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# Quantum groups and interacting quantum fields

## 1 Introduction

Quantum groups appear to be a powerful tool for quantum field calculations. First, Fauser pointed out a connection between Wick’s theorem and the concept of Laplace pairing introduced by Rota and his school . In reference , we showed that the Laplace pairing is a quantum group concept and we solved quantum field problems with quantum group tools. The quantum group approach to free scalar fields was presented in detail in . Here we show that quantum groups can also deal with interacting fields. In the first part, a bialgebra $`S(C)`$ is built from a cocommutative coalgebra $`C`$, the symmetric product of $`S(C)`$ is twisted by a Laplace pairing and general identities are derived. In the second part, these identities are translated into the language of quantum field theory.

## 2 The abstract setting

If $`C`$ is a cocommutative coalgebra with coproduct $`\mathrm{\Delta }^{}`$ and counit $`\epsilon ^{}`$, the symmetric algebra $`S(C)=_{n=0}^{\mathrm{}}S^n(C)`$ can be equipped with the structure of a bialgebra. The product of the bialgebra $`S(C)`$ is the symmetric product (denoted by $``$) and its coproduct $`\mathrm{\Delta }`$ is defined on $`S^1(C)=C`$ by $`\mathrm{\Delta }a=\mathrm{\Delta }^{}a`$ and extended to $`S(C)`$ by $`\mathrm{\Delta }1=11`$ and $`\mathrm{\Delta }(uv)=u{}_{\left(1\right)}{}^{}v{}_{\left(1\right)}{}^{}u{}_{\left(2\right)}{}^{}v_{\left(2\right)}`$. The elements of $`S^n(C)`$ are said to be of degree $`n`$. The counit $`\epsilon `$ of $`S(C)`$ is defined to be equal to $`\epsilon ^{}`$ on $`S^1(C)=C`$ and extended to $`S(C)`$ by $`\epsilon (1)=1`$ and $`\epsilon (uv)=\epsilon (u)\epsilon (v)`$. It can be checked recursively that $`\mathrm{\Delta }`$ is coassociative and cocommutative and that $`\epsilon (u{}_{\left(1\right)}{}^{})u{}_{\left(2\right)}{}^{}=u{}_{\left(1\right)}{}^{}\epsilon (u{}_{\left(2\right)}{}^{})=u`$. Thus, $`S(C)`$ is a commutative and cocommutative bialgebra which is graded as an algebra.

A Laplace pairing is a bilinear map $`(|)`$ from $`S(C)\times S(C)`$ to the complex numbers such that $`(1|u)=(u|1)=\epsilon (u)`$, $`(uv|w)=(u|w{}_{\left(1\right)}{}^{})(v|w{}_{\left(2\right)}{}^{})`$ and $`(u|vw)=(u{}_{\left(1\right)}{}^{}|v)(u{}_{\left(2\right)}{}^{}|w)`$ for any $`u`$, $`v`$ and $`w`$ in $`S(C)`$. The powers $`\mathrm{\Delta }^k`$ of the coproduct are defined by $`\mathrm{\Delta }^0a=a`$, $`\mathrm{\Delta }^1a=\mathrm{\Delta }a`$ and $`\mathrm{\Delta }^{k+1}a=(\mathrm{Id}\mathrm{}\mathrm{Id}\mathrm{\Delta })\mathrm{\Delta }^ka`$. Their action is denoted by $`\mathrm{\Delta }^ka=a{}_{\left(1\right)}{}^{}\mathrm{}a_{\left(k+1\right)}`$.

From the definition of the Laplace pairing and of the powers of the coproduct a straighforward recursive proof yields, for $`u^i`$ and $`v^j`$ in $`S(C)`$

$`(u^1\mathrm{}u^k|v^1\mathrm{}v^l)`$ $`=`$ $`{\displaystyle }{\displaystyle \underset{i=1}{\overset{k}{}}}{\displaystyle \underset{j=1}{\overset{l}{}}}(u{}_{\left(j\right)}{}^{i}|v{}_{\left(i\right)}{}^{j}).`$ (1)
For example $`(uvw|st)=(u{}_{\left(1\right)}{}^{}|s{}_{\left(1\right)}{}^{})(u{}_{\left(2\right)}{}^{}|t{}_{\left(1\right)}{}^{})(v{}_{\left(1\right)}{}^{}|s{}_{\left(2\right)}{}^{})(v{}_{\left(2\right)}{}^{}|t{}_{\left(2\right)}{}^{})(w{}_{\left(1\right)}{}^{}|s{}_{\left(3\right)}{}^{})(w{}_{\left(2\right)}{}^{}|t{}_{\left(3\right)}{}^{})`$.

A Laplace pairing is entirely determined by its value on $`C`$. In other words, once we know $`(a|b)`$ for all $`a`$ and $`b`$ in $`C`$, equation (1) enables us to calculate the Laplace pairing on $`S(C)`$.

The Laplace pairing induces a twisted product $``$ on $`S(C)`$ by $`uv=(u{}_{\left(1\right)}{}^{}|v{}_{\left(1\right)}{}^{})u{}_{\left(2\right)}{}^{}v_{\left(2\right)}`$. By applying the counit to both sides of this equality we obtain the useful relation

$`\epsilon (uv)`$ $`=`$ $`(u|v)`$ (2)
If we follow the proofs given in  we can easily show that the twisted product is associative, $`1`$ is the unit of $``$, $`(uv|w)=(u|vw)`$ and $`\mathrm{\Delta }(uv)=u{}_{\left(1\right)}{}^{}v{}_{\left(1\right)}{}^{}u{}_{\left(2\right)}{}^{}v_{\left(2\right)}`$. If we use the last identity recursively, we obtain for $`u^1,\mathrm{},u^k`$ in $`S(C)`$

$`\mathrm{\Delta }(u^1\mathrm{}u^k)`$ $`=`$ $`{\displaystyle }u{}_{\left(1\right)}{}^{1}\mathrm{}u{}_{\left(1\right)}{}^{k}u{}_{\left(2\right)}{}^{1}\mathrm{}u{}_{\left(2\right)}{}^{k}.`$ (3)
This leads us to the important relation

$`u^1\mathrm{}u^k`$ $`=`$ $`{\displaystyle }\epsilon (u{}_{\left(1\right)}{}^{1}\mathrm{}u{}_{\left(1\right)}{}^{k})u{}_{\left(2\right)}{}^{1}\mathrm{}u{}_{\left(2\right)}{}^{k}.`$ (4)
To show (4) recursively, we observe that it is true for $`k=2`$. We denote $`U=u^1\mathrm{}u^k`$ and we assume that the property is true up to the twisted product of $`k`$ terms. Since, by definition, $`Uv=(U{}_{\left(1\right)}{}^{}|v{}_{\left(1\right)}{}^{})U{}_{\left(2\right)}{}^{}v_{\left(2\right)}`$, equation (3) yields $`Uv=(u{}_{\left(1\right)}{}^{1}\mathrm{}u{}_{\left(1\right)}{}^{k}|v{}_{\left(1\right)}{}^{})u{}_{\left(2\right)}{}^{1}\mathrm{}u{}_{\left(2\right)}{}^{k}v_{\left(2\right)}`$ and the result follows for the twisted product of $`k+1`$ terms because of equation (2).

Finally, we shall prove the second important identity

$`\epsilon (u^1\mathrm{}u^k)`$ $`=`$ $`{\displaystyle }{\displaystyle \underset{i=1}{\overset{k1}{}}}{\displaystyle \underset{j=i+1}{\overset{k}{}}}(u{}_{\left(j1\right)}{}^{i}|u{}_{\left(i\right)}{}^{j})={\displaystyle }{\displaystyle \underset{j>i}{}}(u{}_{\left(j1\right)}{}^{i}|u{}_{\left(i\right)}{}^{j}).`$ (5)
For $`k=2`$, equation (5) is true because of equation (2). Assume that it is true up to $`k`$ and denote $`U=u^1\mathrm{}u^k`$. From equation (2) and $`U=\epsilon (U{}_{\left(1\right)}{}^{})U_{\left(2\right)}`$ we find

$`\epsilon (Uu^{k+1})`$ $`=`$ $`{\displaystyle }\epsilon (U{}_{\left(1\right)}{}^{})(U{}_{\left(2\right)}{}^{}|u^{k+1})={\displaystyle }\epsilon (u{}_{\left(1\right)}{}^{1}\mathrm{}u{}_{\left(1\right)}{}^{k})(u{}_{\left(2\right)}{}^{1}\mathrm{}u{}_{\left(2\right)}{}^{k}|u^{k+1})`$
$`=`$ $`{\displaystyle }\epsilon (u{}_{\left(1\right)}{}^{1}\mathrm{}u{}_{\left(1\right)}{}^{k}){\displaystyle \underset{n=1}{\overset{k}{}}}(u{}_{\left(2\right)}{}^{n}|u{}_{\left(n\right)}{}^{k+1}),`$
where we used equations (3) and (1). Equation (5) is true up to $`k`$ thus

$`\epsilon (u^1\mathrm{}u^{k+1})`$ $`=`$ $`{\displaystyle }{\displaystyle \underset{i=1}{\overset{k1}{}}}{\displaystyle \underset{j=i+1}{\overset{k}{}}}(u{}_{\left(j1\right)}{}^{i}|u{}_{\left(i\right)}{}^{j}){\displaystyle \underset{n=1}{\overset{k}{}}}(u{}_{\left(k\right)}{}^{n}|u{}_{\left(n\right)}{}^{k+1})`$
$`=`$ $`{\displaystyle }{\displaystyle \underset{i=1}{\overset{k1}{}}}{\displaystyle \underset{j=i+1}{\overset{k+1}{}}}(u{}_{\left(j1\right)}{}^{i}|u{}_{\left(i\right)}{}^{j})(u{}_{\left(k\right)}{}^{k}|u{}_{\left(k\right)}{}^{k+1})={\displaystyle }{\displaystyle \underset{i=1}{\overset{k}{}}}{\displaystyle \underset{j=i+1}{\overset{k+1}{}}}(u{}_{\left(j1\right)}{}^{i}|u{}_{\left(i\right)}{}^{j})`$
and the identity is proved for the twisted product of $`k+1`$ elements.

We considered the symmetric algebra $`S(C)`$, but the same results are obtained for the tensor algebra $`T(C)`$. A related construction was made by Hivert in .

## 3 Quantum fields

The previous construction is now applied to interacting quantum field theory. The scalar fields are defined by the usual formula

$`\varphi (x)`$ $`=`$ $`{\displaystyle \frac{\mathrm{d}𝐤}{(2\pi )^3\sqrt{2\omega _k}}\left(\mathrm{e}^{ipx}a(𝐤)+\mathrm{e}^{ipx}a^{}(𝐤)\right)},`$
where $`\omega _k=\sqrt{m^2+|𝐤|^2}`$, $`p=(\omega _k,𝐤)`$, $`a^{}(𝐤)`$ and $`a(𝐤)`$ are the creation and annihilation operators acting on the symmetric Fock space of scalar particles. Interacting fields are products of fields at the same point. Thus, we define the powers of fields $`\varphi ^n(x)`$ as the normal product of $`n`$ fields at $`x`$ (i.e. $`\varphi ^n(x)=:\varphi (x)\mathrm{}\varphi (x):`$). This definition is meaningful for all $`n>0`$ and is extended to $`n=0`$ by saying that $`\varphi ^0(x)`$ is the unit operator. In the following we shall consider the divided powers of fields defined by $`\varphi ^{(n)}(x)=\varphi ^n(x)/n!`$.

We consider the coalgebra $`𝒞`$ generated by $`\varphi ^{(n)}(x)`$, where $`x`$ runs over spacetime and $`n`$ goes from 0 to 3 for a $`\varphi ^3`$ theory and from 0 to 4 for a $`\varphi ^4`$ theory. We do not consider here the topology of this space. The coproduct of $`𝒞`$ is $`\mathrm{\Delta }\varphi ^{(n)}(x)=_{k=0}^n\varphi ^{(k)}(x)\varphi ^{(nk)}(x)`$ and its counit is $`\epsilon (\varphi ^{(n)}(x))=\delta _{n,0}`$. Scalar fields are bosons, so we work with the symmetric algebra $`S(𝒞)`$. The product of $`S(𝒞)`$ is the normal product of operators, which is commutative and denoted by $`:uv:`$. Notice that the counit is equal to the expectation value over the vacuum: $`ϵ(u)=0|u|0`$.

In $`S(𝒞)`$, the Laplace pairing is entirely determined by the value of $`(\varphi ^{(n)}(x)|\varphi ^{(m)}(y))`$, which is itself determined by the value of $`(\varphi (x)|\varphi (y))=G(x,y)`$ if we consider $`\varphi ^{(n)}(x)`$ as a product of fields. More precisely $`(\varphi ^{(n)}(x)|\varphi ^{(m)}(y))=\delta _{n,m}G(x,y)^{(n)}`$, where the right hand side is a divided power $`G(x,y)^{(n)}=(1/n!)G(x,y)^n`$. In general, $`G(x,y)`$ is a distribution. In quantum field theory we use two special cases: the Wightman function $`G_+(x,y)=0|\varphi (x)\varphi (y)|0`$ and the Feynman propagator $`G_F(x,y)=0|T(\varphi (x)\varphi (y))|0`$. As shown in , when the Laplace pairing is defined with $`G(x,y)=G_+(x,y)`$, the twisted product equals the operator product of fields. When it is defined with $`G(x,y)=G_F(x,y)`$ the twisted product equals the time-ordered product.

Notice that $`\mathrm{\Delta }^{k1}\varphi ^{(n)}(x)=\varphi ^{(m_1)}(x)\mathrm{}\varphi ^{(m_k)}(x)`$, with a sum over all nonnegative integers $`m_i`$ such that $`_{i=1}^km_i=n`$. Thus, we can specialize equation (1) to our coalgebra $`𝒞`$

$`(:\varphi ^{(n_1)}(x_1)\mathrm{}\varphi ^{(n_k)}(x_k):|:\varphi ^{(p_1)}(y_1)\mathrm{}\varphi ^{(p_l)}(y_l):)`$ $`=`$ $`{\displaystyle \underset{M}{}}{\displaystyle \underset{i=1}{\overset{k}{}}}{\displaystyle \underset{j=1}{\overset{l}{}}}G(x_i,y_j)^{(m_{ij})},`$ (6)
where the sum is over all $`k\times l`$ matrices $`M`$ of nonnegative integers $`m_{ij}`$ such that $`_{j=1}^lm_{ij}=n_i`$ and $`_{i=1}^km_{ij}=p_j`$. This formula was given in reference .

Equation (4) applied to $`𝒞`$ yields a classical result of quantum field theory

$`\varphi ^{(n_1)}(x_1)\mathrm{}\varphi ^{(n_k)}(x_k)`$ $`=`$ $`{\displaystyle \underset{i_1=0}{\overset{n_1}{}}}\mathrm{}{\displaystyle \underset{i_k=0}{\overset{n_k}{}}}0|\varphi ^{(i_1)}(x_1)\mathrm{}\varphi ^{(i_k)}(x_k)|0`$ (7)
$`:\varphi ^{(n_1i_1)}(x_1)\mathrm{}\varphi ^{(n_ki_k)}(x_k):.`$
This equation was published by Epstein and Glaser for the operator product and the time-ordered product . It is now often used in the Epstein-Glaser approach to renormalisation (see e.g. ). Equation (4) is clearly more compact and also more general than equation (7): it is still valid if the elements of $`𝒞`$ (i.e. $`\varphi ^{(n_i)}(x_i)`$) are replaced by elements of $`S(𝒞)`$.

Finally, if we specialize equation (5) to $`𝒞`$ we obtain

$`0|\varphi ^{(n_1)}(x_1)\mathrm{}\varphi ^{(n_k)}(x_k)|0`$ $`=`$ $`{\displaystyle \underset{M}{}}{\displaystyle \underset{i=1}{\overset{k1}{}}}{\displaystyle \underset{j=i+1}{\overset{k}{}}}G(x_i,x_j)^{(m_{ij})},`$ (8)
where the sum is over all symmetric $`k\times k`$ matrices $`M`$ of nonnegative integers $`m_{ij}`$ such that $`_{j=1}^km_{ij}=n_j`$ and $`m_{ii}=0`$ for all $`i`$.

When the twisted product is the operator product, this expression was given by Brunetti, Fredenhagen and Köhler . Notice that (8) was proved here with a few lines of algebra, whereas the quantum field proof is combinatorial. As remarked by Rota, a great virtue of Hopf algebras is to replace combinatorics by algebra.

When the twisted product is the time-ordered product, equation (8) has a diagrammatic interpretation. The diagrammatic calculation of $`0|T\left(\varphi ^{(n_1)}(x_1)\mathrm{}\varphi ^{(n_k)}(x_k)\right)|0`$ would be: draw all diagrams that have $`k`$ vertices $`x_1`$ to $`x_k`$ and for which each vertex $`x_i`$ has $`n_i`$ edges. There is a one to one correspondence between these diagrams and the matrices $`M`$ satisfying the conditions stated above: $`m_{ij}`$ is the number of edges linking vertices $`x_i`$ and $`x_j`$. The condition $`m_{ii}=0`$ means that there is no tadpoles. The graphs are not directed (i.e. the edges do not carry arrows) because the Feynman propagator $`G_F(x,y)`$ is symmetric (i.e. $`G_F(y,x)=G_F(x,y)`$).

## 4 Perspective

This paper shows that non trivial results of quantum field theory can be derived easily from a general quantum group construction. A word of caution must be added concerning equation (8). When the twisted product is the operator product, equation (8) is valid. It defines a state on $`T(𝒞)`$ by $`\omega (a_1\mathrm{}a_k)=ϵ(a_1\mathrm{}a_k)`$ and the Laplace pairing is a positive semidefinite form on $`T(C)\times T(C)`$. However, when the twisted product is the time-ordered product, equation (8) is ill-defined because the powers $`G_F(x,y)^n`$ are singular products of distributions and renormalisation is necessary. The first step of a “quantum group” renormalisation of scalar field theories was done in . It uses the fact that equation (7) is still valid in renormalised quantum field theory, so that the Laplace pairing must be replaced by a Sweedler’s 2-cocycle  in the definition of a renormalised time-ordered product. To go further, we can implement renormalisation abstractly by starting from a bialgebra $`B`$ and putting a bialgebra structure on the “squared” tensor algebra $`T(T(B)^+)`$ . This construction is inspired by Pinter’s approach to renormalization  and is related to the Faà di Bruno bialgebra of composition of series . These results will be presented in a forthcoming publication.

## 5 Acknowledgements

I am very grateful to Robert Oeckl for his comments on this paper and to Alessandra Frabetti for her enthusiastic support. This is IPGP contribution #0000.

## References


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# Numerical Results for Ground States of Spin Glasses on Bethe Lattices

## I Introduction

In this paper we study the ground state ($`T=0`$) properties of $`\pm J`$ spin glasses on $`k+1`$-Bethe lattices MP2 . The Bethe lattices in this case are $`r`$-regular graphsBollobas  with $`r=k+1`$. These are randomly connected graphs consisting of $`n`$ vertices in which each vertex has a fixed connectivity of $`k+1`$. This constraint contrasts with “random graphs” ER ; Bollobas  in which pairs of vertices are randomly connected, leading to a Poissonian distribution of connectivities around a mean of $`c`$; these graphs will be studied numerically elsewhere eo\_rg . We explore the large-$`n`$ regime of low-connectivity graphs, $`k+1=3,\mathrm{},26`$, which are of great theoretical interest as finite-connected, mean-field models for low-dimensional lattice spin glasses VB ; MPV . A great number of studies have focused on various aspects of this conceptually simple model to hone the complex mathematical techniques required to treat disordered systems MP1 ; MP2 ; PT ; MP ; Motti ; LG ; DG  or optimization problems MPZ ; Monasson ; Zecchina ; Franz ; WS ; Banavar . In this paper we will try to provide a independent numerical check on the validity and accuracy of those techniques.

Our results, in turn, reflect on the flexibility of the extremal optimization (EO) heuristic BoPe1 ; eo\_prl  in finding approximate but high-quality solutions for ground states of spin glasses on an arbitrary graphical structure in a reasonable computational time. These are often NP-hard optimization problems which are believed to require a computational effort that rises faster than any power of $`n`$ to obtain provably exact solutions GJ . Thus, exact methods as of yet are not able to provide results for large-$`n`$ problems, at least not with significant statistics Kobe , except for some special cases PA ; Rinaldi ; Liers . Furthermore, there is only a small number of capable approximate algorithms available for the study of $`T=0`$ properties of spin glasses Pal ; Hartmann ; HM , mostly restricted to $`d`$-dimensional lattice models, and EO provides a distinct alternative which will increase the confidence in the numerical results available. In previous papers, we have demonstrated the capabilities of EO in determining near-optimal solutions by reproducing existing results for $`3d`$ and $`4d`$ spin glasses and obtaining new results for the coloring problemeo\_prl ; eo\_col  and the graph partitioning problem eo\_perc ; BoPe1 ; BoPe2 . The results in this paper show that EO is not only capable of approximating ground states well but also of sweeping the entire configuration space efficiently to determine the degeneracy of ground states eo\_col . Unlike other methods, EO never “freezes” into local minima and proves to be limited only by the ability to store new ground states.

We find that our results for the ground state energies are consistent with the theoretical results of the one-step replica symmetry-broken (1RSB) solution of $`\pm J`$ spin glasses on $`k+1`$-connected Bethe lattices. Our numerical result for $`k+1=3`$ below clearly excludes the replica symmetric (RS) solution and are consistent with the 1RSB results MP2 . Beyond that our results suggest subtle differences between even and odd values of the connectivity $`k+1`$, with no obvious way to continue smoothly between them eo\_bethe . These oscillations may doom perturbative calculation for $`k+1\mathrm{}`$ PT ; LG . While the expectation has been raised that the entropy per spin of the ground states in this model should be vanishing for any $`k+1`$ PT , we find that the entropy is finite and decaying like $`1/(k+1)`$ for large, even $`k+1`$. For odd $`k+1`$ it is non-zero only for small values and may be vanishing already beyond some finite, odd connectivity.

In the following we first introduce the Bethe lattices we used in the numerical calculations. In Sec. III we briefly describe the EO algorithm which is amply discussed elsewhere eo\_prl ; CISE ; BoPe1 . In Sec. IV we present a few simulations to reproduce known results to gauge our procedure. In Sec. V we present our numerical results, followed by an extensive discussion in Sec. V.3. Some conclusions are presented in Sec. VI.

## II Spin Glasses on Bethe Lattices

Disordered spin systems on random graphs have been investigated as mean-field models for low-dimensional spin glasses or optimization problems, since variables are long-range connected yet have a small number of neighbors. Particularly simple are Bethe lattices of connectivity $`k+1`$ MP ; MP1 ; MP2 , also called fixed-valence or $`r`$-regular random graphs Banavar ; eo\_perc ; eo\_jam ; Bollobas . These are graphs consisting of $`n`$ vertices where each vertex possesses a fixed number $`k+1`$ of bonds with randomly selected other vertices. In comparison to the otherwise more familiar random graphs studied by Erdös and Reny ER ; Bollobas , Bethe lattices at a given $`n`$ and $`k`$ avoid fluctuations in the connectivities of vertices and in the total number of bonds.

There are slight variations in the generation of Bethe lattices. For instance, to add a bond one could choose at random two vertices of connectivities $`<k+1`$ to link until all vertices are $`k+1`$-connected. Instead, we have used the method described in Ref. Bollobas  to generate these graphs. Here, all the terminals on the vertices form a list of $`n(k+1)`$ independent variables. For each added bond two available terminals are chosen at random to be linked and removed from the list. Furthermore, for algorithmic convenience, we reject graphs with possess self loops, bonds that connect two terminals of the same vertex. Multiple bonds between any pair of vertices are allowed, otherwise it is too hard to generate feasible graphs for, say, $`n=32`$ and $`k+1=20`$. Since $`k+1`$ remains finite for $`n\mathrm{}`$, the energy and entropy per spin would only be effected to $`O(1/n)`$ by the differences between these choices.

Once a graphical instance is generated, we assign randomly chosen but fixed couplings $`J_{i,j}\{1,+1\}`$ to existing bonds between neighboring vertices $`i`$ and $`j`$. Each vertex $`i`$ is occupied by a spin variable $`x_i\{1,+1\}`$. The energy of the system is defined as the difference in number between violated bonds and satisfied bonds,

$`H={\displaystyle \underset{\{bonds\}}{}}J_{i,j}x_ix_j,`$ (1)
and in this paper we will focus on the energy per spin,

$`e_{k+1}(n)={\displaystyle \frac{H}{n}},`$ (2)
as a function of $`k+1`$ in the limit of $`n\mathrm{}`$. Each instance can have a large degeneracy $`\mathrm{\Omega }`$ in the configurations exhibiting its ground state energy, and we also sample the average entropy,

$`s_{k+1}(n)={\displaystyle \frac{1}{n}}\mathrm{ln}\mathrm{\Omega },`$ (3)
for these instances.

## III $`\tau `$-EO Algorithm for Bethe Lattices

The extremal optimization algorithm, $`\tau `$-EO, which we employ in this paper, has been discussed previously in eo\_prl , and in eo\_jam ; BoPe2  with regard to the setting of its one free parameter, $`\tau `$. Here, we merely describe the implementation of $`\tau `$-EO without further justification.

To obtain the numerical results in Secs. IV-V, we used the following implementation of $`\tau `$-EO: For a given spin configuration on a graph, assign to each spin $`x_i`$ a “fitness”

$`\lambda _i=\mathrm{\#}violatedbonds=0,1,2,\mathrm{},(k+1),`$ (4)
so that

$`e={\displaystyle \frac{1}{2n}}{\displaystyle \underset{i}{}}\lambda _i`$ (5)
is satisfied. Each spin falls into one of only $`k+2`$ possible states. Say, currently there are $`n_{k+1}`$ spins with the worst fitness, $`\lambda =(k+1)`$, $`n_k`$ with $`\lambda =k`$, and so on up to $`n_0`$ spins with the best fitness $`\lambda =0`$. Now draw a “rank” $`l`$ according to the distribution

$`P(l)={\displaystyle \frac{\tau 1}{1n^{1\tau }}}l^\tau (1ln).`$ (6)
Then, determine $`0j(k+1)`$ such that $`_{i=j+1}^{k+1}n_i<l_{i=j}^{k+1}n_i`$. Finally, select any one of the $`n_j`$ spins in state $`j`$ and reverse its orientation unconditionally. As a result, it and its neighboring spins change their fitness. After all the effected $`\lambda `$’s and $`n`$’s are reevaluated, a new spin is chosen for an update.

This EO implementation updates spins with a ($`\tau `$-dependent) bias against poorly adapted spins on behalf of Eq. (6). This process is “extremal” in the sense that it focuses on atypical variables, and it forms the basis of the EO method. The only adjustable parameter in this algorithm is the power-law exponent $`\tau `$. For $`\tau =0`$, randomly selected spins get forced to update, resulting in a random walk through the configuration space which would yield poor results. For $`\tau \mathrm{}`$, only spins in the worst state get updated which quickly traps the update process to a small region of the configuration space which may be far from a near-optimal solution. The arguments given in eo\_jam  and a few experiments indicate that $`\tau =1.3`$ is a good choice to find ground states efficiently on Bethe lattices.

The algorithm never converges or “freezes” into a particular state but perpetually explores new near-optimal configurations. It is, of course, easy to simply store the lowest energy state found so far in a given run of $`\tau `$-EO and terminate when desired. Previous experience with optimizing spin glasses with EO eo\_prl , and a few experiments, suggest a typical number of updates of $`O(n^3)`$ for an EO-run to obtain saturation in the values found for ground states, at least up to the system sizes $`n10^3`$ obtainable here. Instead of pushing to attain larger values of $`n`$, we opt here for obtaining better statistics by sampling more instances at smaller values of $`n`$ while spending even more time on each instance than may seem to be required, in an attempt to ensure accuracy. In particular, our implementation restarts for each instance at least $`r_{\mathrm{max}}=4`$ times with new random initial spin-assignments, executing $`0.1n^3`$ updates per run. If a new, lower-than-previous energy state is encountered in run $`r`$, we adjust $`r_{\mathrm{max}}=2+2r`$ for that instance so that EO runs at least twice as many restarts as were necessary to find the lowest state in the first place. Especially for small $`n`$, $`r_{\mathrm{max}}`$ hardly ever exceeds 4; for larger $`n`$ a few graphs require up to 25 restarts before termination.

Since EO perpetually explores new configurations it is well suited to explore also the degeneracy of low-energy states. In this case we not only store the first configuration found with the lowest energy for that instance. Instead, we consider each configuration with the lowest energy, retaining new ones and rejecting all others. This procedure is somewhat inefficient and at best allows system sizes up to $`n=256`$ beyond which the degeneracy exceeds memory constraints. But it provides a fast way to also determine the $`T=0`$ entropy of the ground states with moderate accuracy. In these runs, we used a similar approach to the above, except for setting $`r_{\mathrm{max}}=8+2r`$ where $`r`$ is the latest run in which another new configuration of the lowest energy was located. Here, for some highly degenerate instances at larger $`n`$, $`r_{\mathrm{max}}`$ could reach up into the $`100`$’s, further limiting attainable system sizes.

## IV Numerical Test

To evaluate the proposed $`\tau `$-EO algorithm, we have run a series of test. First, we can defer to some already published results eo\_prl ; eo\_jam . In Ref. eo\_prl  we have calculate approximations to the ground state energy for $`\pm J`$ spin glasses on a hypercubic lattice for $`d=3`$ and $`d=4`$ for systems up to $`n=12^3=1728`$ which for each $`n`$ reproduced previous results obtained with sophisticated genetic algorithms Pal ; Hartmann  (although there we used a fixed $`r_{\mathrm{max}}`$). To evaluate the ability of the algorithm to determine the degeneracy of low-energy states found, we have reproduced within statistical error the results of Ref. Hartmann\_entro  up to $`n=6^3`$ beyond which EO ran out of time and memory to sample states completely. (Ref. Hartmann\_entro  used a more efficient way to estimate the entropy from sampling only a small number of states.) And it took EO only a fraction of a second to find all 60 ground states of a $`4^3`$ instance that had been exactly enumerated in Ref. Kobe .

To gauge $`\tau `$-EO’s performance for larger $`n`$, we have run our implementation also on two $`3d`$ lattice instances, $`toruspm`$3-8-50 and $`toruspm`$3-15-50, with $`n=8^3=512`$ and $`n=15^3=3375`$, considered in the 7th DIMACS challenge for semi-definite problems DIMACS7 . Bounds Liers\_pc  on the ground-state cost established for the larger instance are $`H_{\mathrm{lower}}=6138.02`$ (from semi-definite programming) and $`H_{\mathrm{upper}}=5831`$ (from branch-and-cut). EO found $`H_{\mathrm{EO}}=6049`$ (or $`H/n=1.7923`$), a significant improvement on the upper bound and already lower than $`lim_n\mathrm{}H/n1.786\mathrm{}`$ found in Refs. Pal ; Hartmann ; eo\_prl . Furthermore, we collected $`10^5`$ such states, which roughly segregate into 3 clusters with a mutual Hamming distance of at least 100 distinct spins; at best a small sample of the $`10^73`$ ground states expected Hartmann\_entro ! For the smaller instance the bounds given are -922 and -912, resp., while EO finds -916 (or $`H/n=1.7891`$) and was terminated after finding $`10^5`$ such states. While this run (including sampling degenerate states) took only a few minutes of CPU (at 800MHz), the results for the larger instance required about 16 hours.

Finally, we note that we have considered the algorithm for making Bethe lattices previously in Refs. eo\_jam ; eo\_perc . In Ref. eo\_perc  we have studied the graph bipartitioning problem and found that the ground state energy was well above previous RS calculations from Ref. MP , but only minutely below numerical calculations obtained using simulated annealing Banavar . In Ref. eo\_jam  we have considered some variations in the generation of Bethe lattices and found that they effect the results only in next-to-leading order.

## V Numerical Results for Bethe Lattices

We have simulated Bethe lattices with the algorithm described in Sec. III for $`k+1`$ between 3 and 26, and graph sizes $`n=2^l`$ for $`l=5,6,\mathrm{},10`$ to obtain results for ground state energies, and for $`n[16\mathrm{}256]`$ to determine their entropy. In the following, we present the results for ground-state energies and entropies from those simulations. The results are discussed in detail in Sec. V.3.

### V.1 Ground State Energies

To reach relative statistical errors of our averages roughly uniform with $`n`$ we generated initially a number of $`10^5/\sqrt{n}`$ instances for each $`n`$ and $`k+1`$. Fortunately, deviations appear to narrow much faster than $`1/\sqrt{n}`$, and thus we added more instances at smaller $`n`$ with small extra computational cost to obtain narrow error bars there as well. In Tab. 1 we list the values of average energies according to Eq. (2), $`e_{k+1}(n)`$, for each $`k+1`$ and $`n`$, the number of instances used, and the average number of update steps required. Tab. 2 lists a few properties of the computations. The results for the number of updates has been also averaged over all connectivities $`k+1`$, although lower-connected graphs require typically fewer updates. Note that this is the minimal number of updates needed to obtain the listed results, the actual number of updates taken up by each run of EO to ensure convergence was at least twice of that but could be much larger, according to the specification of the algorithm in Sec. III.

Unfortunately, when plotted as a function of $`1/n`$, the average energies for each given $`k+1`$ clearly do not extrapolate linearly (as, for example, seems to be the case for spin glasses on a hypercubic lattice Pal ; Hartmann ; eo\_prl ). Instead, using an extrapolation according to 111In a previous simulation eo\_jam , we have attempted to fit those data (at $`k=1=3,4`$) with a $`\mathrm{ln}(n)/n`$ correction with a result that was somewhat above the current extrapolation value.

$`e_{k+1}(n)e_{k+1}+{\displaystyle \frac{A}{n^\nu }}(n\mathrm{}).`$ (7)
We find that for the whole range of connectivities $`k+1`$ studied here, the scaling corrections appeared to be consistent with $`\nu =2/3`$ within a few percent, except for two outliers at $`k+1=10`$ and 25. Thus, we have plotted for each $`k+1`$ the values of $`e_{k+1}(n)`$ as a function of $`1/n^{2/3}`$ in Figs. 1 and 2. Although the extrapolation appears to be linear on that scale for each $`k+1`$, we have fitted the data with the more general form of Eq. (7). (Fits were weighted according to $`n`$ and to the inverse of the standard deviation for each point.) These fits are also shown as dashed lines in each of the Figs. 1 and 2.

The extrapolation results for the ground state energies appear to be quite stable under variation of the scaling form, for instance, when fitting with fixed $`\nu =2/3`$ instead of Eq. (7). We estimate that each has a relative error of about ¡0.3%. Exceptions to this estimate we have to grant for the cases of $`k+1=10`$ and 25, in which case we also observe significant differences to the $`\nu =2/3`$ corrections to scaling.

We can compare our results with existing theoretical predictions at the RS and the 1RSB level at least for the case of $`k+1=3`$. For this case, a recently published calculation MP2  yielded $`e_3=1.2777`$ at the RS, and $`e_3=1.2717`$ at the 1RSB level (further replica corrections are expected to be small). These values are also indicated in Fig. 1. Clearly, our result for $`k+1`$ is consistent with the 1RSB results, but certainly inconsistent with the RS result. Further 1RSB results for other values $`k+1`$ are currently being calculated Mezard\_pc . We will discuss a more detailed analysis of the extrapolated values of $`e_{k+1}`$ at $`n\mathrm{}`$ in Sec. V.3.

### V.2 Ground State Entropy

We have also used EO to sample the degeneracy $`\mathrm{\Omega }`$ of the lowest-energy states found. Due to the discrete nature of the energy of the system, ground-states can be highly degenerate, and the ground-state entropy per spin defined in Eq. (3) may well be non-vanishing for $`n\mathrm{}`$. While the search for a ground state of an instance is certain to provide a rigorous upper bound to the actual ground state energy, the search for the complete set of ground states for an instance entails the risk of a two competing systematic errors. (1) If EO misses to find the exact ground state, one is likely to vastly over-count the degeneracy, since $`\mathrm{\Omega }`$ is expected to rise exponentially with the energy above the ground state Sibani . (2) Even if EO finds ground states, it may simply undercount $`\mathrm{\Omega }`$, since such states could be too far separated in configuration space. Therefore, we have implemented EO with the settings described in Sec. III, which emphasize the desire for accuracy over computational efficiency. Accordingly, we were bound to conduct a separate set of simulations from those that determined the energies only. In these simulations we focused on smaller system sizes of $`n256`$ for $`k+1=3,\mathrm{},9`$ and $`10,14,\mathrm{},26`$ only. The limit on $`n`$ for the smaller $`k+1`$ is mostly dictated by avoiding system sizes at which $`\mathrm{\Omega }`$ typically exceeds $`10^6`$.

As a test for the accuracy of our implementation, we have run the simulation for $`k+1=3`$ twice on the exactly identical instances, using different initial conditions and $`n/5`$ more updates in the second run: The results, both for the energies and $`\mathrm{\Omega }`$, were identical for each instance, producing the same set of configurations independent of the starting point of the search. We therefore assume that systematic errors in our data are small and can be neglected.

Since the range of system sizes $`n`$ is smaller than for the case of the energies, it is more difficult to extrapolate our data for $`s_{k+1}(n)`$. Again, it is clear that the corrections are not linear in $`1/n`$, but instead seems to be scaling close to $`1/n^{2/3}`$ for all $`k+1`$, as for the energies above. Considering the limitations on $`n`$, we assume that the corrections are exactly of that form and extrapolate our data simply with a fit to

$`s_{k+1}(n)s_{k+1}+{\displaystyle \frac{A}{n^{2/3}}}(n\mathrm{}),`$ (8)
again, weighting each data point with respect to $`n`$ and the inverse of its error. While the systematic and statistical uncertainties of our data appears to be small, the uncertainty about the scaling corrections must be considered the most significant limitation on accuracy in our extrapolation. The data and the extrapolation fits according to Eq. (8) are shown in Figs. 3 and 4. The results for $`s_{k+1}`$ for $`n\mathrm{}`$ are listed in Tab. 3.

The data clearly shows a different quantitative behavior between odd and even values of $`k+1`$. This difference for the entropies can be explained in terms of the “free spins:” In a highly frustrated system, even near ground states, many spins are stuck in a situation in which they violate many of their constraints, no matter how they are oriented, and changing from one direction to the other may hardly change the energy of the system. In particular, an even-connected spin that happens to violate exactly half of its bonds (with $`J=\pm 1`$) can flip freely without any change to the energy. Odd-connected spins can only become “free” in a connected pair (that happens to violate exactly half of its external bonds but satisfies their mutual bond) in which both simultaneously flip without changing the energy. The latter situation is naturally far less likely, and thus, purely even-connected graphs exhibit far more potential for degeneracy at the ground state than the corresponding odd-connected graphs. Some preliminary studies for $`k+1=3`$ and 4 show that in ground state configurations the fraction of free spins (zero by design for $`k+1=3`$) converges to a value just around 5% for $`k+1=4`$, while the fraction of free pairs seems to vanish for large $`n`$ for both, even and odd $`k+1`$. We have not explored the clustering of these states Hartmann\_entro . We will explore the different behaviors for even and odd $`k+1`$ in the next Section.

### V.3 Discussion of the Extrapolation Results

In this section, we want to focus on some of the curious properties exhibited by the values of the energies and entropies found by extrapolation in the previous section. We have already noted the difference between the entropies for even and odd values of $`k+1`$. In fact, there are similar differences, although more subtle, for the energies $`e_{k+1}`$. These differences become most apparent when we plot the data asymptotically for large $`k+1`$, where it is known that

$`\underset{k+1\mathrm{}}{lim}{\displaystyle \frac{e_{k+1}}{\sqrt{k+1}}}=E_{SK},`$ (9)
with $`E_{SK}=0.7633`$ being the RSB ground state energy of the Sherrington-Kirkpatrick model SK ; MPV . In Fig. 5 we have plotted $`e_{k+1}/\sqrt{k+1}`$ as a function of $`1/(k+1)`$. On this scale, we notice that the energies split into a set of even and a set of odd values, each located apparently on a straight line. Even though $`k+125`$ is quite small, each line separately extrapolates very close to the exact value for large $`k+1`$ indeed: $`E_{SK}^{even}0.763`$ and $`E_{SK}^{odd}0.765`$. Even more amazing, the value of $`e_2=1`$ \[see Eq. (16) below\] for the trivial $`k+1=2`$ Bethe lattice is very close to the linear fit for the even EO results. Clearly, a function that would interpolate continuously all the data will have to be very complicated (oscillatory). But could it be that its envelope on the even and the odd integers happens to be simple? Then, in case of the even data 222Although the odd data may equally well be fitted in this way, the line can not be determined since only one point on it, $`E_{SK}`$, is exactly known., we could even write down the exact form of the function for $`_{k+1}`$ that would fit the data, since we know it also has to pass $`e_2=1`$ and satisfy Eq. (9):

$`_{k+1}=\sqrt{k+1}E_{SK}{\displaystyle \frac{2E_{SK}+\sqrt{2}}{\sqrt{k+1}}}.`$ (10)
To test Eq. (10), we plot the data in Fig. 6 as $`e_{k+1}/_{k+1}`$ to study its deviations from the conjecture. While the extrapolated values do not fall exactly within their (estimated) error bars on the proposed form, they are indeed within about 0.1% of it. To judge how close the data is to the proposed functional form in Eq. (10), we utilize a closely related example. The ground-state energy as a function of the (continuous) average connectivity $`c`$ is known exactly for the RS case of ordinary random graphs with fluctuating internal connectivities, Eq. (16) in Ref. KS . If one plots that solution (which involves exponentials and modified Bessel functions) in the same way as $`e_{k+1}`$ in Fig. 5, one notes that it, too, could be approximated surprisingly well with a straight line, $`\sqrt{2c/\pi }+\left(\sqrt{2/\pi }\frac{1}{2}\right)/\sqrt{c}`$, now crossing the RS ground state energy $`\sqrt{2/\pi }`$ MPV  for $`c\mathrm{}`$ and reaching the trivial result of $`1/2`$ at the percolation point $`c=1`$. In Fig. 7 we superimpose the relative error of this approximation with respect to the exact RS result with the relative error of our data with respect to the conjecture. It shows that the error of the conjecture is still almost by an order of magnitude smaller than the global bound for the RS example, thus putting a significant bound on any corrections similar in type to Eq. (16) in Ref. KS .

The differences between even and odd connectivities are even more pronounced in case of the entropies, as we have explained in Sec. V. Thus, although our data for the entropy is not nearly as accurate as for the energies, it is still instructive to study it in more detail. In Fig. 8, we plot the extrapolated values of the entropies from Tab. 3 to explore its decrease for large $`k+1`$. Despite the large error bars, a significant qualitative difference between even and odd data points is visible: The entropy for even values of $`k+1`$ decays slowly, apparently linearly with $`1/(k+1)`$. On the other hand, the entropies for odd $`k+1`$ drop much more rapidly, and are already indistinguishable from zero (within our errors) for $`k+1=9`$, while it is clearly non-vanishing for $`k+1=3`$ \[unless our assumption about the scaling corrections in Eq. (8) are incredibly wrong (see Fig. 3)\]. Unfortunately, with only a small, discrete number of data points available that are significantly above zero, it is very hard to decide whether the entropy for odd $`k+1`$ merely decays exponentially, or whether there exists a finite value of $`k+1`$ above which all odd entropies become identically zero.

## VI Conclusion

In this paper we have presented a extensive numerical study of the ground states of spin glasses on Bethe lattices. The available data possessed sufficient accuracy to obtain extrapolated values for ground state energies and entropies at the 0.1% and the 10% level, respectively. In both cases, we significant differences emerged between the data for odd and even values of $`k+1`$. Based on the numerical results, we showed that the extrapolated energies for all even values of $`2k+1\mathrm{}`$ was well fitted with a simple function, Eq. (10). Furthermore, the data suggests that the entropies are generally non-zero at small $`k+1`$, but may vanish above a finite $`k+1`$ for odd values.

Of course, there is plenty of reason to doubt that such a simple result as Eq. (10), albeit confined to discrete integer values of $`k+1`$, could indeed be the solution to a complex RSB problem. In fact, one argument against the conjecture is a discrepancy in its prediction for large $`k+1`$ at next-to-leading order. Several authors DG ; PT  have studied spin glasses on random graphs beyond the RS level perturbatively for $`k+1=z\mathrm{}`$ to determine the $`1/z`$ correction $`f_1`$ to the free energy (at $`T>0`$) in $`E_{SK}+f_1/z`$. It was recently calculated PT , that the correction for fixed connectivities for $`T0`$ would be about $`f_1=0.317`$, while Eq. (10) would predict about $`0.1124`$. It should be noted, though, that the $`1/z`$ expansion implicitly assumes a smooth continuation off the integers which may lead to ambiguities in light of the oscillatory behavior between even and odd integers we found for the ground states in Fig. 5 (similar to the continuation of, say, the function $`\mathrm{cos}(2\pi z)/z`$ for $`z\mathrm{}`$, although this function would not possess a $`1/z`$ expansion at all).

In any case, future calculations like the one in Ref. MP2  but for even $`k+1`$ will provide a check on both, our extrapolated data and the conjecture.

## Acknowledgments

This work has been supported under a grant from the Emory University Research Committee. I am greatly indebted to Marc Mezard for his helpful comments.

## Appendix

### VI.1 The Case $`k+1=2`$

Clearly, a Bethe lattice in which each vertex has exactly 2 connections can only consists of a collection of disconnected loop graphs. We merely need to determine the number of loops and their size distribution to derive the average ground state energy and entropy. Each loop has a 50% chance of being frustrated, thus, the number of cut bonds is equal to one-half of the number of loops, and the degeneracy is equal to the length of these loops to the power of their number.

To analyze the $`k+1=2`$ case we consider each vertex as a node with two terminals. Adding lines can create two types of objects: strings and loops. We consider, after adding $`t`$ lines, an individual vertex as a string of length 0, of which there are $`l_{0,t}`$; in general, we have $`l_{i,t}`$ strings of length $`i`$, each possessing two open terminals. In particular, before we added any lines: $`l_{i,t=0}=\delta _{i,0}`$. A loop of length $`i`$ is created by addition of a line to both open terminals of a string of length $`i1`$. There are $`p_{i,t}`$ loops of length $`i`$ after adding $`t`$ lines which can not evolve further, since they don’t possess any more open terminals. We start with $`2n`$ open terminals and cover 2 of those with each newly added line. We can identify two constraints:

$`{\displaystyle \underset{i=0}{\overset{\mathrm{}}{}}}l_{i,t}=nt,{\displaystyle \underset{i=1}{\overset{\mathrm{}}{}}}i\left(l_{i,t}+p_{i,t}\right)=t.`$ (11)
After adding $`t`$ lines at random, there are $`2(nt)`$ terminals left to accommodate the next line, allowing for $`\left(\genfrac{}{}{0pt}{}{2\left(nt\right)}{2}\right)`$ different choices. Accounting for all possible choices, we obtain

$`l_{0,t+1}`$ $`=`$ $`\left[1{\displaystyle \frac{2}{nt}}+{\displaystyle \frac{1}{\left(\genfrac{}{}{0pt}{}{2\left(nt\right)}{2}\right)}}\right]l_{0,t},`$
$`l_{i,t+1}`$ $`=`$ $`\left[1{\displaystyle \frac{2}{nt}}+{\displaystyle \frac{1}{\left(\genfrac{}{}{0pt}{}{2\left(nt\right)}{2}\right)}}\right]l_{i,t}`$
$`+{\displaystyle \frac{2}{\left(\genfrac{}{}{0pt}{}{2\left(nt\right)}{2}\right)}}\left({\displaystyle \underset{j=0}{\overset{i1}{}}}l_{j,t}l_{i1j,t}l_{\frac{i1}{2},t}|_{i\mathrm{odd}}\right),`$
$`p_{i,t+1}`$ $`=`$ $`p_{i,t}+{\displaystyle \frac{1}{\left(\genfrac{}{}{0pt}{}{2\left(nt\right)}{2}\right)}}l_{i1,t},`$ (12)
where $`i>0`$. It is easy to show that these equations satisfy the constraints in Eqs. (11).

We can transform these equations by defining $`\theta =t/n`$, $`d\theta =1/n`$, $`y(x,\theta )=\frac{1}{n}_{i=0}^{\mathrm{}}l_{i,t}x^i`$, and $`p(x,\theta )=_{i=0}^{\mathrm{}}p_{i,t}x^i`$. Considering $`n`$ large and $`\theta `$ continuous, Eqs. (12) turn into

$`{\displaystyle \frac{dy(x,\theta )}{d\theta }}`$ $`=`$ $`{\displaystyle \frac{2y(x,\theta )}{1\theta }}+{\displaystyle \frac{x[y(x,\theta )]^2}{(1\theta )[1\theta 1/(2n)]}}`$
$`+{\displaystyle \frac{1}{n}}\left[{\displaystyle \frac{y(x,\theta )xy(x^2,\theta )}{2(1\theta )[1\theta 1/(2n)]}}\right],`$
$`{\displaystyle \frac{dp(x,\theta )}{d\theta }}`$ $`=`$ $`{\displaystyle \frac{xy(x,\theta )}{(1\theta )^2}},`$ (13)
$`y(x,0)=1,p(x,0)=0.`$
Luckily, for $`n\mathrm{}`$, the equations are easily solved to give

$`y(x,\theta )={\displaystyle \frac{(1\theta )^2}{1x\theta }},p(x,\theta )={\displaystyle \frac{1}{2}}\mathrm{ln}(1x\theta ).`$ (14)
Finally, the total number of loops for the (almost) completed graph, $`\theta =11/n`$, is given by

$`p(1,11/n)={\displaystyle \underset{i=1}{\overset{\mathrm{}}{}}}p_{i,n1}{\displaystyle \frac{1}{2}}\mathrm{ln}(n).`$ (15)
On average, half of these loops will be frustrated, i. e., they will have one of their bonds violated. Since the Hamiltonian in Eq. (1) counts the difference between violated and satisfied bonds, or twice the violated bonds minus the number of all bonds, $`n(k+1)/2=n`$, we get

$`e={\displaystyle \frac{H}{n}}1+{\displaystyle \frac{\mathrm{ln}(n)}{2n}}.`$ (16)
Similarly, we can calculate the degeneracy $`\mathrm{\Omega }`$ of these ground states, roughly, as the average length of loops, $`i=_x\mathrm{ln}p(x,11/n)|_{x=1}n/\mathrm{ln}(n)`$, taken to the power of one-half of their number, $`\mathrm{ln}(n)/(4n)`$, to give

$`s={\displaystyle \frac{1}{n}}\mathrm{ln}\mathrm{\Omega }{\displaystyle \frac{\mathrm{ln}(n)^2}{4n}}.`$ (17)
Clearly, both the number of violated bonds as well as the entropy vanish in the large-$`n`$ limit.


text:
# Charge and Orbital Ordering in Pr0.5Ca0.5MnO3 Studied by 17O NMR

## I Introduction

The charge ordering phenomena in the hole-doped R1-xAxMnO3 (R is a trivalent rare-earth ion and A is a divalent alkaline-earth ion) have been a subject of extensive studies due to intriguing interplay of the charge, orbital and spin degrees of freedom. The charge ordered (CO) state is formed due to localization of the mobile $`e_g`$-holes.

Above $`T_{CO}`$ the $`e_g`$-holes provide FM correlations between electron spins of neighboring manganese ions through the double-exchange (DE) mechanism proposed by Zener Zener-PRB82 . Pr1-xCaxMnO3 ($`0.3x0.75`$) oxides are the most suitable for investigation of the CO state since the onsets of the charge ($`T_{CO}`$ ) and spin ($`T_N`$) order are well separated in temperature. This doped oxide has an orthorhombic structure (space group, $`Pbnm`$) in a wide temperature and magnetic field ($`<20T`$) range. It remains in the semiconducting state with no admixture of FM metal phase as opposed to Pr1-xSrxMnO3, La1-xCaxMnO3 and La1-xSrxMnO3 Jirak-JMMM53 , Tomioka-PRB53 . In the CO structure of Pr1-xCaxMnO3 with $`x0.5`$ the in-plane pattern of Mn3+ and Mn4+ ions may be represented as a checkerboard related to the corresponding $`t_g^3e_g^1`$ and $`t_g^3`$ electronic configurations of Mn (Fig.1). The lobes of a certain number of occupied $`e_g`$-orbitals are ordered in the direction of the Mn3+-O-Mn4+ bond to maximize DE coupling. Whereas the AF superexchange $`t_{2g}t_{2g}`$ coupling is a dominating magnetic interaction for Mn4+ and Mn3+ which $`e_g`$-lobes are aligned perpendicular to the Mn3+-O-Mn4+ bond. At $`x0.5`$ the competition of these exchange couplings results in the AF spin ordering of CE-type with $`T_N<T_{CO}`$ . The associated Jahn-Teller (JT) distortions of MnO6 octahedra double the unit cell along b-axis of the orthorhombic ($`Pbnm`$) lattice. The ideal CE type charge/orbital order implies FM zigzag arrangement of the ordered $`e_g(3x^2r^2)`$ and $`e_g(3y^2r^2)`$ orbitals of Mn3+ ions in ab-plane. The neighboring zigzags are AF-coupled, the ordering in c-direction is also antiferromagnetic.

Recent resonant x-ray scattering Zimmerman-PRB61 , electron microscopy Mori-PRB59  and neutron diffraction Jirak-PRB61 , Kajimoto-PRB63  studies of Pr0.5Ca0.5MnO3 have shown that the orbital order (OO) below $`T_N=170K`$ results in an orbital domain state commensurate with the lattice. This commensurate OO becomes metastable above $`T_N`$. Its melting is observed in diffraction studies as a commensurate-incommensurate (C-IC) transition at $`T_{CIC}(180200)K>T_N`$. With further increase of temperature the partial orbital disorder turns on the FM spin fluctuations which become dominating near $`T_{CO}250K`$ Kajimoto-PRB58 . The C-IC transition was considered in terms of the $`e_g`$-orbital polarization soft mode. The $`e_g`$-orbital completely polarized along Mn-O bond corresponds to the amplitude of the wave at a given Mn3+ ion Jirak-PRB61  and its wave vector $`\text{q}=\{0,1/2\epsilon ,0\}`$ was considered as the order parameter of the transition.

Further discussion of the CO state requires more detailed microscopic data related to the distribution of spin density and to its dynamic regime in the CO state of manganite. Studies of spatial fluctuations of charge/orbital order with diffraction experiments Jirak-PRB61 , Kajimoto-PRB63  is restricted to short correlation times $`\tau _c<10^{12}s`$. Whereas NMR experiments enable studying time-dependent spin fluctuations at much longer $`\tau _c`$.

In this work we have studied the spin correlations of the neighboring Mn ions developed in the paramagnetic charge ordered (CO PM) state of Pr0.5Ca0.5MnO3 by measuring the 17O NMR spectra. Oxygen atoms being placed between two Mn ions bring valuable information about the spin/orbital configuration of the nearest Mn ions. As expected the nuclear spin of oxygen $`(^{17}I=5/2)`$ probes its magnetic state through the dipolar and transferred hyperfine magnetic fields that depend on the spin/orbital configuration of the neighboring Mn ions Turov . The 55Mn nucleus is a less suitable NMR probe for this task for the following reasons. First, the NMR spectrum of Mn4+ ion ($`t_g^3`$ electron configuration) is available only at low temperatures in the metastable CO AF phase. On the other hand, NMR of Mn3+($`t_g^3e_g^1`$) is hard to detect due to extremely high nuclear spin-spin relaxation rate apparently controlled by abnormal low-frequency spin dynamic of the localized eg-electrons.

This 17O NMR report is focused on the study of the development of the charge/orbital ordering in Pr0.5Ca0.5MnO3. The main result is that in Pr0.5Ca0.5MnO3 the CE-type magnetic correlations develop gradually below $`T_{CO}`$: first those between ab-layers arise and only at lower temperature the correlations within ab-planes appear. The static ($`\tau _c>10^6s`$) orbital order is established only on approaching $`T_N`$.

## II Experimental

We used a powder sample of Pr0.5Ca0.5MnO3 prepared by traditional ceramic technology. The powder was enriched with 17O isotope up to $`25\%`$. The single-phase nature of the enriched sample was confirmed by the x-ray diffraction and Raman scattering studies at room temperature.

17O NMR measurements were carried out on a phase-coherent NMR pulse Bruker spectrometer over the temperature range of $`80330K`$ in magnetic field of $`7T`$. In this field the onset of the CO and AF spin ordering was found to shift slightly down to $`T_{CO}225K`$ and $`T_N170K`$ compared to reported data at zero field and in accordance with $`H`$-dependence of $`T_{CO}`$ reported in Ref.Tomioka-PRB53 . NMR spectra were obtained for a loose-packed powder sample with point-by-point frequency sweep measurements, the intensity of the spin-echo signal formed with the pulse sequence $`(\pi /2)\tau _{del}(\pi /2)`$-echo being measured. The width of the $`\pi /2`$\- exciting pulse was $`t_p=(24.5)\mu s`$ and the distance between pulses varied in the range of $`\tau _{del}=(4080)\mu s`$. For each frequency, the amplitude of the exciting rf-pulse was adjusted in order to optimize the echo signal intensity while keeping the pulse duration fixed. All the echo-intensities were corrected to $`\tau _{del}0`$ by measuring the rate of echo-decay at different frequencies of the broad spectrum. All the spectra for $`T<T_{CO}`$ were measured during cooling down from room temperature to avoid the hysteresis uncertainties. The 17O NMR signal in H2O was used as a frequency reference to determine the shift of NMR line in our sample.

## III RESULTS AND DISCUSSION

### III.1 The charge disordered paramagnetic state

Figure 2 shows the 17O NMR spectra of Pr0.5Ca0.5MnO3 measured in the PM state. In the charge disorder paramagnetic state (CD PM) for $`T>T_{CO}225K`$ the main signal $`(95\%)`$ in the spectrum is a rather asymmetric line. It has a positive and extremely large magnetic shift exceeding $`6\%`$ even at the highest measured temperature, $`T=330K`$ with respect to those observed in nonmagnetic compounds. An additional line of small intensity $`(5\%)`$ is present at zero NMR-shift. It is supposed to originate from a small amount of the Ca-based oxides, which arise as spurious precipitations during the solid-state reaction synthesis. It’s well known that a small concentration of spurious phase formed with light atoms like Ca is hard to detect by x-ray.

Let us now consider the quadrupolar and magnetic shift interactions of the oxygen nuclear spin with its environment. The oxygen atoms are located at the corners of octahedra with Mn at the center. The noncubic local symmetry of oxygen sites leads to the interaction of 17O electric quadrupole moment $`(eQ)`$ with electric field gradient $`(eV_{ZZ}`$). The resulting 17O NMR spectrum is expected to split into $`2I+1`$ lines separated by the quadrupole frequency $`\nu _Q=\frac{3e^2Q}{2I(2I1)hV_{ZZ}}`$ at $`\text{H}O_Z`$ . Experimentally this characteristic first-order quadrupole splitting has never been observed. It shows that $`{}_{}{}^{17}\nu _{Q}^{}`$ does not exceed the NMR linewidth measured at $`T=330K`$ i.e. $`\nu _Q<1.4MHz`$ in agreement with Ref.Reven-Piskunov-Takigawa . Thus the quadrupolar interaction will only provide broadening effects on the observed pattern of NMR spectra, these quadrupolar effects being small compared to the magnetic interaction effects (see below).

The powder pattern spectrum of the Pr0.5Ca0.5MnO3 main line in the CD PM state may be described assuming an axial symmetry of the magnetic shift tensor $`\{K_{},K_{},K_{}\}`$. The subscripts $`\mathrm{"}\mathrm{"}`$ or $`\mathrm{"}\mathrm{"}`$ refer to the shift component $`K_\alpha `$ of oxygen with Mn-O bond directed perpendicular or parallel to the external magnetic field $`H_0`$, respectively. The analysis of the line leads to $`K_{}=7.0\%`$ and $`K_{}=11.5\%`$ at $`T=295K`$. The thermal variation of the shift is shown in Fig.3. With decreasing temperature the peak of the line is further shifted following the Curie-Weiss law with $`K=K_0+a/(T\theta )`$. The corresponding fit curve drawn by a dashed line in Figs. 2,3 results in $`K_0=1.0(6)\%`$ and $`\theta =130(20)K`$. A close value of $`\theta 150K`$ is obtained by fitting the magnetic susceptibility $`(\chi )`$ data measured in the range of $`T=250÷300K`$ in Ref.Jirak-PRB61 . The positive value of $`\theta `$ evidences that FM spin correlations between neighboring Mn are the dominating ones in the CD PM state above $`T_{CO}`$. A similar conclusion about the prevalence of the FM spin correlations between Mn ions in the CD PM phase was inferred from the 139La NMR line shift in La0.5Ca0.5MnO3, which becomes FM-metal in the field of $`4T`$ below $`T220K`$ Yoshinari-PRB60 .

The slope of the $`K`$ vs $`\chi `$ plot corresponds to the local magnetic field $`H_{loc}=\mu _B\mathrm{\Delta }K/\mathrm{\Delta }\chi 110^4Oe/\mu _B`$ (the $`\chi `$-data are taken from Fig.4 in Ref.Jirak-PRB61 . It exceeds the magnitude of the classic dipolar field $`(H_{dip})`$ induced at oxygen by the magnetic moments of the neighboring Mn ions:

$`H_{dip}={\displaystyle \frac{2g_e\mu _Bs_z(Mn)}{r_{MnO}^3}}={\displaystyle \frac{2\chi H}{r_{MnO}^3}}.`$ (1)
At room temperature $`H_{dip}`$ may be estimated as $`H_{dip}1200Oe`$ where $`\chi `$ is defined per spin from Ref.Jirak-PRB61 . The corresponding estimated anisotropic contribution to the total NMR line shift $`\{0.8\%,0.8\%,1.6\%\}`$ is much less than the experimental value. Thus we assume that the classic dipole interaction of 17O nucleus with the effective magnetic moments $`2g_e\mu _Bs_z(Mn)`$ of the nearest Mn has no strong influence on the total shape of the spectrum.

The most probable origin of the observed giant isotropic magnetic shift $`K_{iso}(2K_{}+K_{})/3`$ is the Fermi contact interaction of the nuclear spin $`{}_{}{}^{17}I`$ with the transferred s-spin density of electrons participating both in the Mn-O-Mn bonding and in superexchange coupling of the neighboring Mn,

$`K_{iso}={\displaystyle \frac{8\pi }{3}}g_e\mu _B\varphi _{2s}(0)^2f_ss_z(Mn)=`$
$`{\displaystyle \frac{1}{{}_{}{}^{17}\gamma \mathrm{}}}a(2s)f_ss_z(Mn)`$ (2)
Here $`g_e\mu _Bs_z(Mn)=\chi H`$, $`a(2s)=^{17}\gamma \mathrm{}H_{FC}(2s)=0.15cm^1`$ is the isotropic hyperfine coupling constant for oxygen ion O'Reilly-JCP40 , Fraga-Handbook . $`H_{FC}`$ is the corresponding hyperfine magnetic field due to the Fermi-contact interaction with electron located on 2s-orbital with wave function $`\psi _{2s}(r)`$. Following Shulman-PR108 , Turov  the corresponding isotropic spin density transferred at oxygen from neighboring Mn ions may be defined in terms of the factor $`f_s=H_{loc,iso}/2H_{FC}(2s)`$. This quantity estimated from (2) results in a rather large magnitude of the effective fractional occupancy of O(2s) orbitals by unpaired spins. We found $`f_s=0.01`$ for insulating PM state of Pr0.5Ca0.5MnO3. For comparison the LDA+U band structure calculation results in $`f_s=0.0030.007`$ for the FM-ordered state of LaMnO3 Elfimov .

Another possible isotropic hyperfine interaction is the core-polarization term which provides $`H_{loc}310^4Oe`$ Karplus  when assuming that the doped electron is fully localized within the oxygen 2p-orbital. But this is not the case above $`T_{CO}`$ in Pr0.5Ca0.5MnO3. Thus this interaction may be neglected for the light oxygen atom.

The noncubic local symmetry of oxygen sites gives rise to an anisotropic part of the magnetic shift tensor $`K_{ax}=(K_{}K_{})/3`$. The most reasonable contribution to $`K_{ax}`$ is the magnetic dipole-dipole hyperfine interaction of $`{}_{}{}^{17}I`$ with electrons on 2pσπ, orbitals, which spin occupancies ’up’ and ’down’ become different through the polarizing interactions with neighboring manganese. The corresponding magnetic shift tensor $`K_{dip}`$ may be expressed through the fractional spin density transfer $`f_\alpha s_z(Mn)`$ on O-2pα orbital from paramagnetic neighboring Mn-ion Turov  as:

$`K_{}(2p_\sigma )=2K_{}(2p_\sigma )={\displaystyle \frac{4}{5}}<r^3>_{2p}f_\sigma \chi (Mn);`$ (3)
$`K_{}(2p_\sigma )`$,($`K_{}(2p_\sigma )`$) being defined for $`H_0`$ parallel (perpendicular) to the Mn-O bond respectively. The resulting dipolar contribution to $`K_{ax}`$ is thus determined by the difference of transferred spin density $`(f_\sigma f_\pi )s_z(Mn)`$ for different O-2p orbitals from neighboring Mn-ion Turov :

$`K_{ax}={\displaystyle \frac{2}{5}}<r^3>_{2p}(f_\sigma f_\pi )\chi (Mn)`$ (4)
Taking $`<r^3>_{2p}=4.97a.u.`$ Fraga-Handbook  for neutral oxygen atom we obtain a rather large positive value $`(f_\sigma f_\pi )0.04`$. The direct observation of the positive value of $`(f_\sigma f_\pi )`$ proves for the first time that the $`p_\sigma `$-orbital directed along the Mn-O bond is more polarized than the two other $`p_\pi `$-orbitals.

We showed before that the 17O NMR line position in the CD PM state is mainly determined by the isotropic transferred hyperfine coupling, arising from the hybridization of Mn(3d) and O(2s) orbitals. In the ideal $`Pbnm`$ structure there is no overlap of Mn($`t_{2g}`$)-O(2s) orbitals due to their orthogonality, while $`e_g`$-orbitals of Mn have a rather strong overlap with s-orbital of neighboring oxygen as shown in Fig.1. Hereafter we restrict ourselves to the effects of overlap and covalency between Mn($`e_g`$) and O(2s) orbitals.

### III.2 The charge ordered paramagnetic state

Just below $`T_{CO}`$ the 17O NMR spectrum is substantially broadened. It splits into two parts as shown in Fig.2. The low-frequency spectrum in the range of $`K=(2÷+10\%`$ is asymmetric (A-line). Its width decreases gradually as the temperature approaches $`T_N`$. The high-frequency spectrum is approximately twice larger in intensity and forms a rather complicated pattern which center of gravity is shifted to extremely large positive $`K>20\%`$. At $`T=170KT_N`$ it splits into two broad lines (B- and C-line) of about equal intensity and peaked at $`K_B40\%`$ and $`K_C55\%`$, respectively.

According to x-ray and neutron diffraction studies Jirak-PRB61 , the CO and OO of the CE-type becomes commensurate in the CO PM phase only near $`T_N`$. If the domain structure of the OO Zimmerman-PRB61 ,Jirak-PRB61  is ignored, one finds four groups of the oxygen atoms differentiated by the charge and/or by the direction of occupied $`e_g`$-orbital of the nearest-neighboring Mn-ions. The first and the second groups are formed by apical oxygen located between two Mn3+-ions (O1-site, shown in Fig.1) or between Mn4+ (O2/O3-site), respectively. Note that the $`s_z`$-projections of electron spins are AF correlated for neighboring Mn from adjacent ab-planes. A third group is formed by oxygen (O4) in the ab-plane which participates in the AF coupling of neighboring Mn4+, Mn3+ from adjacent zigzags. The last group (O5) is formed by oxygen in the ab-plane located between two FM coupled Mn4+and Mn3+ ions inside a zigzag. The concentration of each type of oxygen atoms obeys the ”structural” ratio $`1:1:2:2`$.

In order to assign A-C-lines measured in the CO PM phase we analyze first the spectra near $`T_N`$ with resolved structure. We compare the ”structural” ratio with the experimental ”NMR line intensity” ratio, which is close to $`2:2:2`$. We also take into account that the local magnetic fields at different oxygen sites are formed through the Mn-O-Mn exchange interactions which are short-range in space. In CO PM phase the effective magnetic moment of Mn (shown in Fig.1 by arrows) is defined by its projection $`g_e\mu _Bs_z`$ on the direction of the external magnetic field. In turn it controls the sign of the corresponding 17O NMR shift contributed by each of the two neighboring Mn.

A-line is attributed to the apical (O1 and O2/O3) sites whereas B- and C-lines - to the in-plane ones. The magnetic shift of the A-line is small, and the local field at the corresponding 17O is comparable in magnitude to the classic dipolar field estimated above (1). At these apical sites the hyperfine magnetic shifts (2- 4) are greatly reduced since both neighboring Mn-ions are in the same valence state and their effective magnetic moments $`g_e\mu _Bs_z`$ are AF correlated in the CO PM phase of CE-type.

Let us now consider the high-frequency part of the spectra. C-line demonstrating the largest positive shift may be attributed to oxygen positioned in O5 sites whereas B-line is presumably due to oxygen located in O4 sites. Indeed for oxygen in O5 site the transferred s-wave spin density is maximal since within the zigzag the lobe of the partially occupied $`e_g(m_l=0)`$ orbital of Mn3+ ion points toward the neighboring oxygen. Furthermore the two neighboring Mn ions are FM correlated. For O4 we definitely expect a rather large transferred hyperfine field for the following reason. Although the spins of Mn in adjacent zigzags are antiparallel, the O4 oxygen is ”sandwiched” between Mn3+and Mn4+ ions with different spin values and different orbital occupations, i.e. with different covalency. So that the transferred polarization from these two Mn ions should not compensate as they do for the apical oxygen (O1, O2/O3). This should again result in a substantial shift, although smaller than for O5. Moreover the transferred s-wave polarization from Mn4+ ion is expected to be negative due to effects of covalent mixing with the empty $`e_g`$-orbitals Watson-PR134 . As reviewed in Watson-HI  the charge transfer from the occupied O-2s orbital to the empty eg-orbital is spin dependent. It is regulated by the intra-atomic exchange coupling with electrons on $`t_g`$-orbitals.

Thus in the CO PM phase the static s-wave polarization is directed along H, and the isotropic shift at O5 site may be expressed similarly to (2) through the corresponding transferred spin densities $`f_{s,3+}s_z(Mn^{3+})`$ or $`f_{s,4+}s_z(Mn^{4+})`$ of the neighboring Mn (with $`f_{s,3+}>0`$ and $`f_{s,4+}<0`$):

$`K_{iso}(O5)={\displaystyle \frac{8\pi }{3}}g_e\mu _B\psi _{2s}(0)^2\{f_{s,3+}s_z(Mn^{3+})+`$
$`f_{s,4+}s_z(Mn^{4+})\}`$ (5)
The effective magnetic moments of neighboring Mn from adjacent zigzags are AF correlated and we obtain for $`K_{iso}`$(04) the following expression:

$`K_{iso}(O4)={\displaystyle \frac{8\pi }{3}}g_e\mu _B\psi _{2s}(0)^2\{0.25f_{s,3+}s_z(Mn^{3+})`$
$`f_{s,4+}s_z(Mn^{4+})\}`$ (6)
The sign $`\mathrm{"}+\mathrm{"}/\mathrm{"}\mathrm{"}`$ in (5),(6) takes into account the fact that FM/AF spin correlations of the neighboring Mn3+ and Mn4+ ions are considered as static in the time interval which is much longer that the inverse splitting of the B- and C-line ($`10^8s`$) of the spectrum at $`T=170KT_N`$, when the CO and OO are completely formed in PM state. This agrees with the fact that the O(2s)-polarization is provided predominantly by the $`\sigma `$-overlap with the $`e_g`$-orbitals of Mn, and Pauli blocking of part of $`e_g`$-orbitals in Mn3+ gives stronger polarization than in the case of Mn4+,where both 2s$``$ and 2s$``$-electrons of O2- may virtually hop to Mn4+ so that the net oxygen polarization due to covalency with Mn4+ will be smaller than for Mn3+-neighbor and negative. For crude estimate of the transferred s-spin density we have assumed in (5),(6) that the $`\sigma `$-overlap of $`e_g(m_l=0)`$ orbital of Mn3+ with 2s-orbital of O5 in zigzag of the CE-type charge and orbital ordered phase is twice larger than the overlap with corresponding 2s-orbital of oxygen O4 located between the neighboring zigzags in ab-plane. (Of course under detailed consideration it should depend on interatomic distance and on the bending of the Mn3+-O bond in the tilted and JT distorted MnO6 octahedra.) Inserting the value of the peak position of B-line $`(K_{iso}=40\%)`$ and C-line $`(K_{iso}=55\%)`$ into expressions (6),(5) respectively we get that the transferred s-wave polarization from Mn3+ ion is positive and its absolute value exceeds about 4 times the corresponding negative polarization transferred from Mn4+ $`f_{s,4+}s_z(Mn^{4+})`$.

The large difference in spin densities transferred from Mn3+/Mn4+ ions indicates a substantial delocalization of the ”$`e_g`$-hole” within the hybridized $`e_g(Mn^{3+})`$-2pσ(O) orbital Anisimov-PRB55 . It shows that a pure ionic approach where the $`e_g`$-hole is completely localized at the Mn3+ ion is a very rough approximation to describe in detail the CO and OO in doped manganite.

Unfortunately the spatial distribution of the Fermi contact hyperfine fields results in a large broadening of the separate NMR lines in spectrum measured at $`T<T_{CO}`$. It masks the anisotropy of the magnetic shift tensor and does not permit to trace the transfer of the 2p-spin density at oxygen in the CO PM phase, i.e. to address the orbital order more directly by studying polarization of a given p-orbital.

### III.3 The antiferromagnetic state

Different local fields for apical oxygen in O1 and (O2/O3) sites are expected only in the spin-ordered phase below $`T_N`$. In the AF phase the AF moment canting takes place when a rather high magnetic field ($`7T`$) is applied. The canted moment of Mn in adjacent ab-planes will create at the apical oxygen an additional local field dependent on the valence state of neighboring Mn. At O1 sites the neighboring Mn3+ ions create a larger isotropic magnetic shift than Mn4+ ions do at O2/O3 sites. Indeed, as shown in Fig.4 at $`T=100K`$ A-line splits into two lines of roughly equal intensity. A loose packed powder sample in a strong enough external field may be considered as partially oriented with c$``$H. It should be noted that the observed splitting ( 4MHz) is not a result of the classic dipolar fields of the neighboring Mn ions since the difference in their effective magnetic moments is too small ($`\mu _{eff}=2.7\mu _B`$ for Mn3+ and $`2.2\mu _B`$ for Mn4+ as estimated from Fig.4 in Ref.Jirak-PRB61 ).

The only slight additional broadening of the NMR spectra even around $`T_N/2`$ evidences that the line shift is mainly determined by the short-range CO and OO which have been completely formed in the CO PM phase at $`TT_N`$. Below 110K it appears that the optimal rf pulse duration increases about twice from the low to the high frequency part of the A-line as illustrated in Fig.5. The same feature was found for the high-frequency spectrum when the B- and C-lines are resolved. This striking effect of the nonmagnetic ligand atom on the echo formation may be related to a rather strong isotropic hyperfine interaction between 17O nuclear spin and the Mn electron spin system with long-range AF spin order. The detailed analysis of the spectra measured below $`T_N`$ requires additional studies which are now in progress.

### III.4 Development of charge and orbital ordering

Based on the site assignment considered above we propose the following picture of the development of spin correlation in the Pr0.5Ca0.5MnO3 CO PM phase as seen by 17O NMR. In the low-temperature part of the CO PM phase the NMR spectrum represents the spin density distribution on oxygen ions. Its value is determined not just by the Mn effective magnetic moment but, to a greater extent, by the type of spin correlations of the neighboring Mn atoms. The presence of several lines in NMR spectrum, which can be attributed to the various oxygen sites in the lattice, shows that the corresponding spin correlations and effective magnetic moment of the neighboring cations do not change at the time scale $`t10/(\mathrm{\Delta }\omega )10^6s(\mathrm{\Delta }\omega `$ \- line splitting) Abragam . The thermally activated hopping of $`e_g`$-holes seems to be the main mechanism changing the charge state of the ion (Mn3+-Mn4+) and the spin correlations between the neighboring ions, which results in the ”melting” of OO in CO PM phase. With increasing temperature the fine structure of the spectrum is smeared as the corresponding correlation time $`(\tau _c)`$ of the specific hoping becomes comparable with $`(\mathrm{\Delta }\omega )^1`$. As a result the various spin configurations are no more distinguishable at higher temperature.

The splitting of the NMR spectrum just below $`T_{CO}`$ into the A- and (B+C)-lines may be explained as follows. As has been mentioned above the oxygen nuclei responsible for A-line are located between two AF correlated Mn ions from adjacent ab-plane whereas those responsible for (B+C)-line have two neighboring Mn ions in the same ab-plane. The resolution of A-line shows that just below $`T_{CO}`$ the correlation time of the AF correlated spin of neighboring Mn from adjacent ab-planes becomes long compared to the NMR time scale. By contrast (B+C)-line is still unresolved just below $`T_{CO}`$ . Thus in the first stage of the charge ordering the three-dimensional (3D) motion of eg-electrons transforms preferentially into a two-dimensional (2D) hopping within the ab-planes. Such an ordering phase transition may be considered as the nucleation of AF ordered clusters which grow at the expense of the CD PM phase which dominates above $`T_{CO}`$. Furthermore as the temperature decreases and the unresolved (B+C)-line is shifted toward high frequency a shoulder appears on the low frequency part (see spectra for $`T200K`$ at Fig. 2). The temperature dependence of this signal follows the same Curie-Weiss law as the peak in the CD PM phase (dashed line in Figs. 2, 3). Its relative intensity decreases with temperature and becomes negligible only near $`T_N`$. This may indicate that almost down to $`T_N`$ traces of the CD PM phase remain in the CO PM phase.

The proposed NMR interpretation of the ordering in the CO PM phase is in a good agreement with the main results of the resonant x-ray Zimmerman-PRB61  and neutron diffraction studies Jirak-PRB61 , Kajimoto-PRB63 , Kajimoto-PRB58 . It should be noted that the time scales required to get a quasi-static picture of charge distribution in NMR $`(t_{nmr}>10^6s)`$ and in neutron diffraction $`(t_{nd}10^{12}s)`$ experiments are very different. Both methods confirm the presence of FM correlations between Mn as dominant spin fluctuations in the CD PM phase which reduce in intensity below $`T_{CO}`$ . In the neutron scattering experiments the short-range FM correlations are considered as a static whereas it is seen still as a low-frequency dynamic phenomenon in the NMR spectra. In conclusion, the distribution of spin density and the development of the charge and orbital ordering in the paramagnetic state of Pr0.5Ca0.5MnO3 were studied for the first time by means of 17O NMR. It is shown that the main interaction of oxygen is the isotropic hyperfine Fermi-contact interaction with the s-electron spin density transferred from the nearest-neighboring Mn ions. The resulting magnetic line shift is very sensitive to both the electronic configuration of the neighboring cation (Mn+3/Mn4+) and to their specific spin-pair correlations that develop on cooling in the charge and orbital ordered PM phase. It is shown that with increasing temperature the melting of the orbital ordering first develops within the ab-plane whereas the AF correlations between Mn ions in adjacent layers are more stable and disappear only when T approaches $`T_{CO}`$ .

###### Acknowledgements.

We are very grateful to Prof.A. Kaul for supplying us the starting Pr0.5Ca0.5MnO3 material and to Dr.A. Inyushkin for 17O isotope enrichment. The work is supported partly by Russian Foundation for Basic Research (Grant 02-02-16357a) as well as by CRDF RP2-2355 and INTAS 01-2008 Grants. We are especially grateful for support of A.Y. by ESPCI.