n)`$ is contained in $`EW(L_i,n)`$ and for every simplex $`\mathrm{\Delta }`$ of $`K_i`$, $`\omega ^1(\mathrm{\Delta })`$ is contractible if $`dim\mathrm{\Delta }n`$ and $`\omega ^1(\mathrm{\Delta })`$ is homotopy equivalent to $`K(H_n(\omega ^1(\mathrm{\Delta })),n)`$ if $`dim\mathrm{\Delta }n+1`$.

Let us show that $`EW(K_i,n)`$ is suitable for $`X`$. In order to verify that $`dim_{H_n(\omega ^1(\mathrm{\Delta }))}Xn`$ for every simplex $`\mathrm{\Delta }`$ of $`K_i`$ of $`dimn+1`$ we first consider Step 1 of the construction. Let $`\mathrm{\Delta }`$ be an $`(n+1)`$-dimensional simplex of $`K_i`$. By $`\omega _L|_{\mathrm{}}`$ we will denote the map $`\omega _L|_{(\alpha _i\omega _L)^1(\mathrm{\Delta })}:(\alpha _i\omega _L)^1(\mathrm{\Delta })\alpha _{i}^{}{}_{}{}^{1}(\mathrm{\Delta })`$ with the range restricted to $`\alpha _{i}^{}{}_{}{}^{1}(\mathrm{\Delta })`$. Note that by (a), $`H_n(\alpha _i^1(\mathrm{\Delta }))`$ is $`(G)`$-torsion and $`H_n(\omega ^1(\mathrm{\Delta }))=H_n((\alpha _i\omega _L)^1(\mathrm{\Delta }))/\mathrm{Tor}_{(G)}H_n((\alpha _i\omega _L)^1(\mathrm{\Delta }))`$. Let $`(\omega _L|_{\mathrm{}})_{}:H_n((\alpha _i\omega _L)^1(\mathrm{\Delta }))H_n(\alpha _{i}^{}{}_{}{}^{1}(\mathrm{\Delta }))`$. Consider the following cases.

Case 1-1. $`E=_p`$. By Proposition 2.2 $`\mathrm{ker}(\omega _L|_{\mathrm{}})_{}`$ is $`p`$-torsion. Then since $`p`$ is not in $`(G)`$, by Proposition 2.1, (v), $`H_n(\omega ^1(\mathrm{\Delta }))`$ is $`p`$-torsion and by Bockstein’s theorem $`dim_{H_n(\omega ^1(\mathrm{\Delta }))}Xdim__pXn`$.

Case 1-2. $`E=_p^{\mathrm{}}`$. By Proposition 2.2 $`\mathrm{ker}(\omega _L|_{\mathrm{}})_{}`$ is $`p`$-torsion and $`p`$-divisible. Then since $`p`$ is not in $`(G)`$, by Proposition 2.1, (vi), $`H_n(\omega ^1(\mathrm{\Delta }))`$ is $`p`$-torsion and $`p`$-divisible and by Bockstein’s theorem $`dim_{H_n(\omega ^1(\mathrm{\Delta }))}Xdim__p^{\mathrm{}}Xn`$.

Case 1-3. $`E=_{(p)}`$ or $`E=`$. By Proposition 2.2 $`\mathrm{ker}(\omega _L|_{\mathrm{}})_{}`$ is $`𝒟(G)`$-divisible. Then since $`(G)𝒟(G)`$, by Proposition 2.1, (iv), $`H_n(\omega ^1(\mathrm{\Delta }))`$ is $`𝒟(G)`$-divisible and since $`H_n(\omega ^1(\mathrm{\Delta }))`$ is $`(G)`$-torsion free, by Proposition 2.4, $`dim_{H_n(\omega ^1(\mathrm{\Delta }))}Xn`$.

Now let us pass to Step 2 of the construction. We will show that the properties of the homology groups established above will be preserved for simplexes of higher dimensions. Let $`\mathrm{\Delta }`$ be a $`(j+1)`$-dimensional simplex of $`K_i`$, $`jn+1`$ and recall that $`H_n(\omega ^1(\mathrm{\Delta }))=H_n(\omega ^1(\mathrm{\Delta }))/\mathrm{Tor}_{(G)}H_n(\omega ^1(\mathrm{\Delta }))`$. Note that from the construction it follows that the preimage under $`\omega `$ of an $`(n1)`$-connected subcomplex of $`K_i`$ is $`(n1)`$-connected. Also note that the intersection of a $`j`$-dimensional simplex of $`\mathrm{\Delta }`$ with the union of any collection of $`j`$-dimensional simplexes of $`\mathrm{\Delta }`$ is $`(n1)`$-connected. These facts allow us to apply below Proposition 2.3 for assembling $`\omega ^1(\mathrm{\Delta })`$ from $`\omega ^1(\mathrm{\Delta }^{})`$ for $`j`$-dimensional simplexes $`\mathrm{\Delta }^{}`$ of $`\mathrm{\Delta }`$ to show that $`\omega ^1(\mathrm{\Delta })`$ has properties corresponding to propperties of $`\omega ^1(\mathrm{\Delta }^{})`$. Once again we consider separately the following cases.

Case 2-1. $`E=_p`$. If for every $`j`$-dimensional simplex $`\mathrm{\Delta }^{}`$ of $`\mathrm{\Delta }`$, $`H_n(\omega ^1(\mathrm{\Delta }^{}))`$ is $`p`$-torsion then by Proposition 2.3, $`H_n(\omega ^1(\mathrm{\Delta }))`$ is $`p`$-torsion and hence $`H_n(\omega ^1(\mathrm{\Delta }))`$ is $`p`$-torsion. Therefore $`dim_{H_n(\omega ^1(\mathrm{\Delta }))}Xdim__pXn`$.

Case 2-2. $`E=_p^{\mathrm{}}`$. If for every $`j`$-dimensional simplex $`\mathrm{\Delta }^{}`$ of $`\mathrm{\Delta }`$, $`H_n(\omega ^1(\mathrm{\Delta }^{}))`$ is $`p`$-torsion and $`p`$-divisible then by Proposition 2.3, $`H_n(\omega ^1(\mathrm{\Delta }))`$ is $`p`$-torsion and $`p`$-divisible and hence $`H_n(\omega ^1(\mathrm{\Delta }))`$ is $`p`$-torsion and $`p`$-divisible. Therefore $`dim_{H_n(\omega ^1(\mathrm{\Delta }))}Xdim__p^{\mathrm{}}Xn`$.

Case 2-3. $`E=_{(p)}`$ or $`E=`$. If for every $`j`$-dimensional simplex $`\mathrm{\Delta }^{}`$ of $`\mathrm{\Delta }`$, $`H_n(\omega ^1(\mathrm{\Delta }^{}))`$ is $`𝒟(G)`$-divisible then by Proposition 2.3, $`H_n(\omega ^1(\mathrm{\Delta }))`$ is $`𝒟(G)`$-divisible. Then $`H_n(\omega ^1(\mathrm{\Delta }))`$ is $`𝒟(G)`$-divisible and $`(G)`$-torsion free and by Proposition 2.4, $`dim_{H_n(\omega ^1(\mathrm{\Delta }))}Xn`$.

Thus we have shown that $`EW(K_i,n)`$ is suitable for $`X`$. Now replacing $`K_{i+1}`$ by a $`K_l`$ with a sufficiently large $`l`$ we may assume that there is a combinatorial lifting of $`h_{i+1}`$ to $`h_{i+1}^{}:K_{i+1}EW(K_i,n)`$. Replace $`h_{i+1}^{}`$ by its cellular approximation preserving the property of $`h_{i+1}^{}`$ of being a combinatorial lifting of $`h_{i+1}`$.

Consider the $`(n+1)`$-skeleton of $`K_{i+1}`$ and let $`\mathrm{\Delta }_{i+1}`$ be an $`(n+1)`$-dimensional simplex in $`K_{i+1}`$. Let $`\mathrm{\Delta }_i`$ be the smallest simplex in $`K_i`$ containing $`h_{i+1}(\mathrm{\Delta }_{i+1})`$. Then $`h_{i+1}^{}(\mathrm{\Delta }_{i+1})\omega ^1(\mathrm{\Delta }_i)`$. Let $`\tau :(\alpha _i\omega _L)^1(\mathrm{\Delta }_i)\omega ^1(\mathrm{\Delta }_i)`$ be the inclusion. Note that from the construction it follows that for $`\tau _{}:H_n((\alpha _i\omega _L)^1(\mathrm{\Delta }_i))H_n(\omega ^1(\mathrm{\Delta }_i))`$, $`\mathrm{ker}\tau _{}`$ is $`(G)`$-torsion. Recall that the $`n`$-skeleton of $`\omega ^1(\mathrm{\Delta }_i)`$ is contained in $`(\alpha _i\omega _L)^1(\mathrm{\Delta }_i)`$ and consider $`h_{i+1}^{}|_{\mathrm{\Delta }_{i+1}}`$ as a map to $`(\alpha _i\omega _L)^1(\mathrm{\Delta }_i)`$. Let $`a`$ be the generator of $`H_n(\mathrm{\Delta }_{i+1})`$. Since $`h_{i+1}^{}|_{\mathrm{\Delta }_{i+1}}`$ extends over $`\mathrm{\Delta }_{i+1}`$ as a map to $`\omega ^1(\mathrm{\Delta }_i)`$ we have that $`\tau _{}((h_{i+1}^{}|_{\mathrm{\Delta }_{i+1}})_{}(a))=0`$. Hence $`(h_{i+1}^{}|_{\mathrm{\Delta }_{i+1}})_{}(a)\mathrm{ker}\tau _{}`$ and therefore there is $`kS((G))`$ such that $`k((h_{i+1}^{}|_{\mathrm{\Delta }_{i+1}})_{}(a))=0`$. Replace $`\mathrm{\Delta }_{i+1}`$ by a cell $`C`$ attached to the boundary of $`\mathrm{\Delta }_{i+1}`$ by a map of degree $`k`$ if $`(h_{i+1}^{}|_{\mathrm{\Delta }_{i+1}})_{}(a)0`$ and set $`C=\mathrm{\Delta }_{i+1}`$ if $`(h_{i+1}^{}|_{\mathrm{\Delta }_{i+1}})_{}(a)=0`$. Then $`h_{i+1}^{}|_{\mathrm{\Delta }_{i+1}}`$ can be extended over $`C`$ as a map to $`(\alpha _i\omega _L)^1(\mathrm{\Delta }_i)`$ and we will denote this extension by $`g_{i+1}^{}|_C:C(\alpha _i\omega _L)^1(\mathrm{\Delta }_i)`$. Thus replacing if needed $`(n+1)`$-simplexes of $`K_{i+1}^{[n+1]}`$ we construct from $`K_{i+1}^{[n+1]}`$ a CW-complex $`L_{i+1}`$ and a map $`g_{i+1}^{}:L_{i+1}EW(L_i,n)`$ which extends $`h_{i+1}^{}`$ restricted to the $`n`$-skeleton of $`K_{i+1}`$. Now define $`g_{i+1}=\omega _Lg_{i+1}^{}:L_{i+1}L_i`$ and finally define a simplicial structure on $`L_{i+1}`$ for which $`\alpha _{i+1}`$ is a combinatorial map. It is easy to check that the properties (a) and (b) are satisfied. Since the triangulation of $`L_{i+1}`$ can be replaced by any of its barycentric subdivisions we may also assume that

(c) diam$`g_{i+1}^j(\mathrm{\Delta })1/i`$ for every simplex $`\mathrm{\Delta }`$ in $`L_{i+1}`$ and $`ji`$
where $`g_i^j=g_{j+1}g_{j+2}\mathrm{}g_i:L_iL_j`$.

Denote $`Z=\stackrel{\text{lim}}{}(L_i,g_i)`$ and let $`r_i:ZL_i`$ be the projections. For constructing $`L_{i+1}`$ we used an arbitrary map $`f:L_i^{[n]}K(E,n),E\sigma (G)`$. Let us show that choosing $`E\sigma (G)`$ and $`f`$ in an appropriate way for each $`i`$ we can achieve that $`dim_EZn`$ for every $`E\sigma (G)`$ and hence $`dim_GZn`$.

Let $`\psi :FK(E,n)`$ be a map of a closed subset $`F`$ of $`L_j`$. Then by (c) for a sufficiently large $`i>j`$ the map $`\psi g_i^j|_{(g_i^j)^1(F)}`$ extends over a subcomplex $`N`$ of $`L_i`$ to a map $`\varphi :NK(E,n)`$. Extending $`\varphi `$ over $`L_i^{[n]}`$ we may assume that $`L_i^{[n]}N`$ and replacing $`\varphi `$ by its cellular approximation we assume that $`\varphi `$ is cellular. Now define the map $`f:L_i^{[n]}K(E,n)`$ that we use for constructing $`L_{i+1}`$ as $`f=\varphi |_{L_i^{[n]}}`$. Since $`g_{i+1}`$ factors through $`EW(L_i,n)`$, the map $`fg_{i+1}|_{g_{i+1}^1(L_i^{[n]})}:g_{i+1}^1(L_i^{[n]})K(E,n)`$ extends to a map $`f^{}:L_{i+1}K(E,n)`$. Define $`\psi ^{}:L_{i+1}K(E,n)`$ by $`\psi ^{}(x)=(\varphi g_{i+1})(x)`$ if $`xg_{i+1}^1(N)`$ and $`\psi ^{}(x)=f^{}(x)`$ otherwise. Then $`\psi ^{}|_{(g_{i+1}^j)^1(F)}:(g_{i+1}^j)^1(F)K(E,n)`$ is homotopic to $`\psi g_{i+1}^j|_{(g_{i+1}^j)^1(F)}:(g_{i+1}^j)^1(F)K(E,n)`$ and hence $`\psi g_{i+1}^j|_{(g_{i+1}^j)^1(F)}`$ extends over $`L_{i+1}`$. Now since we need to solve only countably many extension problems for every $`L_j`$ with respect to $`K(E,n)`$ for every $`E\sigma (G)`$ we can choose for each $`i`$ a map $`f:L_i^{[n]}K(E,n)`$ in the way described above to achieve that $`dim_EZn`$ for every $`E\sigma (G)`$ and hence $`dim_GZn`$.

The property (b) implies that for every $`xX`$ and $`zZ`$,

(d1) $`g_{i+1}(\alpha _{i+1}^1(st(p_{i+1}(x))))\alpha _i^1(st(p_i(x)))`$ and

(d2) $`h_{i+1}(st((\alpha _{i+1}r_{i+1})(z)))st((\alpha _ir_i)(z))`$
where $`st(a)=`$the union of all the simplexes containing $`a`$.

Define a map $`r:ZX`$ by $`r(z)=\{p_i^1(st((\alpha _ir_i)(z))):i=1,2,\mathrm{}\}`$. Then (d1) and (d2) imply that $`r`$ is indeed well-defined and continuous.

The properties (d1) and (d2) also imply that for every $`xX`$
$`r^1(x)=\stackrel{\text{lim}}{}(\alpha _i^1(st(p_i(x))),g_i|_{\alpha _i^1(st(p_i(x)))})`$, where the map $`g_i|_{\alpha _i^1(st(p_i(x)))}`$ is considered as a map to $`\alpha _{i1}^1(st(p_{i1}(x)))`$.

Since $`r^1(x)`$ is not empty for every $`xX`$, $`r`$ is a map onto and let us show that $`r^1(x)`$ is $`G`$-acyclic.

Since $`st(p_i(x))`$ is contractible, $`T=\alpha _i^1(st(p_i(x)))`$ is $`(n1)`$-connected. From (a) and Proposition 2.3 it follows that $`H_n(T)`$ is $`(G)`$-torsion. Then, since $`G`$ is $`(G)`$-torsion free, by the universal-coefficient theorem $`H^n(T;G)=\mathrm{Hom}(H_n(T),G)=0`$. Thus $`\stackrel{~}{\stackrel{ˇ}{H}}{}_{}{}^{k}(r^1(x);G)=0`$ for $`kn`$ and since $`dim_GZn`$, $`\stackrel{~}{\stackrel{ˇ}{H}}{}_{}{}^{k}(r^1(x);G)=0`$ for $`kn+1`$. Hence $`r`$ is $`G`$-acyclic and this completes the proof. $`\mathrm{}`$

Department of Mathematics
Ben Gurion University of the Negev
P.O.B. 653
Be’er Sheva 84105, ISRAEL
e-mail: mlevine@math.bgu.ac.il


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# Acknowledgments

## Acknowledgments

The author wishes to thank Chao-Qiang Geng and Paul Singer for very helpful communications. This work is supported in part by the NSF of China under Grant No. 19905008.


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# Low temperature value of the upper critical field 𝐻_{𝑐2}(0) of isotropic single band metals

## I Introduction

The standard isotropic single band (ISB) Eliashberg model  is the most developed part of the modern theory of superconductivity. It describes quantitatively the renormalization of the physical properties of metals due to the electron-phonon interaction. The input material parameters are the density of states at $`E_F`$, $`N(0)`$, the bare Fermi velocity $`v_F`$, the impurity scattering rate $`\gamma _{imp}`$, the paramagnetic impurity scattering rate $`\gamma _m`$, the Coulomb pseudopotential $`\mu ^{}(0.1)`$, and the electron-phonon spectral (Eliashberg) function $`\alpha ^2F(\mathrm{\Omega })`$. Thereby the validity of the Born approximation is assumed, i.e. the system is far from the onset of localization.

These days the material parameters $`N(0)`$, the averaged Fermi velocity, and the spectral function become available from microscopic calculations just very soon after the discovery of a new superconducting compound. The standard procedures of analysis of many physical properties of metals include these results as input parameters. For example, the density of states $`N(0)`$ is important for the description of the specific heat data. Similarly, the calculated plasma frequency is used for the interpretation of the optical and transport properties. As a rule, the forthcoming optical measurements do confirm its value later on. At the same time, the upper critical field $`H_{c2}(0)`$, the fundamental quantity of a type-II superconductors is usually analyzed by experimentalists in the framework of the phenomenological Ginzburg-Landau (GL) theory which states $`H_{c2}(0)=\mathrm{\Phi }_0/2\pi \xi ^2`$. Here $`\mathrm{\Phi }_0`$ is the flux quantum and $`\xi `$ is the GL-coherence length, the material parameter of the GL theory.

Within the Eliashberg ISB model $`H_{c2}(T)`$ can be computed using the Schossmann-Schachinger self-consistent theory . This theory treats $`H_{c2}(T)`$ as the field dependence of the critical temperature $`T_c(H)`$. At $`H=0`$ the linear $`H_{c2}(T)`$-problem is reduced to the equations for $`T_c`$. From a numerical point of view the eigenvalue problems for $`T_c`$ and $`H_{c2}(T)`$ are identical and can be computed by the same code. In practice, however, the linearized equations for $`T_c`$ are frequently not exploited even by teams who perform tedious numerical band structure or Eliashberg-theory calculations. Instead the well-known phenomenological Allen-Dynes expression for $`T_c`$ is widely used. In our opinion a similar approach could be applied also to $`H_{c2}(0)`$ calculating it from a simple formula.

Here, for the sake of clarity and simplicity the Pauli limiting, unimportant in many cases of practical interest, is ignored. In the present paper we examine five simple expressions for $`H_{c2}(0)`$ by comparison with the numerical solutions of Eqs. 1-5. One of these formulas valid in the clean limit is presented in the present work for the first time. It is shown that at least three formulas fit reasonably well the numerical values of $`H_{c2}(0)`$ in a wide range of coupling strengths $`\lambda `$. The deviations do not exceed 12%. Extensions to cases of arbitrary impurity content are considered as well. An application example of the approximate phenomenological formula is provided.

## II General equations and approximate semi-analytical formulas

To take into account fully retardation and strong coupling effects in calculating $`H_{c2}`$, we have solved numerically the linearized equations proposed in Ref.

$`\stackrel{~}{\omega }(n)`$ $`=`$ $`\omega _n+{\displaystyle \frac{\gamma _{imp}\mathrm{sgn}\omega _n}{2}}+\pi T{\displaystyle \underset{m}{}}\lambda (mn)\text{sgn}\omega _m,`$ (1)
$`\stackrel{~}{\mathrm{\Delta }}(n)`$ $`=`$ $`\pi T{\displaystyle \underset{m}{}}{\displaystyle \frac{[\lambda (mn)\mu ^{}]\stackrel{~}{\mathrm{\Delta }}(m)}{\chi ^1(m)\gamma _{imp}/2}},`$ (2)
$`\chi (n)`$ $`=`$ $`{\displaystyle \frac{2}{\sqrt{\beta }}}{\displaystyle _0^{\mathrm{}}}𝑑qe^{q^2}\mathrm{atan}\left[{\displaystyle \frac{q\sqrt{\beta }}{|\stackrel{~}{\omega }(n)|}}\right],`$ (3)
$`\beta `$ $`=`$ $`\mathrm{}eH_{c2}v_F^2/2c,`$ (4)
$`\lambda (n)`$ $`=`$ $`{\displaystyle _0^{\mathrm{}}}𝑑\omega \omega \alpha ^2F(\omega )/[\omega ^2+(2\pi Tn)^2].`$ (5)
Here $`\omega _n`$=$`\pi T(2n+1)`$ are the Matsubara frequencies, $`e`$ and $`\stackrel{~}{\mathrm{\Delta }}(n)`$ denote the electron charge and the superconducting order parameter. $`\mathrm{}`$ and $`c`$ are the Plank’s constant and the speed of light.

From the numerical point of view the equations of the Werthamer-Helfand-Hohenberg (WHH)  and the Schossmann-Schachinger theory have the same order of complexity. At the same time the WHH equations allow full analytical solutions, both in the clean and dirty limits. In particular, the clean limit WHH orbital upper critical field for the ISB model reads

$$H_{c2}^{\mathrm{WHH}}(0)=\frac{k_B^2T_c^2\pi ^2ce^{2\gamma }}{2\mathrm{}ev_F^2},$$
(6)
where $`k_B`$ and $`\gamma `$=0.577 denote the Boltzmann’s and the Euler’s constants. In practical units this formula can be rewritten as

$$H_{c2}^{\mathrm{WHH}}(0)[\mathrm{Tesla}]=\frac{0.0231T_c^2[\mathrm{K}]}{v_F^2[10^7\mathrm{cm}/\mathrm{s}]}\frac{0.02T_c^2[\mathrm{K}]}{v_F^2[10^7\mathrm{cm}/\mathrm{s}]}.$$
(7)
Within the BCS theory, where 2$`\mathrm{\Delta }3.53T_c`$, the formula

$$H_{c2}^{Sung}(0)=\frac{13.3c\mathrm{\Delta }_0^2}{2e\mathrm{}v_F^2},$$
(8)
is identical to the basic Eq. (6). It was used by Sung  for an estimation of $`v_F`$ in Nb.

McMillan and Werthamer  were the first who introduced the first order strong coupling corrections ($`Z(0)=1+\lambda `$)

$`H_{c2}^{\mathrm{McM}\mathrm{WHH}}(T)=H_{c2}^{\mathrm{WHH}}(T)(1+\lambda )^2,`$ (9)
$`H_{c2}^{\mathrm{McM}\mathrm{WHH}}(0)={\displaystyle \frac{k_B^2T_c^2\pi ^2ce^{2\gamma }}{2\mathrm{}e[v_F/(1+\lambda )]^2}}={\displaystyle \frac{k_B^2T_c^2\pi ^2ce^{2\gamma }}{2\mathrm{}ev_{F}^{}{}_{}{}^{2}}}.`$ (10)
They conclude, that “this produces a substantial overall increase in $`H_{c2}`$ from that which would be obtained using the bare band Fermi velocity, but being relatively temperature-independent the shift cancels out of $`h(t)`$.” These days Eq. (10) is often regarded as a BCS formula since the “bare” Fermi velocity has to be replaced by the “dressed” Fermi velocity $`v_F^{}=v_F/(1+\lambda )`$ in Eq. 6. Similarly, the renormalized form of Sung’s formula (8) reads

$$H_{c2}^{McMS}(0)=\frac{13.3c\mathrm{\Delta }_0^2}{2e\mathrm{}v_{F}^{}{}_{}{}^{2}}.$$
(11)
For the sake of completeness, we note that in the presence of magnetic pair-breaking the considered renormalization of $`v_F`$ is different .

Since there are no analytical solution of Eqs. (1-5), approximate expressions should be used to estimate $`H_{c2}(0)`$. The parameters in such formulas are determined by the fit of numerical data. The first expression  reads

$$H_{c2}^A(0)=\frac{T_c^2(1+\lambda )^2\pi ^2ce^{2\gamma }}{2\mathrm{}ev_F^2}\left[1+1.44\left(\frac{T_c}{\omega _{\mathrm{ln}}}\right)\right],$$
(12)
where $`\omega _{\mathrm{ln}}`$ is the characteristic phonon frequency introduced by Kirzhnits et al.  and used later on in Ref.  by Allen and Dynes. A similar $`H_{c2}(0)`$ expression was proposed by Masharov  who obtained however different values for the numerical coefficients.

Our factorable  formula, first presented here,

$$H_{c2}^C(0)\frac{k_B^2T_c^2\pi ^2ce^{2\gamma }(1+\lambda )^{2.2}}{2\mathrm{}ev_{F}^{}{}_{}{}^{2}},$$
(13)
is suitable for applications together with other factorable expressions. In practical units it reads

$$H_{c2}^C(0)[\mathrm{Tesla}]\frac{0.0231T_c^2[\mathrm{K}](1+\lambda )^{2.2}}{v_F^2[10^7\mathrm{cm}/\mathrm{s}]}.$$
(14)
Note that the choice of the coefficients in Eq. (14) is not unique. For example, the following expression

$$H_{c2}^B(0)[\mathrm{Tesla}]\frac{0.02T_c^2[\mathrm{K}](1+\lambda )^{2.4}}{v_F^2[10^7\mathrm{cm}/\mathrm{s}]},$$
(15)
demonstrates even better agreement with the numerical data. Eq. 15 is especially designed for the Q-check  in the spirit of the Langmann’s BCS Eq. 24 in Ref..

## III Results and Discussion

To check the accuracy of Eqs. (10-15), we solved the Eq. (1-5) employing an Einstein spectral function with various coupling constants $`\lambda =0.72.9`$ and standard values for the Coulomb pseudopotential $`\mu ^{}`$. Then the $`H_{c2}(0)`$-values from the approximate formulas (10-15) were normalized by the ”exact” numerical values. The result is shown in Fig. 1. If the symbol occurs below the unity line, the corresponding approximate expression underestimates $`H_{c2}(0)`$ and vice versa. The phenomenological formulas Eqs. (12-15) fit well the numerical data. The deviations from unity do not exceed 12% in a wide range of coupling strengths. The formulas Eqs. (10-11) being identical within BCS theory deviates differently and exhibit relatively lower accuracy.

A detailed discussion and collections of the BCS upper critical field formulas are given for instance in Ref. . Here we discuss only the structure of weak coupling formulas Eqs. (10-11) with respect to the general Bergman-Rainer  ansatz

$$H_{c2}(0)=H_{c2}^{BCS}(0)f(\alpha ^2F(\mathrm{\Omega }),\mu ^{},T_c).$$
(16)
For the reason of dimensionality $`H_{c2}^{BCS}(0)`$ is proportional to the square of some typical energy. It could be $`T_c`$, the gap $`\mathrm{\Delta }_0`$, the Debye energy $`\omega _D`$, or the average phonon frequency $`\omega _{ln}`$, and there is a total equivalence between them within the BCS theory due to its universal character. Within the Eliashberg theory the situation is different. Here Eq. (10) is more preferable than the renormalized Sung’s formula (11) (see Fig. 1). In fact, at given $`\lambda `$ the $`H_{c2}^{McMWHH}(0)`$ points accumulate at nearly the same position for different values of $`\mu ^{}`$ in comparison with the $`H_{c2}^{McMS}(0)`$ data which spread out. This accumulation is a clear advantage of the basic Eq. (10). A similar choice in favor of Eq. (10) was made by Carbotte  without comments. We believe that the weak sensitivity of the ratio $`H_{c2}(0)/T_c^2`$ to details of $`\alpha ^2F(\omega )`$ and the actual value of $`\mu ^{}`$ is due to the fact that $`H_{c2}(0)`$ and $`T_c`$ are the solution of the same linearized system of Eqs. (1-5) .

In Sec. II various $`H_{c2}(0)`$ formulas are presented in different styles. The first group consists of “textbook-like” expressions(6,10,12,13) which contain explicitly fundamental physical and mathematical constants. Eqs. 7,14,15 written in practical units are preferred by insiders working in the field. Sung’s formulas (8,11) occupy an intermediate position. In our opinion the complete “textbook-like” presentation is necessary when a formula is derived for the first time from a general theory without simplifying additional assumptions. Otherwise, all styles are equivalent. In the present context a proof means a comparison of values given by a formula and a related computer code.

In view of a reasonable accuracy the question might arise: “Should we truncate higher digits in the prefactor $`B_1=0.0231`$ of Eq. 7 to $`B_2=0.02`$ before substitution into Eq. 16 or not?” because the Fermi velocity is not constant across the Fermi surface, and it is usually known with some uncertainty. The alternative possibilities led to Eqs. (13,14) and Eq. (15).

The Carbotte formula (12) also derived from Eqs. (1-5) through a series of simplifying assumptions, includes second order strong coupling corrections in terms of the small parameter $`T_c/\omega _{ln}`$. The leading linear term 1.44$`T_c/\omega _{\mathrm{ln}}`$ is introduced on a pure phenomenologically basis to get the best fit of numerical data (see remark below Eq. (7.15) in Ref. ). The Carbotte formula contains the additional parameter $`T_c/\omega _{\mathrm{ln}}`$ in comparison with “bare” BCS one and is not factorable.

For the overwhelming majority of ISB superconductors the Allen-Dynes formula

$$k_BT_c=\frac{\mathrm{}\omega _{ln}f_1f_2}{1.2}\mathrm{exp}\left\{\frac{1.04(1+\lambda )}{\lambda \mu ^{}(1+0.62\lambda )}\right\},$$
(17)
describes $`T_c`$ within an accuracy of about 5%. In a rigorous sense, it can be reduced to the BCS expression

$$k_BT_c=1.13\mathrm{}\omega _c\mathrm{exp}\left(\frac{1+\lambda }{\lambda \mu ^{}}\right),$$
(18)
at $`\lambda \mu ^{}0`$ only, when $`T_c`$0. The coupling constant $`\lambda `$, the Coulomb pseudopotential $`\mu ^{}`$, and the characteristic boson energy $`\omega _c=\omega _{ln}/(1.131.2)`$ are the parameters which enter Eqs. 17, 18. Despite the formal “contradiction” to the standard BCS Eq. (18), the Allen-Dynes formula is widely used, especially for qualitative discussions where possible slight uncertainties may be ignored. Our formulas Eqs. (13-15) were designed in the same manner and can be treated as the counter part of the “Allen-Dynes formulas” for the clean limit $`H_{c2}(0)`$ of isotropic single band metals.

$`H_{c2}(0)`$ does not depend on $`N(0)`$ and in view of Eq. (4), $`H_{c2}(0)1/v_F^2`$. As discussed above, the relation $`H_{c2}(0)T_c^2`$ captures with high accuracy the dependences on $`\mu ^{}`$ and on the shape of the spectral function. The remaining material parameter $`\lambda `$ measures the overall strength of the spectral function $`\alpha ^2F(\omega )`$. Since $`\lambda `$ enters the basic BCS formula as the mass renormalization (1+ $`\lambda `$) it is natural at first to make for the correction function entering Eq. (16) the following ansatz

$$f=(1+\lambda )^A.$$
(19)
The chi-by-eye  fit is shown in Fig. 1 for the prefactor values $`B_1`$=0.0231 and $`B_2`$=0.02. The round-off before the fit leads to $`A_2`$0.4 in comparison with $`A_1`$=0.23 obtained for BCS $`B_2`$0.0231. The additional calculations using various spectral functions and Coulomb pseudopotentials $`\mu ^{}`$ yield a deviation of $`\delta A`$0.08. Thus we adopt $`A_1=`$0.2 and $`A_2`$=0.4. Notice that an attempt to renormalize the Fermi velocities by the $`(1+\lambda )^{1+A/2}(1+(1+A/2)\lambda )`$ and the reciprocal BCS-coupling constant as $`1.04(1+\lambda )/[\lambda \mu ^{}(1+0.62\lambda )]`$ are in a rigorous sense incorrect, since the meaning of “dressing” and mass renormalization correspond to linear relations.

Formally speaking, the discussed above approximate formulas should be supplemented by a clean limit criterion. We remind the reader that there is no natural criterion for $`H_c2`$ in the weak coupling BCS regime. Instead the general case of arbitrary impurity scattering rate can be described approximately by a sum of two terms . It is shown  that the second order corrections with an accuracy of about 6% coincide in the clean and extreme dirty limits. Hence, one expects that $`H_{c2}(0,\gamma _{imp})/H_{c2}^{clean}(0)`$, the upper critical field at finite $`\gamma _{imp}`$ normalized on its clean limit value, can be approximated by the BCS formula. We solved Eqs. 1-5 for Einstein spectra. The results are shown in Fig. 2. For comparison the ratio of the BCS clean and dirty limit expressions

$$\frac{H_{c2}(0,\gamma _{imp})}{H_{c2}^{clean}(0,0)}1+\frac{3\gamma _{imp}}{\pi e^2T_c(1+\lambda )}=1+\frac{0.13\gamma _{imp}}{T_c(1+\lambda )},$$
(20)
is depicted too.

One realizes that this simple BCS-type relationship holds in the moderate strongly coupled case, too.

To summarize, for nearly isotropic single band metals the upper critical field at low temperature can be estimated with high accuracy by rather simple semi-analytical formulas Eqs. (12-15) and Eq. (20).

###### Acknowledgements.

The authors thank H. Eschrig, W. Weber, W.E. Pickett, H. Rosner, A.A. Golubov, O.V. Dolgov, and E. Schachinger for discussions. Support from the DFG and the SFB 463 is gratefully acknowledged.

## A  An instructive example from MgB2

Recently Manske et al.  suggested that experimental data for the novel superconductor MgB2 which we interpreted in terms of a multi-component gap approach , can be also described within the standard isotropic single-band Eliashberg model using Eq. (12). They reported 2$`\mathrm{\Delta }_0/k_BT_c4.1`$ and H$`{}_{c2}{}^{}(0)`$= 14 T in seemingly good agreement with experimental data for $`H_{c2}(0)`$. The other reported quantities are $`\omega _{ln}`$=30 meV, $`T_c`$=30 K. Using their input (material) parameters presented in that paper we checked their calculations and find that their model gives actually $`\omega _{ln}`$=53 meV, $`T_c`$=26 K, 2$`\mathrm{\Delta }_0/k_BT_c=`$3.8, and $`H_{c2}(T=0)`$ = 1.2 T in sharp contrast with their set mentioned above. Thus, at first, we confirm our earlier result  that the standard ISB model can not be applied to MgB2. At second, we note that the use of formulas written in practical units might be helpful to avoid such incorrect estimations.


text:
# Orientational and induced contributions to the depolarized Rayleigh spectra of liquid and supercooled ortho-terphenyl

## I INTRODUCTION

Depolarized light scattering (DLS) spectroscopy has been proved to be a valuable tool to explore the dynamical properties of molecular fluids Pecora76 . In the case of supercooled and glass forming liquids, DLS has been used by several researchers with the aim to elucidate the dynamical mechanisms underlying the liquid-glass transition Tao91 ; Li92 ; Du94 ; Wuttke94 ; Pick94 ; Lebon95 ; Alba95 . However, the uncertainties in the scattering mechanisms giving rise to the Raman spectra, and the consequent hypotheses that have been introduced to interpret the experiments, leave open the problem of a reliable analysis.

In some glass forming liquids, DLS spectra have been interpreted as arising primarily from interaction-induced mechanisms — namely dipole-induced-dipole (DID) — and so they have been related directly to the dynamics of the density fluctuations and compared with the outcomings of mode-coupling theories (MCT) Goetze92 . Following this line, Cummins et al. Li92  have interpreted the spectra of salol as arising entirely from the DID mechanism; in a more recent work Cummins96 , however, the authors assume that orientational contributions dominate the DLS spectra of salol at least up to $`4000`$ GHz, and the connection with the density fluctuations dynamics has to rely on a strong coupling between rotational and translational degrees of freedom. The situation is similar also for other systems. In the case of an other prototype of fragile glass-forming liquid, the ortho-terphenyl (OTP), Patkoswski et al. Pecora97  state that the low frequency part of the spectrum, up to about $`10`$ GHz, is due to collective reorientation, while at higher frequency the DID contribution is dominating.

We think that a careful investigation of the scattering mechanisms which contribute to DLS spectra is needed in order to clarify what type of information is possible to extract from the experimental data, and to ascertain the connections with the density fluctuation correlators treated by MCT.

In the present work we investigate the low frequency DLS spectra of liquid OTP for temperatures above and close to the MCT critical temperature $`T_c`$. We use the new realistic intra- and inter-molecular potential model set up by some of us very recently Mossa00 ; Mossa01 ; soundwaves ; fast . Various single particle correlation functions have already been studied through classical molecular dynamics (MD) simulations, yielding noticeable results. It is now possible to combine realistic dynamical configurations with plausible polarizability models, and try to discriminate among the different hypotheses on the origin of the different contributions to DLS experimental spectra.

The paper is organized as follows: Sec. II is a brief recall of our potential model and of the methods used to produce the dynamical configurations. In Sec. III we recall the main polarizability models that have been used so far to calculate the DLS spectra of simple molecular liquids; moreover, we show how they can be used to estimate the DLS spectra for our realistic flexible model. The computational details are treated in Sec. IV, while the results and a discussion are presented in Sec. V. In Sec. VI we address some conclusions.

## II THE MOLECULAR MODEL

In our flexible model Mossa00  the OTP molecule is constituted by three rigid hexagons (phenyl rings) of side $`L_a=0.139`$ nm. Two adjacent vertices of the parent (central) ring are bonded to one vertex of the two side rings by bonds whose length at equilibrium is $`L_b=0.15`$ nm. Each vertex of the hexagons is thought to be occupied by a fictious atom of mass $`M_{CH}=13`$ a.m.u. representing a carbon-hydrogen (C-H) pair. In the isolated molecule equilibrium configuration, the two lateral rings lie in planes that form an angle of about 54o with respect to the central ring’s plane. The three rings of a given molecule interact among themselves by an intramolecular potential $`V_{intra}`$. This potential is chosen in such a way to preserve the molecule from dissociation, to give the correct relative equilibrium positions for the three phenyl rings, and to represent at best the isolated molecule vibrational spectrum. In particular, it is written in the form $`V_{intra}=_kc_kV_k(𝒓)`$, where each term $`V_k(𝒓)`$ controls a particular degree of freedom; the actual values of the coupling constants $`c_k`$ have been determined in order to have a realistic isolated molecule vibrational spectrum. Several internal motions have been taken into account, like the stretching along the ring-ring bonds and between the side rings, and the rotation of the lateral rings along the ring-ring bonds.

The intermolecular part of the potential, concerning the interactions among the rings pertaining to different molecules, is described by a site-site pairwise additive Lennard Jones (LJ) $`612`$ potential, each site corresponding to one of the six hexagons vertices. The details of the intramolecular and intermolecular interaction potentials, together with the values of the potential parameters, are reported in Ref. Mossa00 .

It is worth noting that previous studies of the temperature dependence of the self diffusion constant Mossa00  and of the structural ($`\alpha `$) relaxation times Mossa00 ; Mossa01 , indicate that this model is capable to quantitatively reproduce the dynamical behavior of the real system, but the actual simulated thermodynamical point has to be shifted by $``$ 20 K upward. In the following, when we compare the simulation results with the experiments, the reported MD temperatures are rescaled by such an amount.

## III POLARIZABILITY MODELS

In a liquid composed of $`N`$ optical anisotropic units (a unit can be the entire molecule, a group of atoms in the molecule, or a single atom inside the molecule), characterized by a permanent polarizability tensor $`𝜶`$, the classical low frequency DLS spectrum in the dipole approximation is proportional — apart from a trivial frequency factor — to the Fourier transform of the time correlation function of the traceless tensorial part $`𝚷_2`$ of the collective polarizability $`𝚷`$. $`𝚷`$ can be approximated by the sum of two terms: the first, $`𝚷^M`$, is the sum of all the permanent polarizabilities dependent on the orientational variables $`𝑸_i`$ of the units; the second, $`𝚷^I`$, is due to all the interaction induced contributions, and its leading part can be written in term of the dipole propagator tensor $`𝑻^{(2)}(i,j)=\mathbf{}^2R_{ij}^1`$ (where $`R_{ij}`$ is the distance between the i-th and j-th units):

$$𝚷=𝚷^M+𝚷^I$$
(1)
$$𝚷^M=\underset{i}{}\left\{𝜶_i(𝑸_i)\right\}=\underset{i}{}(\alpha \mathrm{𝟏}+\frac{2}{3}\gamma 𝑸_i)$$
(2)
$`𝚷^I`$ $`=`$ $`{\displaystyle \underset{i}{}}{\displaystyle \underset{j}{}}𝜶_i𝑻^{(2)}(i,j)𝜶_j`$
$`+`$ $`{\displaystyle \underset{i}{}}{\displaystyle \underset{j}{}}{\displaystyle \underset{k}{}}𝜶_i𝑻^{(2)}(i,j)𝜶_j𝑻^{(2)}(j,k)𝜶_k`$
$`+`$ $`\mathrm{}`$
Here $`𝚷^M`$ is written for units with symmetric top symmetry, $`\alpha `$ and $`\gamma `$ are the isotropic and anisotropic polarizabilities, and $`𝑸_{\alpha \beta }=(3/2)\widehat{𝐮}_\alpha \widehat{𝐮}_\beta (1/2)𝜹_{\alpha \beta }`$, where $`\widehat{𝐮}`$ is a unit vector along the symmetry axis.

Usually only the first order DID is considered in Eq. (III), the second order DID being sometimes completely disregarded. The relative importance of the higher order DID contributions with respect to the first one is dependent on the strength of the permanent polarizability tensor, and on the minimum approach distances of the units Birnbaum85 . However, it is well known from the study of noble gas systems, that at short distances, when high order contributions become important, also other multi-pole and quantum electron correlation effects have to be considered. These terms are usually found to be of opposite sign respect to the DID contribution Dacre82 ; Hunt85 . Empirical diatomic induced polarizabilities have negative corrections at short distances for all noble gases Barocchi85 , and only for gaseous mercury a small positive correction to the second order DID has been used to fit the experimental spectra Sampoli95 . From these considerations, in the present work we discuss only the contributions from the first and second order DID.

We want to underline that, in the case of OTP, the choice of the unit is not so obvious as for monatomic fluids or simple molecular fluids such as $`N_2`$. Thus, the subsequent choices are based on the following considerations. Even for simple molecular systems, like $`CO_2`$ or $`CS_2`$ fluids, we can consider as unit the entire molecule, each atom, or the peripheral (most polarizable) atoms. In the case more units are pertaining to the same molecule, these units are at short distance each other, so their induced contributions are tentatively treated in a more refined scheme. The major attempt in this way has been made by Applequist Applequist72 . His formalism, introduced to reproduce the molecular polarizabilities with transferable atomic polarizabilities, is equivalent to take into account the DID at all orders. Indeed the distances are so short that the major contributions come from higher order DID interactions. Irrespective to the relative success of the method, various authors Olson78 ; Thole81 ; Applequist93  have modified the scheme adding mono-pole polarizability, and/or using non isotropic atomic polarizability, and/or separating atoms of the same species on the base of chemical bonds. Only a few attempts have been made so far to use the Applequist formalism to calculate the experimental spectra Birnbaum85 , and with doubtful improvements. Thus, at present we are not confident in using classical dipole interactions at short distances.

So far we have not tried to use a complex polarizability scheme for our molecular model, and we have chosen to adopt two models that can give a rough estimate of a lower and upper limit of the induced interactions. In our potential model, three six sites rigid rings form the molecule and this suggests to consider as units the rings themselves (R scheme), or the six sites of each ring (S scheme). We have always neglected the effects on the polarizability due to the change of one (or two) H-C with a C-C bond. In the R scheme, the polarizability tensor is taken equal to that of benzene ($`C_6H_6`$). In the S scheme, we have simply divided by six the polarizability tensor of benzene, and we have neglected the DID contributions coming from atoms pertaining to the same ring. The induced contributions grow up at least with the sixth power of the inverse of the distance, so we expect the R scheme to be a lower limit to the induced contributions, while the S scheme to be an upper one. Indeed, in the S scheme the mean distances are shorter than in R scheme. We want to underline that, if in the S scheme the DID interactions inside the ring were taken into account, this would have reduced the polarizabilities of the six sites.

Using a notation similar to that of Stassen et al. Ladanyi94 , we can work out the collective polarizability correlation function for the depolarized scattering:

$$C(t)=\frac{1}{10V}𝚷_2(t)\mathbf{:}𝚷_2(0),$$
(4)
where $`V`$ is the volume occupied by the $`N`$ units. $`C(t)`$ can be divided in three terms, namely the orientational term $`C_{or}(t)`$, the interaction-induced or DID term $`C_{ii}(t)`$, and the cross contribution term $`C_{cr}(t)`$:

$$C(t)=C_{or}(t)+C_{ii}(t)+C_{cr}(t),$$
(5)
with

$`C_{or}(t)`$ $`=`$ $`{\displaystyle \frac{2}{45V}}\gamma ^2𝑸(0)\mathbf{:}𝑸(t)`$
$`C_{ii}(t)`$ $`=`$ $`{\displaystyle \frac{1}{10V}}𝚷_2^I(0)\mathbf{:}𝚷_2^I(0)`$ (6)
$`C_{cr}(t)`$ $`=`$ $`{\displaystyle \frac{1}{15V}}\gamma [𝑸(0)\mathbf{:}𝚷_2^I(t)+𝚷_2^I(0)\mathbf{:}𝑸(t)].`$
Here $`𝑸=_i𝑸_i`$ and all the sums are extended over the $`N`$ units.

Although the importance of the three terms in Eq. (6) has been found similar in various systems Birnbaum85 , the cross term $`C_{cr}(t)`$ has been neglected, without sound arguments, in various works on glass-forming liquids. The integrated intensities of the orientational contribution, i.e., the value at $`t=0`$ of the correspondent correlation function, can be written as:

$$C_{or}(t=0)=\frac{N}{15V}\gamma ^2(1+f_2),$$
(7)
where $`g_2=1+f_2`$ is the static angular pair correlation factor between our units, defined as Gershon69

$$g_2\frac{2}{3N}\underset{i}{}\underset{ji}{}𝑸_i(0)\mathbf{:}𝑸_j(0).$$
(8)
It is well known that, if the units are spherically symmetric ($`\gamma =0`$), the orientational and cross contributions do vanish, as in the case of DLS from monatomic fluids. In both R and S schemes, we expect a value of $`g_2`$ rather different from $`1`$. Indeed, also in the R scheme we have a strong orientational correlation between different units (rings pertaining to the same molecule). This is quite different from the case of simple molecular fluids, such as $`N_2`$, where only very small orientational correlations exist between different molecules, even in the liquid phase near the melting point. If all the rings of OTP molecules were in the equilibrium positions, while there was no correlation between the orientation of different molecules, we can calculate the $`g_2`$ factor for both R and S models. Using the equilibrium values of the cosines between the normals to the ring planes ($`𝐧_1𝐧_2=𝐧_1𝐧_3=0.588`$, and $`𝐧_2𝐧_3=0.673`$, with the index $`1`$ standing for the central ring Mossa00 ), we have

$$g_2^{R,eq}1.14,g_2^{S,eq}=6\times g_2^{R,eq}6.84.$$
(9)
Obviously, the obtained $`g_2`$ factors make the orientational contribution integrated intensity — in this idealized condition — independent of the adopted scheme. Since the relation $`g_2^{R,eq}=g_2^{S,eq}/6`$ holds always, in the following we refer simply to $`g_2`$ in the R scheme. Further, we can evaluate the average value of the analogous of $`g_2`$ for the rings pertaining to the same molecules, i.e.

$$K_2=\frac{3}{2N}\underset{i}{}\underset{ji}{}\mathrm{cos}^2(\theta _{ij})1/3,$$
(10)
where the sum is extended over the rings of a molecule, $`\theta _{ij}`$ is the angle between the normals of the i-th and the j-th ring, and $``$ means a configuration or time average. The value of $`K_2`$ for the isolated molecule at equilibrium is always $`K_2^{eq}1.14`$.

## IV COMPUTATIONAL DETAILS

We study a system composed by $`108`$ OTP molecules ($`324`$ rings, $`1944`$ LJ interaction sites) enclosed in a cubic box with periodic boundary condition. The MD runs are performed in the microcanonical (NVE) ensemble. To integrate the equations of motion we treats each ring as a separate rigid body, identified by the position of its center of mass $`𝑹_i`$ and by its orientation, expressed in terms of quaternions $`𝒒_i`$ allen . The standard Verlet leap-frog algorithm allen  has been implemented to integrate the translational motion while, for the most difficult orientational part, a refined algorithm has been used ruosam . The integration time-step is $`\mathrm{\Delta }t`$=2 fs, which gives rise to an overall energy conservation better than 0.01 % of the kinetic energy.

We consider two series of runs. For temperature $`T=420`$ K, to be compared with the experimental results, we perform one run $`24`$ ns long with a saving time of $`1`$ ps; using windows $`800`$ ps wide we achieve a resolution of 0.04 cm-1. For the temperatures $`T=`$ 280, 290, 300, 310, 320, 330, 350, 370, 390, 410 and 430 K we run for $`640`$ ps with a saving time of $`0.04`$ ps; using windows of $`320`$ ps we reach a resolution of 0.1 cm-1.

In the R scheme, the components of the polarizability tensor (in the molecular fixed frame) are $`\alpha _{}=12.31`$ $`\AA ^3`$, $`\alpha _{}=6.35`$ $`\AA ^3`$, $`\alpha =1/3(\alpha _{}+2\alpha _{})=10.32`$ $`\AA ^3`$, $`\gamma =\alpha _{}\alpha _{}=5.96`$ $`\AA ^3`$, where $``$ stands for orthogonal to the phenyl ring’s plane, i.e. parallel to the symmetry axis. These values are taken from the polarizability tensor of the benzene hirsch . For the S scheme, to each site have been attributed the previous values divided by $`6`$ and the same orientation.

## V RESULTS AND DISCUSSION

In Fig. 1 the DID spectrum at first order is reported in the liquid phase at $`420`$ K for both S (Fig. 1(a)) and R (Fig. 1(b)) schemes. The dashed lines refer to the obtained resolution, which depends on the time length of the MD run. In the insets the same data, rescaled to the peak intensity, are shown in semi-logarithmic (left) and logarithmic (right) scale in order to emphasize the power law behavior of the tails.

As expected, the overall intensity in the S scheme is much higher than the one in the R scheme. On the contrary, the shape is very similar, although the relative intensity of the spectral wings (at 10 $`cm^1`$) with respect to the peak intensity is about three times higher in the R scheme. As a consequence the absolute wing intensities are comparable. On the overall, the shape is similar to the induced contribution from heavy noble gases, i.e., an exponential decay of the form $`\mathrm{exp}(\omega /\omega _o)`$ with $`\omega _o`$ of the order of 2 $`cm^1`$.

Only for the S scheme the second order DID is of some importance, so in Fig. 2 the corresponding spectrum (Fig 2(b)) is compared with the first order DID (Fig 2(a)). At all frequencies the second order contribution is a relatively small fraction of the first one; above 0.25 cm-1 it is less than about 10$`\%`$, so the DID’s at higher order can be safely neglected.

The sum of the first and second order DID, and the orientational spectra in the S scheme are compared in Fig. 3(a) and (b) respectively. As we can see, the relative shapes and intensities in this case are quite similar (apart from the shape of the peak at frequency comparable to the spectral resolution, where the simulation statistical errors are large and prevent any reliable comparison). We want to stress that no time scale separation is detectable between translational and orientational dynamics. This is reflected also in the shape and high intensity of the cross contribution; at this temperature, indeed, the spectra of orientational, DID and cross contributions practically superimpose each other, as shown in Fig. 4.

In the case of the R scheme, the situation is quite different. Beyond the smaller relative importance of the DID and cross terms, at high frequency (above 5 cm-1) the spectrum is dominated by the DID contributions, even if at 10 cm-1 the ratio of DID, cross and orientational contributions is not so high, being $`4:2:1`$ (see Fig. 5).

Again, even in R scheme our simulations are in poor agreement with the assumptions made by Patkowski et al. Pecora97  about the spectral separation between orientational and DID contributions. Indeed, it is evident from Fig. 5 that no time scale separation can be effective and the cross term cannot be neglected.

The resulting — total — simulated DLS spectra for the two schemes are reported in Fig. 6(a). In Fig. 6(b) we show, in double logarithmic scale, a comparison of the two line shapes with the experimental spectrum at $`444`$Angelini99 . The agreement among the sets of data is quite good, considering the approximations we have made in the dynamical and polarizability model. This shape comparison gives some preference to the S scheme, but it is hard to really discriminate between these two limiting polarizability models on this basis. R and S DLS spectra differ essentially in intensity rather then in shape, and some help would come from an absolute intensity comparison; unfortunately, the OTP experimental absolute intensity has not been calculated so far. Anyway, the large uncertainties usually present in both experimental and simulated determinations of DLS absolute spectral intensities, could not allow this kind of comparison.

In Fig. 7 we plot the temperature dependence of the relative integrated intensities of the various spectral contributions. We see that the relative intensities do not show any significant trend with temperature, apart from a tendency of the orientational part to increase at the lowest investigated temperatures. The increase has to be attributed to a change in the relative orientation of the rings, i.e., to an increasing of $`g_2`$. This is clearly seen in Fig. 8 where $`g_2`$ (main panel) and $`K_2`$ Inset) are plotted as a function of temperature. It is interesting to note that also $`K_2`$ increases on decreasing temperature, being less than the reference value $`K_2^{eq}`$ 1.14 at high temperatures and more than that value at low temperatures. On the basis of the value of the angles between the symmetric top axis of the rings, $`K_2`$ increases fast if there is a spread of $`𝐧_1𝐧_2`$ and $`𝐧_1𝐧_3`$, but decreases with the spread of $`𝐧_2𝐧_3`$. The distribution of angle cosines is reported in Fig. 6 of Ref. Mossa00 . At high temperatures, the large spread of $`𝐧_2𝐧_3`$ is, anyway, able to decrease $`K_2`$ under $`K_2^{eq}`$, but at low temperature the situation is reversed by the spread of $`𝐧_1𝐧_2`$ and $`𝐧_1𝐧_3`$.

We expect a similar situation to hold for the DLS of a large class of molecular glass forming liquids: the DLS would be a mixture of orientational, DID and cross contributions in the entire low frequency range, with no significant time scale separation. Further, the better agreement with the experimental results of the S scheme in the case of OTP, underlines the importance to take into account the internal degrees of freedom to obtain a realistic description of the DLS of glass forming liquids consisting of large flexible molecules.

## VI CONCLUSIONS

In this paper we have studied, by means of molecular dynamics simulations, the orientational and induced contributions to the low frequency depolarized Rayleigh spectra of supercooled ortho-terphenyl. We have used a realistic flexible intramolecular model recently introduced by some of us, taking into account the most important internal degrees of freedom of the OTP molecule. Two polarizability models have been introduced, each of them considering a different scattering unit. In the ring’s model R, we have assigned to each phenyl ring the polarizability of the benzene. In the site’s model S, we have assigned to the sites of each ring the same polarizability divided by six. This procedure has allowed us to study the single contributions to the DLS spectra in both cases. Our main findings are the following: i) Although in the two schemes the intensities of the DID contributions are very different, their overall shape is very similar; ii) The second order DID is at all frequencies already a relatively small fraction of the first order contributions, so that all the higher induced terms can be safely neglected; iii) For the S model first order DID and orientational contributions are very similar in both shape and intensity; iv) In both models the cross correlation between induced and orientational terms cannot be neglected. This fact is in striking contrast with the analysis of the experimental data of Ref. Pecora97  and support the conclusion that: v) No time scale separation is present between DID and orientational contribution. In other words we expect that, similarly to the present case, for a broad class of molecular glass forming liquids the DLS spectra would be a superposition of DID, orientational and mixed contributions, and none of them should be disregarded. Finally: vi) the better agreement of the S scheme calculated spectra with the experimental results underlines the importance of taking into account the molecular internal degrees of freedom in order to obtain a realistic description of complex molecular liquids.

ACKNOWLEDGEMENTS

This work was supported by MURST PRIN 2000.