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# On the entropy of spanning trees on a large triangular lattice

## 1 Introduction

It is well-known that spanning trees on an $`n`$-vertex graph $`G`$ can be enumerated by computing the eigenvalues of the Laplacian matrix $`𝐐`$ associated with $`G`$ as

$$N_{\mathrm{ST}}(G)=\frac{1}{n}\underset{i=1}{\overset{n1}{}}\lambda _i,$$
(1)
where $`\lambda _i,i=1,2,\mathrm{},n1`$, are the $`n1`$ nonzero eigenvalues of $`𝐐`$ . In physics one often deals with lattices. For large lattices the number of spanning trees $`N_{ST}`$ grows exponentially in $`n`$. This permits one to define the entropy of spanning trees for a class of lattices $`G`$ as the limiting value

$$S_G=\underset{n\mathrm{}}{lim}\frac{1}{n}\mathrm{ln}N_{\mathrm{ST}}(G).$$
(2)
The resulting finite number $`S_G`$ is a quantity of physical interest.

For regular lattices in $`d`$ dimensions the eigenvalues $`\lambda _i`$ can be computed by standard means  leading to expressions of $`S_G`$ in terms of $`d`$-dimensional definite integrals. The resulting integrals, which are independent of boundary conditions, have been given for a number of regular lattices , but very few of the definite integrals have been evaluated in closed forms.

To be sure, the entropy for the square lattice has been known and computed . It is found to be

$`S_{\mathrm{sq}}`$ $`=`$ $`(4\pi ^2)^1{\displaystyle _0^{2\pi }}𝑑\theta {\displaystyle _0^{2\pi }}𝑑\varphi \mathrm{ln}(42\mathrm{cos}\theta 2\mathrm{cos}\varphi )`$ (3)
$`=`$ $`{\displaystyle \frac{4}{\pi }}\mathrm{Gl}_2\left({\displaystyle \frac{\pi }{2}}\right)`$
$`=`$ $`{\displaystyle \frac{4}{\pi }}\left[1{\displaystyle \frac{1}{3^2}}+{\displaystyle \frac{1}{5^2}}{\displaystyle \frac{1}{7^2}}+{\displaystyle \frac{1}{9^2}}\mathrm{}\right]`$
$`=`$ $`{\displaystyle \frac{4}{\pi }}𝐆`$
$`=`$ $`\mathrm{1.166\; 243\; 616}\mathrm{}`$
where

$$\mathrm{Cl}_2(\theta )=\underset{n=1}{\overset{\mathrm{}}{}}\frac{\mathrm{sin}(n\theta )}{n^2}$$
(4)
is the Clausen’s function and $`𝐆`$ is the Catalan constant. The algebra reducing the double integral in (3) into the series given in the third line is straightforward and can be found in .

The only other published closed-form numerical result on the entropy of spanning trees is that of the triangular lattice  for which one has

$`S_{\mathrm{tri}}`$ $`=`$ $`(4\pi ^2)^1{\displaystyle _0^{2\pi }}𝑑\theta {\displaystyle _0^{2\pi }}𝑑\varphi \mathrm{ln}\left[62\mathrm{cos}\theta 2\mathrm{cos}\varphi 2\mathrm{cos}(\theta +\varphi )\right]`$ (5)
$`=`$ $`{\displaystyle \frac{5}{\pi }}\mathrm{Cl}_2\left({\displaystyle \frac{\pi }{3}}\right)`$
$`=`$ $`{\displaystyle \frac{3\sqrt{3}}{\pi }}\left[1{\displaystyle \frac{1}{5^2}}+{\displaystyle \frac{1}{7^2}}{\displaystyle \frac{1}{11^2}}+{\displaystyle \frac{1}{13^2}}\mathrm{}\right]`$
$`=`$ $`\mathrm{1.615\; 329\; 736\; 097}\mathrm{}.`$
However, no details leading from the double integral in (5) to the final series expression have been published. The expression in the second line is new.

The purpose of this note is to provide some details of the steps leading to the second and third lines in (5) which, as we shall see, are nontrivial. We evaluate the integral in (5) using two different methods: a direct evaluation and a graphical approach. We first evaluate the integral algebraically, and then in an alternate approach we use graphical considerations to convert the spanning tree problem to a Potts model which is in turn related to an $`F`$ model solved by Baxter . In either case, the same series expression in (5) is deduced.111The numerical values of $`S_{\mathrm{tri}}`$ reported in  and  contain typos in the last two digits.

## 2 Algebraic approach

In this section we evaluate the integral (5) directly.

Using the integration formula

$`{\displaystyle \frac{1}{2\pi }}{\displaystyle _0^{2\pi }}𝑑\varphi \mathrm{ln}\left[2A+2B\mathrm{cos}\varphi +2C\mathrm{sin}\varphi \right]=\mathrm{ln}\left[A+\sqrt{A^2B^2C^2}\right],`$
one of the two integrations in (5) can be carried out, giving

$$S_{\mathrm{tri}}=\frac{1}{\pi }_0^\pi 𝑑\theta \mathrm{ln}\left[3\mathrm{cos}\theta +\sqrt{(7\mathrm{cos}\theta )(1\mathrm{cos}\theta )}\right].$$
(6)
Next, we use the identity

$$3\mathrm{cos}\theta +\sqrt{(7\mathrm{cos}\theta )(1\mathrm{cos}\theta )}=\frac{2}{3}\left(v+\sqrt{3+v^2}\right)\left(2v+\sqrt{3+v^2}\right)$$
(7)
where $`v=\mathrm{sin}(\theta /2)`$. Then (6) becomes

$$S_{\mathrm{tri}}=\mathrm{ln}\left(\frac{2}{3}\right)+I_1+I_2,$$
(8)
where

$$I_m=\frac{2}{\pi }_0^{\pi /2}𝑑\theta \mathrm{ln}\left(m\mathrm{sin}\theta +\sqrt{3+\mathrm{sin}^2\theta }\right),m=1,2$$
(9)
after a change of variable $`\theta /2\theta `$.

To evaluate $`I_1`$, we consider the more general integral

$`f(a)={\displaystyle \frac{2}{\pi }}{\displaystyle _0^{\pi /2}}\mathrm{ln}\left(\mathrm{sin}\theta +\sqrt{a^2+\mathrm{sin}^2\theta }\right)`$
such that $`f(\sqrt{3})=I_1`$. Using

$$\frac{2}{\pi }_0^\pi 𝑑\theta \mathrm{ln}\mathrm{sin}\theta =\frac{2}{\pi }_0^\pi 𝑑\theta \mathrm{ln}\mathrm{cos}\theta =\mathrm{ln}2,$$
(10)
we have

$`f(0)`$ $`=`$ $`{\displaystyle \frac{2}{\pi }}{\displaystyle _0^\pi }𝑑\theta \mathrm{ln}(2\mathrm{sin}\theta )𝑑\theta =0,`$
$`f^{}(a)`$ $`=`$ $`{\displaystyle \frac{2a}{\pi }}{\displaystyle _0^{\pi /2}}{\displaystyle \frac{d\theta }{(\mathrm{sin}\theta +\sqrt{a^2+\mathrm{sin}^2\theta })\sqrt{a^2+\mathrm{sin}^2\theta }}}`$
$`=`$ $`{\displaystyle \frac{2}{\pi a}}\mathrm{tan}^1a.`$
The reduction of $`f^{}(a)`$ is effected by noting that $`(\sqrt{\mathrm{sin}^2\theta +a^2}+\mathrm{sin}\theta )^1=(\sqrt{\mathrm{sin}^2\theta +a^2}\mathrm{sin}\theta )/a^2`$. Hence, $`f(a)=(2/\pi )\mathrm{Ti}_2(a)`$ and

$`I_1={\displaystyle \frac{2}{\pi }}\mathrm{Ti}_2(\sqrt{3})`$ (11)
where

$`\mathrm{Ti}_2(a)`$ $`=`$ $`{\displaystyle _0^a}{\displaystyle \frac{\mathrm{tan}^1t}{t}}𝑑t`$
$`=`$ $`a{\displaystyle \frac{a^3}{3^2}}+{\displaystyle \frac{a^5}{5^2}}{\displaystyle \frac{a^7}{7^2}}+\mathrm{}`$
is the inverse tangent integral function described in .

To evaluate $`I_2`$, we introduce the following identity

$$2\mathrm{sin}\theta +\sqrt{3+\mathrm{sin}^2\theta }=\sqrt{3}\mathrm{cos}\theta \sqrt{\frac{1+u(\theta )}{1u(\theta )}},0\theta \pi /2,$$
(13)
where

$`u(\theta )={\displaystyle \frac{2\mathrm{sin}\theta }{\sqrt{3+\mathrm{sin}^2\theta }}}.`$
Substituting (13) into $`I_2`$ in (9) and making use of (10), we obtain

$`I_2`$ $`=`$ $`{\displaystyle \frac{1}{2}}\mathrm{ln}3\mathrm{ln}2+{\displaystyle \frac{1}{\pi }}{\displaystyle _0^{\pi /2}}\mathrm{ln}\left[{\displaystyle \frac{1+u(\theta )}{1u(\theta )}}\right]𝑑\theta `$ (14)
$`=`$ $`{\displaystyle \frac{1}{2}}\mathrm{ln}3\mathrm{ln}2+{\displaystyle \frac{\sqrt{3}}{2\pi }}{\displaystyle _0^1}{\displaystyle \frac{1}{(1u^2/4)\sqrt{1u^2}}}\mathrm{ln}\left({\displaystyle \frac{1+u}{1u}}\right)𝑑u`$
after an obvious change of integration variable in the last step.

Next we express the factor in the integrand as

$`{\displaystyle \frac{1}{1u^2/4}}={\displaystyle \frac{1}{2}}\left[{\displaystyle \frac{1}{1u/2}}+{\displaystyle \frac{1}{1+u/2}}\right]`$
and set

$`x=\sqrt{(1u)/(1+u)}.`$
After a little reduction we obtain

$`I_2={\displaystyle \frac{1}{2}}\mathrm{ln}3\mathrm{ln}2{\displaystyle \frac{2\sqrt{3}}{\pi }}{\displaystyle _0^1}{\displaystyle \frac{\mathrm{ln}x}{3x^2+1}}𝑑x{\displaystyle \frac{2\sqrt{3}}{\pi }}{\displaystyle _0^1}{\displaystyle \frac{\mathrm{ln}x}{x^2+3}}𝑑x.`$
From integration by parts one has

$`{\displaystyle _0^1}{\displaystyle \frac{\mathrm{ln}x}{x^2+a^2}}𝑑x`$ $`=`$ $`\left({\displaystyle \frac{1}{a}}\right){\displaystyle _0^1}{\displaystyle \frac{dx}{x}}\mathrm{tan}^1\left({\displaystyle \frac{x}{a}}\right)`$ (15)
$`=`$ $`\left({\displaystyle \frac{1}{a}}\right)\mathrm{Ti}_2\left({\displaystyle \frac{1}{a}}\right).`$
This yields

$`I_2={\displaystyle \frac{1}{2}}\mathrm{ln}3\mathrm{ln}2+{\displaystyle \frac{2}{\pi }}\left[\mathrm{Ti}_2\left(\sqrt{3}\right)+\mathrm{Ti}_2\left({\displaystyle \frac{1}{\sqrt{3}}}\right)\right].`$ (16)
To express $`I_1`$ and $`I_2`$ in terms of the Clausen’s series (4), we have from Eqs. (2.6), (4.31) and (4.18) of  the identities

$`\mathrm{Ti}_2\left(y^1\right)`$ $`=`$ $`\mathrm{Ti}_2(y){\displaystyle \frac{\pi }{2}}\mathrm{ln}y,y>0`$ (17)
$`\mathrm{Ti}_2(\mathrm{tan}\theta )`$ $`=`$ $`\theta \mathrm{ln}(\mathrm{tan}\theta )+{\displaystyle \frac{1}{2}}\left[\mathrm{Cl}_2(2\theta )+\mathrm{Cl}_2(\pi 2\theta )\right],\theta >0`$ (18)
$`\mathrm{Cl}_2\left({\displaystyle \frac{2\pi }{3}}\right)`$ $`=`$ $`{\displaystyle \frac{2}{3}}\mathrm{Cl}_2\left({\displaystyle \frac{\pi }{3}}\right).`$ (19)
Setting $`y=\sqrt{3}`$ in (17) and $`\theta =\pi /3`$ in (18), we obtain after making use of (19)

$`\mathrm{Ti}_2(\sqrt{3})`$ $`=`$ $`\mathrm{Cl}_2\left({\displaystyle \frac{\pi }{3}}\right)+{\displaystyle \frac{\pi }{6}}\mathrm{ln}3`$
$`\mathrm{Ti}_2\left({\displaystyle \frac{1}{\sqrt{3}}}\right)`$ $`=`$ $`\mathrm{Cl}_2\left({\displaystyle \frac{\pi }{3}}\right){\displaystyle \frac{\pi }{12}}\mathrm{ln}3.`$ (20)
Thus, combining (11) and (16) with (8), we obtain

$$S_{\mathrm{tri}}=\frac{5}{\pi }\mathrm{Cl}_2\left(\frac{\pi }{3}\right)$$
(21)
as given in the second line in (5).

To express $`S_{\mathrm{tri}}`$ in the form of the series given in (5), we note that

$$\mathrm{Cl}_2\left(\frac{\pi }{3}\right)=\frac{\sqrt{3}}{2}S$$
(22)
where

$`S`$ $`=`$ $`{\displaystyle \underset{m=0}{\overset{\mathrm{}}{}}}\left[{\displaystyle \frac{1}{(6m+1)^2}}+{\displaystyle \frac{1}{(6m+2)^2}}{\displaystyle \frac{1}{(6m+4)^2}}{\displaystyle \frac{1}{(6m+5)^2}}\right]`$
$`=`$ $`S_1+{\displaystyle \frac{1}{2^2}}S_2`$
with

$`S_1`$ $`=`$ $`{\displaystyle \underset{m=0}{\overset{\mathrm{}}{}}}\left[{\displaystyle \frac{1}{(6m+1)^2}}{\displaystyle \frac{1}{(6m+5)^2}}\right],`$
$`S_2`$ $`=`$ $`{\displaystyle \underset{m=0}{\overset{\mathrm{}}{}}}\left[{\displaystyle \frac{1}{(3m+1)^2}}{\displaystyle \frac{1}{(3m+2)^2}}\right].`$
Separating terms in $`S_2`$ with odd and even denominators, we have

$`S_2=S_1{\displaystyle \frac{1}{2^2}}S_2.`$
It follows that $`S_2=(4/5)S_1`$ hence $`S=(6/5)S_1`$, and from (21) and (22) we obtain

$`S_{\mathrm{tri}}`$ $`=`$ $`{\displaystyle \frac{3\sqrt{3}}{\pi }}S_1`$
$`=`$ $`{\displaystyle \frac{3\sqrt{3}}{\pi }}\left[1{\displaystyle \frac{1}{5^2}}+{\displaystyle \frac{1}{7^2}}{\displaystyle \frac{1}{11^2}}+{\displaystyle \frac{1}{13^2}}\mathrm{}\right].`$
This is the result given in (5).

## 3 Graphical approach

In this section we evaluate the integral (5) with the help of a graphical mapping.

The medial graph (or the surrounding lattice) $``$’ of a triangular lattice $``$ is the kagome lattice shown in Fig. 1, where we have shaded its triangular faces for convenience. We start from a well-known equivalence between the $`q`$-state Potts model on $``$ and an ice-rule vertex model on $``$ \- . Denote the respective partition functions by $`Z_{\mathrm{Potts}}`$ and $`Z_{\mathrm{kag}\mathrm{ice}}`$. Then the equivalence reads

$$Z_{\mathrm{Potts}}(q,\sqrt{q}x)=q^{n/2}Z_{\mathrm{kag}\mathrm{ice}}(1,1,x,x,t^1+xt^2,t+xt^2)$$
(23)
where

$`x`$ $`=`$ $`(e^K1)/\sqrt{q},`$
$`t^3+t^3`$ $`=`$ $`\sqrt{q},`$ (24)
$`K`$ being the nearest-neighbor interaction of the Potts model, and the arguments of $`Z_{\mathrm{kag}\mathrm{ice}}`$ are weights222In comparing vertex weights with those in , it should be noted that for the triangular lattice which we are considering, roles of shaded and unshaded faces are reversed from those indicated in . of the ice-rule model as depicted in Fig. 2.

On the other hand, it is also known that by taking an appropriate $`q0`$ limit the Potts partition function generates spanning trees . Write the spanning tree generating function in a slightly more general form by attaching a weight $`x`$ to each line segment of the tree. Since the number of lines in a spanning tree on an $`n`$-vertex graph is fixed at $`n1`$, this merely adds an overall factor $`x^{n1}`$. Then, the equivalence reads

$$x^{n1}N_{\mathrm{ST}}=\underset{q0}{lim}q^{(n+1)/2}Z_{\mathrm{Potts}}(q,\sqrt{q}x).$$
(25)
The equivalences (23) and (25) hold quite generally for finite lattices, provided that appropriate vertex weights are defined for the boundary .

We next combine (23) and (25) and take the thermodynamic limit $`n\mathrm{}`$. Assuming the two limits on $`n`$ and $`q`$ commute, this leads to

$$S_{\mathrm{tri}}=\mathrm{ln}x+z_{\mathrm{kag}\mathrm{ice}}(1,1,x,x,t^1+xt^2,t+xt^2),t=e^{i\pi /6}$$
(26)
where

$`z_{\mathrm{kag}\mathrm{ice}}=\underset{n\mathrm{}}{lim}n^1\mathrm{ln}Z_{\mathrm{kag}\mathrm{ice}}.`$
We note in passing that the vertex weights in (26) now satisfy the free-fermion condition

$`11+xx=(t^1+xt^2)(t+xt^2)`$
so $`z_{\mathrm{kag}\mathrm{ice}}`$ can be evaluated by standard means such as using Pfaffians . This verifies the integral expression of $`S_{\mathrm{tri}}`$ given in (5).

Alternately, using a mapping introduced by Lin  (see also ), the kagome ice-rule model can be mapped into an ice-rule model on the triangular lattice. The trick is to ’shrink’ each shaded face of the kagome lattice into a point as shown in Fig. 1. This results in a 20-vertex ice-rule model on the triangular lattice which has 3 arrows in and 3 arrows out at every vertex.

There are 4 different vertex types in the 20-vertex model: (i) six vertices in which the 3 incoming arrows are adjacent, (ii) two vertices in which the incoming and outgoing arrows alternate around the vertex, (iii) six vertices in which 2 incoming arrows are adjacent while the third in-arrow points in a direction opposite to one of the 2 adjacent incoming arrows, and (iv) six vertices in which 2 incoming arrows are adjacent while the third in-arrow points opposite to the other adjacent incoming arrow. These 4 configurations are shown in the left-side column in Fig. 3 to which we assign respective energies $`ϵ_i,i=1,2,3,4`$. The other 16 ice-rule configurations are obtained by rotations.

The shrinking processes from which these ice-rule configurations are deduced are also shown in Fig. 3. Write the 4 weights as $`a,b,c,c^{}`$, respectively. We read off from Fig. 3 to obtain

$`a`$ $`=`$ $`e^{ϵ_1/kT}=11x`$
$`b`$ $`=`$ $`e^{ϵ_2/kT}=(t+xt^2)^3+x^3`$
$`c`$ $`=`$ $`e^{ϵ_3/kT}=x(t+xt^2)^2+x^2(t^1+xt^2)`$
$`c^{}`$ $`=`$ $`e^{ϵ_4/kT}=x^2(t+xt^2)+x(t^1+xt^2)^2.`$ (27)
Thus, we have established the equivalence

$`z_{\mathrm{kag}\mathrm{ice}}(1,1,x,x,t^1+xt^2,t+xt^2)=z_{\mathrm{tri}\mathrm{ice}}(a,b,c,c^{}),`$ (28)
where $`z_{\mathrm{tri}\mathrm{ice}}`$ is defined similar to $`z_{\mathrm{kag}\mathrm{ice}}`$.

Baxter  has considered the evaluation of $`z_{\mathrm{tri}\mathrm{ice}}`$ in the subspace of $`c=c^{}`$. Now the right-hand side of (26) is independent of the value of $`x`$ so we have the freedom to choose a value of $`x`$ for which $`z_{\mathrm{ice}\mathrm{tri}}`$ can be evaluated. It is readily verified that by taking $`x=1/\sqrt{3}`$ and $`t=e^{i\pi /6}`$ we have

$`a=1/\sqrt{3},b=3a,c=c^{}=2a`$
which is a case solved by Baxter. In this case Baxter obtained

$`z_{\mathrm{tri}\mathrm{ice}}(a,3a,2a,2a)`$ $`=`$ $`\mathrm{ln}a+P{\displaystyle _{\mathrm{}}^{\mathrm{}}}{\displaystyle \frac{dx}{x}}{\displaystyle \frac{1+e^x}{(e^x1+e^x)(1+e^{2x}+e^{4x})}}`$ (29)
$`=`$ $`\mathrm{ln}a+{\displaystyle \frac{3\sqrt{3}}{\pi }}\left[1{\displaystyle \frac{1}{5^2}}+{\displaystyle \frac{1}{7^2}}{\displaystyle \frac{1}{11^2}}+{\displaystyle \frac{1}{13^2}}\mathrm{}\right],`$
where $`P`$ denotes the principal value. Combining (26) and (28) with (29) and $`a=1/\sqrt{3}`$, we obtain

$`S_{\mathrm{tri}}={\displaystyle \frac{3\sqrt{3}}{\pi }}\left[1{\displaystyle \frac{1}{5^2}}+{\displaystyle \frac{1}{7^2}}{\displaystyle \frac{1}{11^2}}+{\displaystyle \frac{1}{13^2}}\mathrm{}\right].`$
This is the result given in (5) as first reported in .

## Acknowledgment

Work has been supported in part by NSF Grants DMR-0121146 (MLG) and DMR-9980440 (FYW). We thank W. T. Lu for assistance in preparing the graphs.

Figure captions

Fig. 1. The shrinking of a kagome lattice into a triangular lattice. Each shaded triangular face is shrunk into a point.

Fig. 2. The six ice-rule configurations of the kagome lattice and the associated vertex weights.

Fig. 3. The four types of ice-rule configurations of the triangular lattice and the associated shrinking processes.


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# First principles electronic structure of spinel LiCr2O4: A possible half-metal ?

## I Introduction

The stoichiometric, self-doped oxide spinels LiM2O4 (with M = Ti, V and Mn) can be said to constitute a periodic “hall of fame”. In all of them, Li is monovalent and the oxygen ion, negative and divalent; this means that the transition metal oxidation state is formally 3.5+. The number of $`d`$ electrons per transition metal atom would therefore be 0.5, 1.5, 2.5 or 3.5 when M = Ti, V, Cr or Mn respectively. LiTi2O4 is a superconductor with a $`T_C`$ of 12 K. When first prepared in 1973 liti2o4  it was described as a high temperature superconductor. Along with BaBi1-xPbxO3 sleight , it was amongst the only oxide superconductors with $`T_C>10`$ K until the advent of the layered cuprates. It is also the only metallic oxide spinel known. Its neighbor, LiV2O4 is already on the verge of localization, and as a result, displays heavy-fermion behavior liv2o4  — one of the few systems without $`f`$ electrons that is known to do so — LiMn2O4, one more member from this family, is not only a very important cathode material in secondary Li-ion batteries battery , but also displays charge-ordering rodriguez ; basu1 , associated with half-integral charge that can order over two distinct sites. Indeed, the well-known Verweij transition in ferrite associated with the ordering of charge on the spinel lattice verweij  can perhaps be best understood by examining LiMn2O4. Near the charge-ordering temperature of this compound, a magnetic field can influence electrical transport and this translates to negative magnetoresistence basu2 .

Conspicuous in this list by its absence is the spinel LiCr2O4. Attempts to prepare this compound are fraught with the difficulty of stabilizing Cr in a formal oxidation state that is somewhere between 3+ and 4+. Indeed ferromagnetic CrO2 with the rutile structure is well known to require high oxygen partial pressures for its preparation. CrO2 decomposes at ambient oxygen partial pressures when the temperature exceeds 473 K cro2\_prepn ; kaemper . Given that (i) the isostructural compounds neighboring LiCr2O4 are so interesting, and (ii) the structure and oxidation state of LiCr2O4 are reminiscent of CrO2, the prototypic oxide half-metal kaemper ; cro2\_point , we thought the compound LiCr2O4 worthy of study.

In this work, we use spin-polarized first principles density functional calculations within two different schemes: Full potential linearized augmented plane-wave calculations WIEN97 ; WIEN2k  that permit an optimization of the geometry of the cubic spinel compound (lattice parameter and internal structural parameter) and Linear Muffin Tin Orbital (LMTO) calculations andersen  which are geared to the visualization of spin-resolved bonding. The electronic structure of LiCr2O4 is compared with that of rutile CrO2, LiM2O4 (M = Ti, V and Mn), and ZnV2O4. The parameter space of half-metallicity in LiCr2O4 is mapped out in terms of the two structural parameters.

## II Crystal structures and computational methods

The cubic spinel crystal structure AB2O4 is completely described by two parameters, the cubic cell parameter $`a`$, and the internal oxygen positional parameter $`(x,x,x)`$ where $`x0.25`$ spinel\_struc . The A atoms (Li) occupy tetrahedral sites created by a network of BO6 octahedra where B is here a transition metal. The octahedra of oxygen around B are perfectly regular when $`x=0.25`$. Deviations $`\delta `$, $`x=0.25+\delta `$ indicate either a trigonal expansion ($`\delta >0`$) or compression ($`\delta <0`$), achieved by pushing two opposite triangular faces of the octahedron apart or together. The B atom sublattice (Cr in LiCr2O4) comprises a network of B4 tetrahedra. Because the B atoms form tetrahedra, antiferromagnetic ordering is frustrated on the B site of the spinel anderson  in a manner reminiscent of the residual entropy problem in the crystal structure of ice Ih pauling . Various views of the spinel crystal structure, and the structure of rutile CrO2 are shown in Fig. 1.

Scalar-relativistic Kohn-Sham equations were solved taking all relativistic effects into account except for the spin-orbit coupling. We performed both full potential linearized augmented plane-wave (LAPW) calculations based on the WIEN97 and WIEN2k codes WIEN97 ; WIEN2k  as well as Linear muffin-tin orbital (LMTO) calculations andersen  within the atomic sphere approximation (ASA) where we used the stuttgart tb-lmto-asa program stuttgartLMTO . The generalized gradient approximation (GGA) for the calculation of exchange correlation was considered following the Perdew-Burke-Ernzerhof Perdew\_96  parameterization for the LAPW calculations and the Perdew-Wang prescription perdew-wang  for the LMTO calculationcomment\_GGA .

In our LAPW calculations we considered twenty inequivalent sampling $`k`$ points and the modified tetrahedron method Bloechl\_94  for the Brillouin zone integration during the self-consistent iterations. In order to test the accuracy of the sampling, we also performed calculations with up to 120 and 195 irreducible $`k`$-points without observing significant qualitative changes in the results apart that some spikes in the density of states plots get rounded. We set the energy threshold between core and valence states at -6 Ryd comment\_2 . For the number of plane waves, the criterion used was RMT (Muffin-Tin Radius) $`\times `$ $`k_{\mathrm{max}}`$ (for the plane waves) = 8. We considered various sets of muffin-tin radii to ensure well converged spin-polarized calculations.

In our LMTO calculations 256 irreducible $`k`$ points were used in the primitive wedge of the BZ. Space filling in the unit cell of LiCr2O4 was ensured through the use of two empty spheres with bases of $`s`$ and $`p`$ orbitals at (0, 0, 0) and ($`y`$, 1/8, 1/8) where the value of $`y`$ is set automatically by the code according to the oxygen position. LMTO electronic structures were analyzed by calculating crystal orbital Hamiltonian populations (COHPs) cohp  which are densities of states weighted by appropriate Hamiltonian matrix elements. COHPs are indicative of the strength and nature of a bonding (positive COHP) or antibonding (negative COHP) interaction. The signs we use here are the opposite of what is used in the original definition of Dronskowski and Blöchl cohp . LMTO-ASA calculations do not allow for structural relaxation while structural relaxation process is implemented in the LAPW package. We will present in what follows a comparison of the results obtained by both methods.

## III Crystal and electronic structure of $`\text{LiCr}_2\text{O}_4`$

### III.1 Structure optimization

Within the LAPW scheme we performed a structure optimization for LiCr2O4 where the cubic cell parameter $`a`$ and the oxygen position $`x`$ were varied till the optimal structure was obtained. In order to perform the optimization we considered two steps: (i) We first took several crystal structures with different lattice constants $`a`$ and the same $`x`$. For each of them we performed an iteration procedure up to self-consistency and we compared the total energies. The energy minimum then defines the optimal $`a`$. For LiCr2O4 the energy minimum was reached at $`a`$ = 8.11(4) Å (see Fig. 2).

(ii) In a second step we proceeded to optimize the oxygen positions by evaluating the atomic forces Kohler\_96 . The equilibrium oxygen position was obtained using a damped Newton dynamics method according to the expression

$`R_m^{t+1}=R_m^t+\eta _m(R_m^tR_m^{t1})+\delta _mF_m^t`$ (1)
where $`R_m^t`$ and $`F_m^t`$ are the coordinate and force for the atom $`m`$ at time step $`t`$. $`\delta _m`$ determines the speed of motion and $`\eta _m`$ changes from $`\eta _m`$ to $`1\eta _m`$ if the force changes its direction from one step to the next. The optimal value we obtained for the oxygen position was $`x`$= 0.253(5) which implies a small distortion from the perfect spinel structure. A further unit-cell optimization did not change the result significantly.

In the previous calculation scheme the unit-cell is first optimized and then the structure relaxed. Since the two operations do not necessarily commute, we considered also first a structural relaxation in a bigger unit cell followed by a lattice constant optimization. The two procedures do not yield exactly the same optimal value for $`a`$ and $`x`$, but deviations from $`a=8.11(4)`$ and $`x=0.253(5)`$ are small and can be considered within the error bars.

We checked both in LAPW and LMTO that the ferromagnetic spin-polarized configuration is lower in energy than the non-spin-polarized case. We also considered within LAPW an antiferromagnetic spin arrangement of the Cr atoms in the spinel lattice which showed to be energetically unfavourable with respect to the ferromagnetic arrangement.

### III.2 Density of states (DOS)

Figure 3 compares the partial density of chromium $`d`$ states and oxygen $`p`$ states from spin polarized (a) LAPW calculations and (b) LMTO calculations. In both plots, the Fermi energy is taken as the origin on the energy axis. The upper panel of each plot displays majority (up) spin states and the lower panel minority (down) spin states. Cr-$`d`$ states are shown using black traces and O-$`p`$ state using grey traces. The optimized crystal structure obtained from the LAPW calculations was used as the input crystal structure for the (unrelaxed) LMTO calculations. We note immediately that in terms of gross features, the two computational methods yield quite similar results, in terms both of band positions and widths, as well as details in the structures of the projected densities of state. Differences in the two plots arise only as a result of slightly larger gaps between occupied and unoccupied states between the two computational schemes; the LAPW calculations indicate larger (by 0.5 eV) crystal field splitting as well as larger exchange splitting (by the same magnitude). This different energy shift can be understood in terms of the different nature of the two schemes and that for open structures -as the spinels are- the LMTO approach is not as accurate as the LAPW approach. We use here therefore the LAPW results as a reference for accuracy.

O $`p`$ states are found to be largely centered around -4.5 eV and possess a width of about 5 eV. There are also Cr $`d`$ states in this energy region, indicative of covalency. Near $`E_\mathrm{F}`$ we find majority Cr $`t_{2g}`$ ($``$) and no minority spins in the LAPW DOS, i.e. the polarization is 100% what characterizes the system as half-metallic. In the LMTO DOS there is a residual spin density of minority Cr $`t_{2g}`$ ($``$) spins at $`E_\mathrm{F}`$. While strictly speaking the LMTO results predict an approximate half-metal behavior, the small overall differences between both LMTO and LAPW approaches justifies the use of the LMTO-ASA calculations in some of the subsequent discussion.

The $`t_{2g}()`$ states have a width of about 2 eV and are bimodal, with the two modes separated by a pseudo-gap. The $`E_\mathrm{F}`$ lies in the center of a peak in the DOS. The crystal field splitting between $`t_{2g}()`$ and $`e_g()`$ is of the order of 3 eV (taking the midpoints of the different manifolds) and the exchange splitting between $`t_{2g}()`$ and $`t_{2g}()`$ is of the order of 2 eV. These values are in the LMTO DOS -as discussed above- about 0.5 eV larger.

The two-peaked $`t_{2g}()`$ DOS is puzzling. One suspect is the trigonal distortion of the oxygen octahedron around the Cr atoms. In LiCr2O4, the calculated oxygen position 0.253(5) suggests a very small distortion from perfect octahedral coordination. We have performed LMTO calculations using the ideal oxygen position $`x`$ = 0.250 corresponding to perfect CrO6 octahedra. The differences in the DOS (between the structures where $`x`$ = 0.25 and $`x`$ = 0.253) are negligible and the two-peaked structure of the $`t_{2g}()`$ DOS is retained, and $`E_\mathrm{F}`$ continues to fall in the second DOS peak even when O atoms are in the ideal position and the CrO6 octahedra are undistorted.

Bimodal $`t_{2g}()`$ states, also observed in the electronic structure of spinel LiTi2O4 satpathy , could arise from the restricted B-O-B dispersion in the spinel structure; this network can be built up from B4O4 cubes that are interconnected through B atoms. The B-O-B bond angles are therefore 90. This limits dispersion significantly. In fact, through the analysis of the COHP in LiCr2O4 in the next section we can identify that the upper lobe of the DOS corresponds mainly to Cr-O interactions and less to Cr-Cr interactions.

The most important conclusion that we draw from the DOS of ferromagnetic LiCr2O4 is that states at and near $`E_\mathrm{F}`$ are strongly spin-polarized and the system is indeed a magnetic half-metal. However, the fact that $`E_\mathrm{F}`$ falls on a sharply peaked region of the DOS suggests (i) that the compound might be unstable/difficult to prepare and (ii) if it is prepared, might be subject to electronic instabilities associated with electron correlation, i.e. the opening of a Mott-Hubbard gap, or charge-ordering. We suggest that various different scenarios could stabilize the structure of LiCr2O4, for instance the presence of a slightly distorted antiferromagnetic structure as it is the case in ZnV2O4. Also if the system gets a little oxidized, by removing for instance some Li to form LiδCr2O4, where $`\delta <1`$, it may be then possible to have EF sitting in the pseudogap of the DOS, i.e. at the center of the bimodal DOS and therefore to have a stable structure. A third possibility, as mentioned above, is the explicit consideration of the electron correlation which may open a Mott-Hubbard gap at EF and therefore settle stability.

### III.3 Comparisons with CrO2

It is important to compare the electronic structure of LiCr2O4 with the prototypic oxide half metal CrO2. Present understanding of this material has been reviewed recently coey . This rutile compound Fig. 1(d)) has $`d^2`$ Cr4+ surrounded octahedrally by O2-. The octahedra form ribbons that share edges, and each Cr can therefore be said to bond with two others through the shared edge with a Cr-Cr distance of 2.92 Å burdett . A number of authors cro2\_calc  have described the electronic structure of this material, including Korotin et al. korotin  who performed LDA + $`U`$ calculations and argue thereof that the one-electron description of a ferromagnetic band metal does not suffice and that $`U`$ = 3.0 eV is required to explain the essential features of this compound. Mazin et al. Mazin\_99  argued that when the local interaction is small compared to the bandwidth (W) U/W$``$ 0.5 as in CrO2, it is disputable which method spin-polarized LDA or LDA+U provides a better description of the system.

We have performed spin-polarized LDA calculations in the LMTO scheme on CrO2 for two reasons. The first is that it provides us a consistent comparison with LiCr2O4. The second is that spin-polarized bonding through the use of COHPs has not been presented before for this important compound. Figure 4 compares the Cr $`d`$ and O $`p`$ DOS of (a) LiCr2O4 and (b) CrO2. O $`p`$ states of CrO2 are found to be quite similar to what is seen for LiCr2O4, spreading from around -7 eV to -2 eV. Once again, there is a strong admixture of Cr $`d`$ states in this energy region. The region near the Fermi energy comprised largely of Cr $`d`$ states. The crystal field splitting between $`t_{2g}()`$ and $`e_g()`$ is also similar in both compounds, as might be expected considering the similarity in charge and coordination. What is significantly different is the larger $`t_{2g}()`$ bandwidth in CrO2, as a result of the different Cr-O topology in the rutile structure, that allows for easier metal-oxygen-metal hopping. Unlike what we see in LiCr2O4, the $`E_\mathrm{F}`$ in CrO2 does not lay on a peak but instead, lies on the edge of a pseudo-gap in the $`t_{2g}()`$ states. This gap arises due to a two-in, four-out Jahn-Teller distortion of the CrO6 octahedra burdett .

Crystal orbital Hamiltonian populations (COHPs) permit a better understanding of the precise nature of the different states that would determine the properties of LiCr2O4. In Fig. 5, we plot (a) Cr-Cr COHPs and (a’) Cr-O COHPs as a function of energy for LiCr2O4, per primitive unit cell. This means Cr interacts with six O (at a distance of 2.00 Å) and to six other Cr (at a distance of 2.86 Å). The COHPs are spin resolved into interactions between orbitals with majority spin, and orbitals with minority spin. In the absence of spin-orbit coupling, majority states cannot bond with minority states. In the region of the DOS which was predominantly O-$`p`$ (-7 eV to -2 eV) we find evidence for quite strong Cr-O covalency. At the $`E_\mathrm{F}`$, we find a combination of majority antibonding Cr-Cr interactions and majority antibonding Cr-O interactions, being the Cr-O interaction predominant. There are no minority interactions near the $`E_\mathrm{F}`$ suggesting that the bonding is highly spin-polarized. This is what makes this compound a putative half-metal.

Similar COHPs for CrO2 \[Fig. 5(b) and (b’)\] are depicted per unit cell. In CrO2, each Cr has 6 oxygen neighbors (4 at 1.90 Å and 2 at 1.91 Å), but only two Cr neighbors (at 2.92 Å). The shorter Cr-O distance in CrO2, compared with LiCr2O4 reflects the slightly higher oxidation state of Cr. The Cr-O COHP suggests strong Cr-O bonding in both spin directions in the region where O $`p`$ states are found. Cr-Cr bonding is insignificant in this structure, as a result of the larger Cr-Cr distance than what is found in the spinel, as well as fewer neighbors. This means that Cr $`t_{2g}()`$ states at the $`E_\mathrm{F}`$ are largely non-bonding. As in LiCr2O4, the Cr-O antibonding states at $`E_\mathrm{F}`$ are completely spin-polarized and correspond to interactions in the majority spin channel.

### III.4 Comparisons with other LiM2O4, M = Ti, V and Mn, and with ZnV2O4

It is of interest to compare the DOS of the compounds LiM2O4, M = Ti, V, Cr and Mn. LiTi2O4 is a superconductor. LiV2O4 is a metal on the verge of a metal-insulator transition, with correspondingly, an unusually large effective carrier mass liv2o4 . LiMn2O4 is a correlated antiferromagnetic insulator at low temperatures and displays a charge-ordering transition near the room temperature rodriguez ; basu1 ; basu2 . A number of recent papers describe the electronic structure of LiV2O4 liv2o4\_elec\_struc . For example, Singh et al. singh  have performed LAPW calculations on LiV2O4. They find some evidence for a separation of the $`t_{2g}`$ manifold into $`a_{1g}`$ and $`e_g^{}`$ states as a result of the trigonal distortion of the VO6 octahedra, which is large in this compound. This results in the presence of both flat and disperse bands near the $`E_\mathrm{F}`$, the flat bands presumably giving rise to the effective mass enhancement. Mishra and Ceder mishra  have reported density functional calculations on LiMn2O4, but with an emphasis on structural stability, rather than on magnetism.

Figure 6 compares the LMTO DOS of LiM2O4, M = Ti, V, Cr, Mn. For the V, Cr and Mn compounds, we found that the ferromagnetic spin-polarized configuration was energetically more favourable that the non-spin-polarized configuration. For the Ti compound, the ferromagnetic solution lies in LAPW and LMTO higher in energy than the non-spin-polarized solution. In fact in LMTO we started for this system with a ferromagnetic spin-polarized configuration and in the self-consistency cycles it gets increasingly non-spin-polarized. The width of the O $`p`$ states in all three compounds is similar. The separation between O $`p`$ and metal $`d`$ states is largest in the V compound and smallest in the Mn compound. This is in keeping with the expectation that for a given oxidation state and coordination, moving to the right amongst transition metals results in a stabilization of metal $`d`$ states. Such stabilization is in fact the basis of the evolution of the band gap in correlated transition metal compounds; from the Hubbard $`U`$ type (arising from $`dd`$ Coulomb correlation) for the early transition metals to charge-transfer $`\mathrm{\Delta }`$ (arising from ligand to metal charge transfer) in the later transition metals zaanen ; arima . The width and gross features of metal $`t_{2g}`$ states in these compounds display many similarities, and in fact, a simple rigid band picture of the DOS would perhaps suffice to describe the evolution on going from Ti through Mn. The $`t_{2g}`$ manifold possesses a peaked region at the highest energy in all four compounds. In the Cr compound, this peaked region coincides with the Fermi energy. Interestingly, LiMn2O4 seems to be a low-spin system, with the electronic configuration $`t_{2g}^3()`$, $`t_{2g}^{0.5}()`$, which is distinctly different from the manganese oxides perovskites that display colossal magnetoresistance pickett ; felser . In the perovskites, there is a gap between filled $`t_{2g}^3()`$ states and the partially filled states which are mostly $`e_g()`$ with some small admixture of O $`p`$ and $`t_{2g}()`$.

The compound ZnV2O4 which is isostructural (spinel) and nearly isoelectronic ($`d`$ electron count of 2 on the B site) with LiCr2O4 is known to be a Mott insulator fujimori  ordering antiferromagnetically at 45 K ueda , associated with a tetragonal distortion of the spinel unit cell. Recently Reehuis et al. reehuis  have performed a careful neutron diffraction study on this system. They find a structural transition from cubic $`Fd\overline{3}m`$ to tetragonal $`I4_1/amd`$ at 51(1) K which breaks the magnetic frustration of the spinel structure and allows an antiferromagnetic ground state to be obtained (with $`T_\mathrm{N}`$ = 40(2) K). These authors have obtained precise nuclear and magnetic structures at 60 K (cubic, paramagnetic) and 1.8 K (tetragonal, antiferromagnetic). We have performed LAPW calculations on the cubic phase, and LMTO calculations on using both the cubic as well as the low temperature tetragonal structure reehuis . The LAPW structure optimization gave a cell parameter of 8.348(3) Å to be compared with the 60 K experimental value of 8.4028(4) Å. The calculated internal $`x`$ parameter of O was 0.259(4) Å (experiment = 0.2604(2)). The very close correspondence in this system provides confidence for the optimized LiCr2O4 structure. A magnetic moment of 1.84 $`\mu _\mathrm{B}`$ per V was obtained from LMTO calculations on the cubic phase (1.85$`\mu _{rmB}`$ from LAPW), indicating some reduction of the moment from the spin-only value of 2 $`\mu _\mathrm{B}`$. The DOS for V $`d`$ states and O $`p`$ states for spin-polarized cubic ZnV2O4 is displayed in Fig. 7(a). Key differences in the DOS of ZnV2O4 and LiCr2O4 include reduced metal-oxygen covalency corresponding to fewer V $`d`$ states in the region of O $`p`$ states. In addition, the Fermi energy no longer lies on a sharp DOS peak, despite similarities in the shapes of the $`t_{2g}()`$ manifolds. Cubic ZnV2O4 is a poorer half-metal when compared with LiCr2O4 as already manifest in the reduced magnetic moment. The $`d`$ density of states of one of the V atoms in antiferromagnetic ZnV2O4 is displayed in Fig. 7(b). The LMTO calculations were performed on the experimental structure explicitly considering four independent V atoms forming a distorted tetrahedron with a short and a long V-V distance. The antiferromagnetic structure corresponds to spins on the tetrahedron being antiparallel when proximal (2.962 Å) and parallel when far (2.963 Å) in correspondence with experiment reehuis . We observe that the DOS remains metallic, indicating that correlation must play an important role in this compound, and that the one-electron description does not suffice. The changes in the DOS on going from the ferromagnetic cubic structure to the antiferromagnetic tetragonal structure include a slight narrowing of $`t_{2g}`$ states and a reduction in the contribution from the DOS peak just below the $`E_\mathrm{F}`$.

### III.5 Magnetism of LiCr2O4

Spin polarized LMTO calculations suggested that the magnetic ground state for LiCr2O4 is more stable than the non-magnetic ground state obtained from a non-spin polarized calculation, by 0.4 eV per Cr atom. The converged magnetic moment on Cr was 2.49 $`\mu _\mathrm{B}`$ in calculations that made use of the non-local Perdew-Wang exchange correlation prescription. Since there are 2.5 $`d`$ electrons per Cr3.5+ in LiCr2O4, the value of the magnetic moment corresponds to nearly 100% spin polarization (an extensive discussion was given in section II B.

Withing the usual von-Barth-Hedin LSDA vonBarth , the value was reduced to 2.42 $`\mu _\mathrm{B}`$ per Cr. We were interested in how changes in the crystal structure might affect the magnetism and half-metallicity in LiCr2O4. To this end, we have mapped in Table 1, the magnetization $`M`$ per Cr, as well as the extent of half-metallicity at $`E_\mathrm{F}`$ defined

$$P=\frac{N_{}(E_\mathrm{F})N_{}(E_\mathrm{F})}{N_{}(E_\mathrm{F})+N_{}(E_\mathrm{F})}\times 100\%$$

as a function of the two structural parameters, the cubic cell parameter $`a`$ and the structural parameter $`\delta `$ which is a measure of the trigonal distortion of CrO6 octahedra as described in section II. From Table 1, we see that larger unit cells favor a larger magnetic moment and larger $`P`$. This is due to the narrowing of bands as the separation between atoms becomes larger. Large values of $`\delta `$ seem to be contraindicated for magnetism and half-metallicity; the best half-metals correspond to nearly perfect CrO6 octahedra. These results were confirmed by the structure optimization procedure of the LAPW calculations.

###### Acknowledgements.

This work was partially supported by the MRL program of the National Science Foundation under the Award No. DMR00-80034. RS would like to acknowledge a start-up grant from the Dean, College of Engineering, UCSB. RV thanks A. Krimmel for discussions and acknowledges financial support from the German Science Foundation.


text:
# Finite size effect in Bi2Sr2CaCu2O8+δ and YBa2Cu3O6.7 probed by the in-plane and out of plane penetration depths

## Abstract

We report on a systematic finite size scaling analysis of in-plane penetration depth data taken on Bi2Sr2CaCu2O8+δ epitaxially-grown films and single crystals, and of in-plane and out of plane data taken on YBa2Cu3O6.7 aligned powder. It is shown that the tails in temperature dependence of the penetration depths, appearing around the transition temperature, are fully consistent with a finite size effect. This uncovers the granular nature of these cuprates, consisting of superconducting homogeneous domains of nanoscale extent, embedded in a non-superconducting matrix.

Since the discovery of superconductivity in cuprates by Bednorz and Müller a tremendous amount of work has been devoted to their characterization. The issue of inhomogeneity and its characterization is essential for several reasons, including: First, if inhomogeneity is an intrinsic property, a re-interpretation of experiments, measuring an average of the electronic properties, is unavoidable. Second, inhomogeneity may point to a microscopic phase separation, i.e. superconducting grains, embedded in a non superconducting matrix. Third, there is neutron spectroscopic evidence for nanoscale cluster formation and percolative superconductivity in various cuprates. Fourth, nanoscale spatial variations in the electronic characteristics have been observed in underdoped Bi2Sr2CaCu2O8+δ with scanning tunnelling microscopy (STM). They reveal a spatial segregation of the electronic structure into 3nm diameter superconducting domains in an electronically distinct background. On the contrary, a large degree of homogeneity has been observed by Renner and Fischer. As STM is a surface probe, the relevance of these observations for bulk and thermodynamic properties has been clarified in terms of a finite size scaling of specific heat and London penetration depth data, revealing $`L_{ab}50\AA `$ and $`L_c68\AA `$ for the length scale of the superconducting domains along the c-axis and in the ab-plane, respectively . Fifth, superconducting domains with $`L_{ab}300\AA `$ were revealed by x-ray diffraction in oxygen doped La2CuO4 single crystal . Sixth, in YBa2Cu3O7-δ, MgB2, 2H-NbSe2 and Nb77Zr23 considerably larger domains have been established. The magnetic field induced finite size effect revealed lower bounds ranging from $`L=182`$ to $`814`$Å.

This paper addresses these issues by performing a detailed finite size scaling analysis of the tails in the measured temperature dependence of the penetration depths, appearing around the transition temperature. Specifically we analyze the data taken on Bi2Sr2CaCu2O8+δ in the form of epitaxially-grown films and high quality single crystals, and on magnetically aligned YBa2Cu3O6.7 powder. The paper is organized as follows. Next we sketch the finite size scaling theory adapted for the analysis of penetration depth data. Then we analyze the experimental data and establish the consistency with a finite size effect, uncovering the granular nature of these cuprates, consisting of homogeneous superconducting domains with nanoscale extent, embedded in a non-superconducting matrix.

Supposing that cuprate superconductors are granular, consisting of spatial superconducting domains, embedded in a non-superconducting matrix and with spatial extent $`L_a`$, $`L_b`$ and $`L_c`$ along the crystallographic a, b and c-axis. in this case the correlation length $`\xi _i`$ in direction $`i`$, increasing strongly when $`T_c`$ is approached cannot grow beyond $`L_i`$. Consequently, for finite superconducting domains, the thermodynamic quantities, like the specific heat and penetration depth, are smooth functions of temperature. As a remnant of the singularity at $`T_c`$ these quantities exhibit a so called finite size effect, namely a maximum or an inflection point at $`T_{p_i}`$, where $`\xi _i\left(T_{p_i}\right)=L_i`$. There is mounting experimental evidence that, for the accessible temperature ranges, the effective finite temperature critical behavior of the cuprates is controlled by the critical point of uncharged superfluids (3D-XY). In this case there is the universal relationship

$$\frac{1}{\lambda _i^2\left(T\right)}=\frac{16\pi ^3k_BT}{\mathrm{\Phi }_0^2\xi _i^t\left(T\right)},$$
(1)
between the London penetration depth $`\lambda _i`$ and the transverse correlation length $`\xi _i^t`$ in direction $`i`$. As aforementioned, when the superconductor is inhomogeneous, consisting of superconducting grains with length scales $`L_i`$, embedded in a non-superconducting matrix, the $`\xi _i^t`$’s do not diverge but are bounded by

$$\xi _i^t\xi _j^tL_k^2,ijk.$$
(2)
A characteristic feature of the resulting finite size effect is the occurrence of an inflection point at $`T_{p_k}`$ below $`T_c`$, the transition temperature of the homogeneous system. Here

$$\xi _i^t\left(T_{p_k}\right)\xi _j^t\left(T_{p_k}\right)=L_k^2,ijk,$$
(3)
and Eq.(1) reduces to

$$\frac{1}{\lambda _i\left(T\right)\lambda _j\left(T\right)}|_{T=T_{p_k}}=\frac{16\pi ^3k_BT_{p_k}}{\mathrm{\Phi }_0^2}\frac{1}{L_k}.$$
(4)
In the homogeneous case $`1/\left(\lambda _i\left(T\right)\lambda _j\left(T\right)\right)`$ decreases continuously with increasing temperature and vanishes at $`T_c`$, while for superconducting domains, embedded in a non-superconducting matrix, it does not vanish and exhibits a turning point at $`T_{p_k}<T_c`$, so that

$$d\left(\frac{1}{\lambda _i\left(T\right)\lambda _j\left(T\right)}\right)/dT|_{T=T_{p_k}}=0$$
(5)
Since the experimental data for the temperature dependence of the penetration depths is available in the form $`\lambda _{ab}`$ and $`\lambda _c`$ only, we rewrite Eq.(4) as

$$L_c=\frac{16\pi ^3k_BT_{p_c}\left(\lambda _a\left(T\right)\lambda _b\left(T\right)\right)_{T=T_{p_c}}}{\mathrm{\Phi }_0^2}\frac{16\pi ^3k_BT_{p_c}\lambda _{ab}^2\left(T_{p_c}\right)}{\mathrm{\Phi }_0^2},$$
(6)
and

$$L_b=\frac{16\pi ^3k_BT_{p_b}\left(\lambda _a\left(T\right)\lambda _c\left(T\right)\right)_{T=T_{p_b}}}{\mathrm{\Phi }_0^2}L_{ab}=\frac{16\pi ^3k_BT_{p_b}\left(\lambda _{ab}\left(T\right)\lambda _c\left(T\right)\right)_{T=T_{p_{ab}}}}{\mathrm{\Phi }_0^2}$$
(7)
to derive estimates for the diameter of the superconducting grains along the c-axis and parallel to the ab-plane. Noting that in the homogeneous system the transverse correlation lengths diverge as

$$\xi _i^t\left(T\right)=\xi _{0i}^t\left|t\right|^\nu ,t=\frac{T}{T_c}1,\nu 2/3,$$
(8)
the critical amplitudes and associated critical properties of the homogeneous system can also be derived from a finite size analysis. From Eqs.(6) and (7) we obtain the relations

$$\xi _{ab}^t\left(T_{p_c}\right)=L_c,\sqrt{\xi _{ab}^t\left(T_{p_{ab}}\right)\xi _c^t\left(T_{p_{ab}}\right)}=L_{ab}.$$
(9)
Indeed, the transverse correlation lengths cannot grow beyond the corresponding limiting length scales. Thus given $`T_{p_c}`$and $`L_c`$, $`T_{p_{ab}}`$ and $`L_{ab}`$, the critical amplitudes $`\xi _{0ab}^t`$ and $`\xi _{0c}^t`$ are readily derived. The anisotropy follows then from

$$\gamma =\left(\frac{\xi _{0c}^t}{\xi _{0ab}^t}\right)^{1/2}=\frac{\lambda _{0c}}{\lambda _{0ab}}.$$
(10)
As the system feels its finite size when the correlation length becomes of the order of the confining length, a physical quantity $`O`$ adopts the scaling form

$$\frac{O(t,L)}{O\left(t,L=\mathrm{}\right)}=f\left(x\right),x=\frac{L}{\xi \left(t,L=\mathrm{}\right)}.$$
(11)
The point is that the scaling function $`f`$ depends only on the dimensionless ratio $`L/\xi \left(t,L=\mathrm{}\right)`$ and it does not depend on microscopic details of the system. It does, however, depend on the observable $`O`$, the type of confining geometry and on the conditions imposed (or not, in the case of free boundaries) at the boundaries of the domains. Considering the London penetration depth, it reduces to

$$\frac{\lambda _{0i}\lambda _{0j}}{\lambda _i\lambda _j}\left|t\right|^\nu =f\left(\frac{sign\left(t\right)L_k\left|t\right|^\nu }{\sqrt{\xi _{0i}^t\xi _{0j}^t}}\right)=g\left(y\right),y=sign\left(t\right)\left|t\right|\left(\frac{L_k}{\sqrt{\xi _{0i}^t\xi _{0j}^t}}\right)^{1/\nu }=sign\left(t\right)\left|\frac{t}{t_{p_k}}\right|$$
(12)
For $`t`$ small and $`L_k\mathrm{}`$, $`\pm y\mathrm{}`$ and

$$g\left(y\mathrm{}\right)=1,g\left(y\mathrm{}\right)=0$$
(13)
while for $`t=0`$ and $`L_k0`$

$$g\left(y0\right)=g_{0k}y^\nu =g_{0k}\left(\left|\frac{t}{t_{p_k}}\right|\right)^\nu ,$$
(14)
so that in this limit

$$\frac{\lambda _{0i}\lambda _{0j}}{\lambda _i(T_c,L_k)\lambda _j(T_c,L_k)}=g_{0k}\frac{\sqrt{\xi _{0i}^t\xi _{0j}^t}}{L_k}.$$
(15)
As expected, a sharp superconductor to normal state transition requires domains of infinite extent. Moreover at $`t_p`$, $`y=1`$ and $`d\left(\lambda _{0i}\lambda _{0j}/\left(\lambda _i\left(T\right)\lambda _j\left(T\right)\right)\right)/dt=0`$. Accordingly, there is an inflection point at $`T_{p_k}`$. Since the scaling function $`g\left(y\right)`$ depends on the type of confining geometry and on the conditions imposed (or not, in the case of free boundaries) at the boundaries of the domains, this applies to the amplitude $`g_{0k}`$ as well.

We are now prepared to analyze the extended and systematic penetration depth data of Osborn  *et al.* derived from complex conductivity measurements on epitaxially-grown Bi2Sr2CaCu2O8+δ films using a two-coil inductive technique at zero applied field. In Fig.1 we displayed the temperature dependence of the real part of the complex superfluid density which is proportional to $`1/\lambda _{ab}^2`$ for films A, B and C with different doping level. For comparison we included the leading critical behavior in terms of

$$Re\left(\rho \right)=Re\left(\rho \right)_0\left|t\right|^\nu ,\nu 2/3$$
(16)
with the parameters listed in Table I. Apparently the data is inconsistent with such a sharp transition. It clearly uncovers a rounded transition which occurs smoothly and with that a finite size effect at work. Indeed the extreme in $`d\mathrm{}\left(\rho \right)/dT`$ clearly reveals the existence of an inflection point at $`T_p`$ below the bulk $`T_c`$, where the transverse correlation length $`\xi _{ab}^t`$ attains the limiting length along the c-axis (Eq.(9)). Using the estimates for $`T_p`$, derived from the location of the extremum in $`d\mathrm{}\left(\rho \right)/dT`$ values for $`L_c`$ are now readily calculated with the aid of Eq.(6) and the parameters listed in Table I. The results included in this table clearly point to the nanoscale nature of the inhomogeneities along the c-axis. Nevertheless, due to the small critical amplitude of the transverse correlation length $`\xi _{0ab}^t`$, which follows from Eq.(3) and the corresponding parameters listed in Table I, and the fact that $`L_c`$ is considerably smaller than the film thickness $`d`$, the critical 3D-XY critical regime is attained.

|  | A | B | C | SC1 | SC1 | SC2 |
| --- | --- | --- | --- | --- | --- | --- |
| $`T_c`$ (K) | 78.15 | 84 | 84.4 | 87.5 | 87.5 | 91 |
| $`T_{p_c}`$ (K) | 77.97 | 83.77 | 83.73 | 87 | 87 | 90.5 |
| $`t_{p_c}`$ | 0.0023 | 0.0027 | 0.0079 | 0.0057 | 0.0057 | 0.0055 |
| $`Re\left(\rho \right)_0`$ ( K ) | 450 | 650 | 180 | - | - |  |
| $`\left(\lambda _{ab}\left(0\right)/\lambda _{0ab}\right)^2`$ | - | - | - | 1.25 | 1.25 | 1.65 |
| $`\lambda _{ab}\left(0\right)`$ (nm) | 235 | 265 | 285 | 180 | 250 | 185 |
| $`Re\left(\rho \left(0\right)\right)`$ ( K ) | 169.3 | 135.1 | 116.9 | - | - |  |
| $`Re\left(\rho \left(T_{p_c}\right)\right)`$ ( K ) | 8.51 | 13.66 | 7.1 | - | - |  |
| $`\left(\lambda _{ab}\left(0\right)/\lambda _{ab}\left(T_{p_c}\right)\right)^2`$ | - | - | - | 0.066 | 0.066 | 0.062 |
| $`L_c`$ (Å) | 137 | 93 | 180 | 68 | 132 | 80 |
| $`\xi _{0ab}^t`$ (A) | 2.39 | 1.8 | 7.14 | 2.17 | 4.21 | 2.5 |
| $`d`$ ( Å) | 323 | 616 | 924 | - | - |  |
| $`\left(\lambda _{0ab}\left(0\right)/\lambda _{ab}\left(T_c\right)\right)^2`$ | - | - | - | 0.045 | 0.045 | 0.038 |
| $`Re\left(\rho \left(T_c\right)\right)/Re\left(\rho \right)_0`$ | 0.097 | 0.011 | 0.018 | - | - |  |
| g0 | 0.6 | 0.6 | 0.6 | 1.6 | 1.6 | 1.2 |
| $`g_0\xi _{0ab}^t/L_c`$ | 0.010 | 0.011 | 0.024 | 0.051 | 0.051 | 0.038 |

Table I: Estimates entering and resulting from the finite size scaling analysis of the in-plane penetration depth data of Bi2Sr2CaCu2O8+δ films (A,B,C) and single crystals (SC1 and SC2). The films are respectively, A overdoped, B slightly overdoped and C underdoped.

To extend the analysis further we consider the finite size scaling function entering Eq.(12) in terms of

$$g\left(\frac{t}{\left|t_{p_c}\right|}\right)=\left|t\right|^\nu \frac{Re\left(\rho \right)}{Re\left(\rho \right)_0}.$$
(17)
In Fig.2 we displayed this finite size scaling function for films A, B and C. The collapse of the data on a single curve indicates that the inhomogeneities, also differing in their extent $`L_c`$, have nearly the same shape and are subject to the same boundary conditions. Indeed close to $`t=0`$ the data approaches the expected behavior (Eq.(12))

$$g\left(\frac{t}{\left|t_{p_c}\right|}\right)=g_{0c}\left|\frac{t}{t_{p_c}}\right|^{2/3},$$
(18)
and $`g_{0c}0.6`$. Moreover rewriting Eq.(15) in the form

$$\frac{Re\left(\rho \left(T_c\right)\right)}{Re\left(\rho \right)_0}=g_{0c}\left|t_{p_c}\right|^\nu =\frac{g_{0c}\xi _{0ab}^t}{L_c},$$
(19)
this relation provides a consistency test of the estimates for $`g_{0c}`$, $`\xi _{0ab}^t`$ and $`L_c`$. From Table I it is seen that there is satisfactory agreement.

Next we turn to the microwave surface impedance data for the in-plane penetration depth of a high-quality Bi2Sr2CaCu2O8+δ single crystal. In Fig.3 we displayed the data of Jacobs *et al.* . In analogy to the film data shown in Fig.1 there is clear evidence for a rounded transition, giving rise to an inflection point. Using Eq.(6) the finite size scaling analysis yields the estimates listed in Table I (SC1). In this context it should be kept in mind that there is still a considerable uncertainty in the absolute value of the zero temperature in-plane penetration depth $`\lambda _{ab}\left(0\right)`$, the estimates ranging from $`1800`$ to $`2690`$ Å. For this reason we considered in Table I $`\lambda _{ab}\left(0\right)=1800`$ and $`2500`$ Å, leading to $`L_c68`$ and $`132`$ Å, respectively. In any case, due to the small critical amplitude of the transverse correlation length $`\xi _{0ab}^t`$, the critical 3D-XY regime is attainable in both cases and in agreement with Fig.3.

To substantiate the occurrence of a finite size effect and to clarify whether or not the rather small $`L_c`$ value is associated with a different shape of the superconducting domains and different boundary conditions, we derived and display in Fig.4 the finite size scaling function. The parameters entering this derivation are listed in Table I. Although the curve adopts the generic shape, in analogy to the film data shown in Fig.3, there is an essential difference. Indeed, $`g_{0c}=1.6`$, entering Eq.(18), differs substantially from the film value $`g_{0c}=0.6`$.

To provide some hints concerning the extrinsic or intrinsic nature of the inhomogeneities, we consider next the data taken on a high quality optimally doped Bi2Sr2CaCu2O8+δ single crystal of different provenance. In Fig.5 we displayed the data for the sample with $`T_c=91`$K, obtained with the single coil inductance method. In analogy to the data shown in Figs.1 and 3 there is clear evidence for a rounded transition, giving rise to an inflection point. Invoking the finite size scaling analysis outlined above and the parameters listed in Table I (SC2) we obtain with Eq.(6) for the limiting length along the c-axis the estimate $`L_c80`$Å. Although the data is not very dense around $`T_c`$, the resulting scaling function shown in Fig.6 is consistent with the expected behavior of the finite size scaling function. The solid lines are Eq.(18) with $`g_{0c}=1.2`$.

Summarizing the in-plane penetration depth data taken on three Bi2Sr2CaCu2O8+δ films and two single crystals, we uncovered in all these samples clear evidence for a finite size effect, stemming from the tail in the temperature dependence of the in-plane penetration depth. We have shown that the scaling behavior of this tail is fully consistent with a finite size effect, arising from the finite extent of the superconducting domains along the c-axis (see Figs.2, 4 and 6). Noting that in these five samples $`L_c`$ is of nanoscale and varies from $`68`$ to $`137`$ Åonly, it is suggestive to trace the occurrence of domains back to an intrinsic phenomenon. Furthermore, from Table I it is seen that the $`g_{0c}`$ value of the films differs substantially from that of the single crystals. Since $`g_{0c}`$ depends on the shape of the superconducting domains and the boundary conditions at their surface, it becomes clear that the inhomogeneities in the films differ in an essential manner from those in single crystals. Moreover, given the estimates for $`g_{0c}`$, $`\xi _{0ab}^t`$and $`L_c`$, $`g_{0c}\xi _{0ab}^t/L_c`$ is readily calculated. The resulting estimates provide an independent check of the consistency of the finite size scaling analysis. Indeed, according to Eq.(15), this quantity should equal $`\left(\lambda _{0ab}\left(0\right)/\lambda _{ab}\left(T_c\right)\right)^2`$. In Table I we observe satisfactory consistency.

To substantiate the generic occurrence of the finite size effect we turn to the data taken on magnetic field c-axis aligned YBa2Cu3O6.7 powder, where both, the temperature dependence of the in-plane and out of plane penetration depths, have been measured. In Fig.7 we displayed respectively, $`\left(1/\lambda _{ab}\left(T\right)\right)^2`$, $`d\left(1/\lambda _{ab}\left(T\right)\right)^2/dT`$ versus $`T`$ and $`d\left(1/\lambda _{ab}\left(T\right)/\lambda _c\left(T\right)\right)/dT`$ versus $`T`$. The solid lines are respectively, $`\left(1/\lambda _{ab}\left(T\right)\right)^2=\left(1/\lambda _{0ab}\right)^2\left|t\right|^{2/3}`$ and $`1/\lambda _{ab}\left(T\right)/\lambda _c\left(T\right)=1/\left(\lambda _{0ab}\lambda _{0c}\right)\left|t\right|^{2/3}`$, while the dashed lines are the respective derivatives. These lines indicate the leading critical behavior of the homogeneous system. The corresponding values for $`T_c`$ and the critical amplitude $`1/\left(\lambda _{0ab}\lambda _{0c}\right)`$ are listed in Table II, while the parameters of the finite size scaling analysis are summarized in Table III. Here we used Eqs.(6) and (7) to obtain the estimates for $`L_c`$ and $`L_{ab}`$, the diameters of the superconducting domains. While $`L_c`$ is comparable to the values found in Bi2Sr2CaCu2O8+δ (see Table I), $`L_{ab}`$ turns out to be an order of magnitude larger. Its value $`L_{ab}=592`$Åis consistent with the lower bound $`L_{ab}>576`$Å, derived from the magnetic field induced finite size effect on the specific heat of YBa2Cu3O6.6.

| $`T_c`$ | $`\left(\lambda _{0ab}\right)^2`$ | $`\left(\lambda _{0ab}\lambda _{0c}\right)^1`$ | $`\left(\lambda _{0c}\right)^2`$ | $`\gamma `$ | $`\left(\lambda _{ab}\left(T_c\right)\right)^2`$ | $`\left(\lambda _{ab}\left(T_c\right)\lambda _c\left(T_c\right)\right)^1`$ | $`\left(\frac{\lambda _{0ab}}{\lambda _{ab}\left(T_c\right)}\right)^2`$ | $`\frac{\lambda _{0ab}\lambda _{0c}}{\lambda _{ab}\left(T_c\right)\lambda _c\left(T_c\right)}`$ |
| --- | --- | --- | --- | --- | --- | --- | --- | --- |
| (K) | $`\left(\mu \text{m}\right)^2`$ | $`\left(\mu \text{m}\right)^2`$ | $`\left(\mu \text{m}\right)^2`$ |  | $`\left(\mu \text{m}\right)^2`$ | $`\left(\mu \text{m}\right)^2`$ |  |  |
| 61.5 | 18.5 | 1.4 | 0.11 | 13.2 | 0.874 | 0.076 | 0.047 | 0.054 |

Table II: Estimates for $`T_c`$, $`\left(\lambda _{0ab}\right)^2`$, $`\left(\lambda _{0ab}\lambda _{0c}\right)^1`$, $`\lambda _{0c}`$, $`\gamma =\lambda _{0c}/\lambda _{0ab}`$, $`\lambda _{ab}\left(T_c\right)`$ and $`\lambda _{ab}\left(T_c\right)\lambda _c\left(T_c\right)`$ for YBa2Cu3O6.7 derived from the data shown in Figs.7.

| $`T_{p_c}`$ | $`T_{p_{ab}}`$ | $`\left(\frac{1}{\lambda _{ab}\left(T_{p_c}\right)}\right)_{T_{p_c}}^2`$ | $`\left(\frac{1}{\lambda _{ab}\left(T\right)\lambda _c\left(T\right)}\right)_{T_{p_{ab}}}`$ | $`L_c`$ | $`L_{ab}`$ | $`\xi _{0ab}^t`$ | $`\sqrt{\xi _{0ab}^t\xi _{0c}^t}`$ | $`g_{0c}`$ | $`\frac{g_{0c}\xi _{0ab}^t}{L_c}`$ | $`g_{0ab}`$ | $`\frac{g_{0ab}\sqrt{\xi _{0ab}^t\xi _{0c}^t}}{L_{ab}}`$ |
| --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- |
| (K) | (K) | $`\left(\mu \text{m}\right)^2`$ | $`\left(\mu \text{m}\right)^2`$ | (Å) | (Å) | (Å) | (Å) |  |  |  |  |
| 59.66 | 59.3 | 1.85 | 0.16 | 52 | 592 | 5 | 64.3 | 0.5 | 0.05 | 0.55 | 0.06 |

Table III: Finite size scaling estimates for YBa2Cu3O6.7 derived from the data shown in Figs.7.

(( (a) $`\left|t\right|^\nu \left(\lambda _{0ab}/\lambda _{ab}\left(T\right)\right)^2`$ versus $`t/\left|t_{p_c}\right|`$ and (b) $`\left|t\right|^\nu \left(\left(\lambda _{0ab}\lambda _{0c}\right)/\left(\lambda _{ab}\left(T\right)\lambda _c\left(T\right)\right)\right)`$ versus $`t/\left|t_{p_{ab}}\right|`$ derived from the data shown in Fig.7 for YBa2Cu3O$`_{6.7}.`$ ))

To complete the finite size scaling analysis and the evidence for superconducting domains with diameters $`L_c`$ and $`L_{ab}`$, we displayed in Fig.8 the scaling functions $`\left|t\right|^\nu \left(\lambda _{0ab}/\lambda _{ab}\left(T\right)\right)^2`$ versus $`t/\left|t_{p_c}\right|`$ and $`\left|t\right|^\nu \left(\left(\lambda _{0ab}\lambda _{0c}\right)/\left(\lambda _{ab}\left(T\right)\lambda _c\left(T\right)\right)\right)`$ versus $`t/\left|t_{p_{ab}}\right|`$. Together with Eqs.(13) to (14) we observe the required agreement with the behavior of the respective finite size scaling function. The near coincidence $`g_{0c}g_{0ab}0.5`$ implies nearly identical shape and boundary condition along the c-axis and the ab-plane. Moreover, $`g_{0c}0.5`$ is close to the value in the Bi2Sr2CaCu2O8+δ films (Table I). To provide a consistency check of the finite size scaling analysis we note that, given the estimates for $`g_{0k}`$, $`\sqrt{\xi _{0i}^t\xi _{0j}^t}`$ and $`L_k`$, the quantity $`g_{0k}\sqrt{\xi _{0i}^t\xi _{0j}^t}/L_k`$ is readily calculated and should be equal to $`\left(\lambda _{0i}\lambda _{0j}\right)/\left(\lambda _i\left(T_c\right)\lambda _j\left(T_c\right)\right)`$(Eq.(15)). Tables II and III reveal satisfactory agreement.

To summarize, we have shown that the tail in the temperature dependence of the in-plane and out of plane penetration depth around $`T_c`$, as observed in the experimental data considered here, is fully consistent with a finite size effect, arising from homogeneous nanoscale superconducting domains with diameters $`L_{ab}`$ and $`L_c`$. Clearly this finite size effect is not restricted to the penetration depth but should be visible in other thermodynamic properties, including the specific heat, as well. In the specific heat it leads to a rounding of the peak and its consistency with a finite size effect was established for the data taken on YBa2Cu3O7-δ high quality single crystals. In these samples the domain size was found to range from 300 to 400 Å. Although the investigations of Gauzzi *et al.* on YBa2Cu3O6.9 films with reduced long-range structural order clearly reveal that the size of the domains depends strongly on the growth conditions, we established their nanoscale size and their thermodynamic relevance in a variety of samples.

We thank K. D. Osborn *et al.* for providing their experimental data.


text:
# Precision frequency measurement of visible intercombination lines of strontium

## Abstract

We report the direct frequency measurement of the visible 5s21S0-5s 5p3P1 intercombination line of strontium that is considered a possible candidate for a future optical frequency standard. The frequency of a cavity-stabilized laser is locked to the saturated fluorescence in a thermal Sr atomic beam and is measured with an optical-frequency comb-generator referenced to the SI second through a GPS signal. The 88Sr transition is measured to be at 434 829 121 311 (10) kHz. We measure also the 88Sr-86Sr isotope shift to be 163 817.4 (0.2) kHz.

PACS 32.30.Jc, 06.30.Ft, 42.62.Fi, 39.30.+w, 32.80.-t

The recent development of optical-frequency comb generation has made possible, for the first time, relatively easy optical frequency measurements . This, in turn, opened the way to atomic clocks based on optical frequency transitions. Because of their higher frequency, these transitions have potential for greatly improved accuracy and stability relative to conventional atomic clocks based on microwave frequency transitions . Different transitions are now considered as optical frequency standards, involving single ions and neutral atoms . While single ions offer an excellent control on systematic effects, clouds of laser cooled atoms have the potential for extremely high precision. Amongst the neutral atoms, Sr has long been considered one of the most interesting candidates . Several features, some of which are specific to this atom, allow different possibilities for the realization of a high precision optical clock. The intercombination 51S-53P lines from the ground state are in the visible and easily accessible with semiconductor lasers (Fig.1). Depending on the specific fine-structure component and on the isotope - Sr has four natural isotopes, three bosonic, 88Sr (82%), 86Sr (10%), 84Sr (0.5%) with nuclear spin I=0 and one fermionic, 87Sr (7%) with I=9/2 - a wide choice of transitions with different natural linewidths is possible. These span from the 7.5 kHz linewidth of the 51S0-53P1 line, which is the subject of the present paper, down to the highly forbidden 51S0-53P0,2 transitions. In 87Sr, the presence of hyperfine mixing makes the 0-0 transition weakly allowed with an expected natural width of about 1 mHz.

From the point of view of laser cooling and manipulation, Sr has several interesting features which are also important for the final operation of a precise frequency standard: two-stage cooling using the intercombination transition allows extremely low temperatures and magneto-optical trapping; atoms can be trapped in optical lattices with negligible shift of the optical clock transition . After initial laser spectroscopy experiments based on wavelength metrology and discharges as atomic sources , recently Sr has been the subject of several experiments aiming to all-optical cooling down to quantum degeneracy for bosonic and fermionic isotopes , continuous atom laser , and detection of ultra-narrow transitions . This atom is also considered interesting for the understanding of its spectrum  and for the investigation of cold collisions .

In this paper, we report the first precision frequency measurements on the intercombination 51S0-53P1 transition. Using a femtosecond laser comb, we determine the absolute frequency of the transition for 88Sr and 86Sr and a very accurate value for the isotope shift. The improvement by several orders of magnitude with respect to previous data and the use of a relatively simple and compact apparatus demonstrate the potentialities of this system.

The experimental setup we use is composed of a laser-diode frequency-locked to an optical cavity whose modes are locked to keep the laser on resonance with the atomic line. The optical frequency is measured with a self-referenced optical-comb stabilized against a Global Positioning System (GPS) controlled quartz. A scheme of the experimental setup is given in Fig. 2. The extended cavity laser-diode (ECDL) is a Hitachi HL6738MG mounted in the Littrow configuration which delivers typically 15 mW. Optical feedback to the ECDL is prevented by a 40 dB optical isolator and a single pass acusto-optic modulator in cascade. The laser linewidth is reduced by locking the laser to an optical reference cavity (RC) with the classic Pound-Drever-Hall scheme ; the phase modulation is produced by a resonant electro-optic modulator (EOM) driven at 21 MHz. To avoid residual standing wave in the EOM, which induces spurious AM on the locking signal, a 25 dB optical isolator is placed between the EOM and the cavity. The reference cavity has a free spectral range (FSR) of 1.5 GHz and a finesse of 10000. On one side of the quartz spacer we glued a concave mirror (R=50 cm) while on the other side a piezoelectric transducer (PZT) is glued between the spacer and a flat mirror in order to steer the modes of the cavity by more than one FSR.

The lock of the laser onto the cavity includes a low frequency loop acting on the PZT of the ECDL (1 kHz bandwidth), and a high frequency loop acting on the laser-diode current supply (1 MHz bandwidth). Under lock condition more than 55 % of the incident light is transmitted through the cavity. From the noise spectra of the locking signal and by comparison with another cavity we can infer a laser linewidth less than 2 kHz, and more than 90 % of the optical power in the carrier . We do not passively stabilize the RC in a vacuum chamber  since the acoustic and sub acoustic noise is removed by the servo to the atomic signal which acts on the PZT of the RC with a 200 Hz bandwidth.

The strontium atomic beam is obtained from the metal heated to 830 K in an oven and using a bundle of stainless steel capillaries to collimate it . The residual atomic beam divergency is 25 mrad and the typical atomic density in the detection region is $`10^8`$ cm-3.

The Doppler-free atomic line is resolved by saturation spectroscopy using two counterpropagating laser beams perpendicular to the atomic beam. The fluorescence light from the laser excited atoms is collected on a photomultiplier tube with an efficiency of 0.4 % including quantum efficiency and solid angle. Orthogonality between atomic and laser beams is optimized by centering the Lamb dip with respect to the Doppler profile.

The laser beam is filtered using a single mode fiber and collimated at a $`1/e^2`$ diameter of 14 mm (wavefront distortion less than $`\lambda `$/6); the beam is retro-reflected using a mirror at a distance of 65 mm from the interaction region and coupled back into the fiber. We estimate the indetermination on the angle of the retroreflected beam to be less than 10 $`\mu `$rad maximizing the transmitted power through the fiber. The peak beam intensity of 60 $`\mu `$Wcm-2 (to be compared to the saturation intensity of 3 $`\mu `$Wcm-2) was chosen to obtain sufficient signal to noise for the RC lock onto the atomic resonance. A uniform magnetic field of 10 G defines the quantization axis in the interrogation region such that the light is $`\pi `$ polarized.

The acusto-optic modulators between the ECDL and the EOM (AOM1) and between the ECDL and the slave laser (AOM2) are driven from the same oscillator and both deliver the -1 order such that the frequency instability and indetermination of their driving RF does not affect the optical frequency measurement. The double pass AOM next to the atomic detection (AOM3) is frequency modulated at 10 kHz to derive the locking signal of the cavity onto the atomic line.

Fig. 3 shows the Doppler broadened resonances of 88Sr, 86Sr and the hyperfine structure of 87Sr. The residual atomic beam divergency produces a residual Doppler broadening of 60 MHz FWHM. In the inset, the sub-Doppler signal for 88Sr is shown. Two independent measurements  of the sub-Doppler resonance show a FWHM of about 50 kHz, which is in agreement with the expected value considering the saturation and transit time broadening, and the recoil splitting.

We measure the optical frequency through a commercial optical frequency comb generator based on a Kerr-lens mode-locked Ti:Sa laser with a repetition rate of 1 GHz (MenloSystems GmbH, Model FC8003). The repetition rate and carrier offset envelope frequency are locked to a GPS stabilized quartz oscillator, as well as counters and RF generators for AOM’s. Figure 4 shows the result of the measurement of the 88Sr transition frequency taken over a period of several days. Each data point corresponds to the averaging of the values resulting from consecutive measurements taken with a 1 s integration time over 100-200 s. The error bars correspond to the standard deviation for each data set. The Allan deviation of each set shows a flicker floor varying between 1 and 2 kHz in the region from 1 to 100 seconds.

We evaluated 1st and 2nd order Doppler and Zeeman effects, AC Stark shift, collisional shifts, and mechanical effects of light (table I). The 1st order Doppler shift resulting from imperfect alignment in the standing wave was randomized by realigning the retroreflected beam after each measurement; the resulting contribution in the final uncertainty is included as 2 kHz. The offsets and lineshape asymmetries introduced by the recoil, atom deflection induced by the light field, and 2nd order Doppler were calculated by numerically integrating the 1D optical Bloch equations along the atomic trajectories considering the experimental conditions . The resonance linewidth obtained from this simulation is in good agreement with the experimental value proving that we do not have unexplained line broadening mechanisms. Since we observe a closed transition we estimate the offset introduced by unbalanced counter-propagating beams and curved wavefront , and wavefront distortion less than 2 kHz . There is no first order Zeeman shift because we observe the J = 0 to J = 1, $`\mathrm{\Delta }`$m = 0 transition. The second-order Zeeman shift in our magnetic field is of the order of few Hz. The collisional shift coefficient for this transition has not been measured but the self broadening coefficient is known to be about 50 MHz/torr . Assuming as an upper limit for the collisional shift the self broadening coefficient and considering the background pressure of the order of 10-6 torr, we expect a pressure induced shift of less than 50 Hz. Unbalanced sidebands on the interrogating laser were measured to be more than 40 dB below the carrier leading to a shift smaller than 1% of the atomic linewidth. In our experimental conditions, we did not experimentally observe any dependence of the measured optical frequency on the modulation depth and laser intensity, which is in agreement with numerical simulations. The resulting value for the 88Sr transition frequency, including the corrections discussed previously, is 434 829 121 311 (10) kHz, corresponding to a $`1\sigma `$ relative uncertainty of $`2.3\times 10^{11}`$.

With a minor change in the apparatus, we locked simultaneously the frequency of two laser beams to the sub-Doppler signals of 86Sr and 88Sr. This system allowed us to measure the isotope shift by counting the beatnote between the two interrogating beams. For this purpose, the reference cavity is locked to 88Sr resonance as described previously and the light for 86Sr is derived from the same laser beam and brought to resonance through AOM’s. The two beams are overlapped in a single mode optical fiber and sent to the interrogation region. By frequency modulating the beams at different rates and using phase sensitive detection we get the lock signal for both the isotopes from the same photomultiplier. The lock on 86Sr acts on the voltage-controlled oscillator that drives one of its AOMs. The 86Sr lock bandwidth of 1 Hz, limited by lower signal to noise, is enough since the short term stability is insured by the lock to the reference cavity and 88Sr. In this isotope shift measurement most of the noise sources are basically common mode and rejected; the Allan variance shows a white noise spectrum of 1 kHz at 2 s and does not show any flicker noise for times longer than 500 s resulting in precision better than 100 Hz. At this level of precision we observe the servo loop offset compensation limiting the reproducibility to 200 Hz. The measured 88Sr-86Sr isotope shift for the 1S0-3P1 transition is 163 817.4 (0.2) kHz. This value represents an improvement in accuracy of more than 3 orders of magnitude with respect to previously available data . The 86Sr optical frequency then amounts to 434 828 957 494 (10) kHz.

The isotope-shift experiment provides also an indication of the stability of the lock to the atomic line for periods longer than 2 s . We conclude that the observed flicker noise at $`5\times 10^{12}`$ in the absolute frequency measurement may be attributed to the optical frequency comb including its frequency reference. Moreover the relative uncertainty of $`1.2\times 10^{11}`$ due to uncontrolled systematic effects does not explain completely the data scatter of $`5\times 10^{11}`$ in the absolute frequency measurement. We did not evaluate the noise performance in the GPS disciplined quartz oscillator that is our local frequency reference. Possible sources of noise are oscillation frequency sensitivity of quartz to vibration and the behaviour of the complex, adaptive filter used to discipline the quartz local oscillator to the GPS signal in the 103-104 s region, which is the time period in which we are making our measurements.

In conclusion, we demonstrated locking of a laser-diode to the visible 5s21S0-5s 5p3P1 intercombination line of Sr and measured its frequency using an optical-frequency comb-generator referenced to the SI second through a GPS signal. The optical frequency measurement is obtained with a relative uncertainty of $`2.3\times 10^{11}`$, which represents an improvement of more than 4 orders of magnitude with respect to previous data . We also obtain an accurate value for the 88Sr-86Sr isotope shift improving the accuracy by more than 3 orders of magnitude.

Future improvements and developments involve cooling and trapping of Sr atoms. Using cold atoms a precision in the range of one part in 1014 in one second can be expected with the transition investigated in this work. Probing the ultra-narrow $`00`$ or $`02`$ transitions in cold trapped atoms should lead to a dramatic improvement in stability and accuracy opening the way to the $`10^{17}10^{18}`$ range. A Sr-based optical reference could employ all-solid-state laser sources (including light at 461 nm required for cooling and trapping). The realization of ultra-precise optical frequency standards based on compact and eventually transportable systems will enable future tests of fundamental physics on Earth and in space.

We are grateful for the experimental assistance of T. Brzozowski and C. De Mauro. We thank P. Lemonde for a critical reading of the manuscript. G.M.T. also acknowledges seminal discussions with J.L. Hall and C. Salomon. This work was supported by MIUR, EC (contract No. HPMT-CT2000-00123), ASI and INFM.


text:
# Sensitivity to 𝜃₁₃ and 𝛿 in the Decaying Astrophysical Neutrino Scenario

(23 September 2003)

## Abstract

We have previously shown that the decay of high-energy neutrinos from distant astrophysical sources would be revealed by flavor ratios that deviate strongly from the $`\varphi _{\nu _e}:\varphi _{\nu _\mu }:\varphi _{\nu _\tau }=1:1:1`$ expected from oscillations alone. Here we show that the deviations are significantly larger when the mixing angle $`\theta _{13}`$ and the CP phase $`\delta `$ are allowed to be nonzero. If neutrinos decay, this could allow measurement of $`\theta _{13}`$ and $`\delta `$ in IceCube and other near-term neutrino telescopes.

Traveling over cosmological distances, neutrino wave packets decohere into mass eigenstates. The probability to measure a neutrino flavor $`\beta `$ at Earth is therefore

$$P_\beta =\underset{\alpha }{}w_\alpha \underset{j}{}|U_{\alpha j}|^2|U_{\beta j}|^2,$$
(1)
where $`U_{\alpha j}`$ are elements of the neutrino mixing matrix, and $`w_\alpha `$ are the weights of the flavors produced in the astrophysical source. As is well-known, the weights from a pion-muon decay chain, $`w_e:w_\mu :w_\tau =1:2:0`$, lead to flavor ratios at Earth of $`\varphi _{\nu _e}:\varphi _{\nu _\mu }:\varphi _{\nu _\tau }=1:1:1`$ 111 . Variation of the mixing angles from the assumed $`\nu _\mu \nu _\tau `$ symmetry limit ($`\theta _{23}=45^{}`$ and $`\theta _{13}=0`$) leads to only small ($`20\%`$) deviations.

We have recently shown that the expected flavor ratios would be dramatically altered if neutrinos decay cosmicDK . The strongest lifetime limits, from solar neutrinos, are too weak to restrict the possibility of astrophysical neutrino decay by a factor of about $`10^7`$ solarDK ; cosmicDK . Other scenarios, small-$`\delta m^2`$ active-sterile mixing in pseudo-Dirac pDirac  or mirror models steriles , or CPT violation Barenboim , produce more subtle deviations from the expected $`1:1:1`$. While neutrino decay can be tested with IceCube IceCube  and other near-term detectors, the latter scenarios may require future detectors flavors .

The most interesting decay scenario is that in which $`\nu _3`$ and $`\nu _2`$ decay (either into active $`\nu _1`$ or sterile states), but the lightest neutrino $`\nu _1`$ is stable. In this case, the beam contains just the single mass eigenstate $`\nu _1`$, and the flavor ratios at Earth are simply

$$\varphi _e:\varphi _\mu :\varphi _\tau =|U_{e1}|^2:|U_{\mu 1}|^2:|U_{\tau 1}|^2.$$
(2)
We present here further analysis of this scenario, taking into account the broken $`\nu _\mu \nu _\tau `$ symmetry that arises when $`U_{e3}=\mathrm{sin}\theta _{13}e^{i\delta }0`$. Even for small $`\theta _{13}`$, we find that the flavor ratios are very sensitive to the CP phase $`\delta `$, which was set to zero for simplicity in our earlier work cosmicDK .

We assume a normal neutrino mass hierarchy. For the case of an inverted hierarchy (or no decay), varying $`\theta _{13}`$ has little effect. Note that in this decay scenario, there is no dependence on the initial astrophysical flux ratios, and hence on the production mechanism of the ultra high energy neutrinos, since the flux reaching Earth consists only of the lightest neutrino $`\nu _1`$.

Expressing the flavor ratios in Eq. (2) in terms of the mixing parameters (using the conventions of Ref. RPP  and $`c_{ij}\mathrm{cos}\theta _{ij}`$, $`s_{ij}\mathrm{sin}\theta _{ij}`$),

$$\frac{\varphi _\tau }{\varphi _\mu }=\frac{s_{12}^2(1\mathrm{cos}2\theta _{23})+s_{13}^2c_{12}^2(1+\mathrm{cos}2\theta _{23})4\widehat{J}}{s_{12}^2(1+\mathrm{cos}2\theta _{23})+s_{13}^2c_{12}^2(1\mathrm{cos}2\theta _{23})+4\widehat{J}}.$$
(3)
We have defined

$$\widehat{J}\frac{1}{4}\mathrm{sin}2\theta _{12}\mathrm{sin}2\theta _{23}(s_{13}\mathrm{cos}\delta ),$$
(4)
which is related to the Jarlskog invariant $`J`$ according to $`J=\widehat{J}c_{13}^2\mathrm{tan}\delta `$. It is known, and is evident in Eq. (3), that either a nonzero $`\mathrm{cos}2\theta _{23}`$ or $`s_{13}`$ breaks $`\nu _\mu \nu _\tau `$ symmetry. In Fig. 1, we show the ratio $`\varphi _\tau /\varphi _\mu `$ as a function of $`|U_{e3}|^2`$ (within the range allowed by reactor experiments reactors ), with $`\theta _{23}=\pi /4`$ fixed. Even a small $`\theta _{13}`$ has a relatively large effect, particularly when the CP phase $`\delta `$ is allowed to be nonzero. However, direct measurement of the ratio $`\varphi _\tau /\varphi _\mu `$ is very difficult, since events which are unique to $`\nu _\tau `$ (double-bang and lollipop events) have much lower detection probabilities flavors .

In contrast, the $`\varphi _e/\varphi _\mu `$ ratio can be directly probed in a detector like IceCube by comparing the rate of shower events to muon events flavors . This flavor ratio is

$$\frac{\varphi _e}{\varphi _\mu }=\left(\frac{|U_{e1}|^2}{1|U_{e1}|^2}\right)\left(1+\frac{\varphi _\tau }{\varphi _\mu }\right).$$
(5)
The $`\nu _e`$ fraction in the $`\nu _1`$ mass eigenstate is insensitive to values of $`\theta _{13}`$ in the allowed range, shown by the first factor in Eq. (5), where $`|U_{e1}|(c_{12}c_{13})^2`$. However, the broken $`\nu _\mu \nu _\tau `$ symmetry affects the $`\varphi _e/\varphi _\mu `$ ratio through the second factor in Eq. (5), and this is a large effect. When $`\mathrm{cos}\delta `$ is negative (positive) it decreases (increases) the $`\nu _\mu `$ fraction of $`\nu _1`$ with respect to the $`\nu _\tau `$ fraction, resulting in an enhanced (suppressed) $`\nu _e/\nu _\mu `$ ratio. This is shown in Fig. 2. The curve with $`\delta =0`$ is as in Ref. cosmicDK , though we have updated the solar angle $`\theta _{12}`$. For nonzero $`\delta `$, new to this work, the flavor ratio is significantly farther from the no-decay value of 1.

Note that the dependence of Eqs. (3) and (5) on the CP phase $`\delta `$ occurs only through $`\mathrm{cos}\delta `$, since this is a CP-conserving observable. Therefore, it is not necessary to separate astrophysical neutrinos and antineutrinos, which would be very difficult. The phase $`\delta `$ is of crucial importance in terrestrial long-baseline oscillation experiments since CP-violating observables, based on the comparison of neutrino and antineutrino oscillation probabilities, are proportional to $`\mathrm{sin}\delta `$ LB . Farzan and Smirnov have shown that a nonzero $`\mathrm{sin}\delta `$ may in principle also be inferred by direct construction of the leptonic unitarity triangle Farzan . A key distinction is that the terrestrial experiments use a beam of flavor eigenstates, whereas neutrino decay can produce a pure mass eigenstate, allowing for very large variation with $`\delta `$. Since measurement of $`\delta `$ in terrestrial experiments will be an extremely challenging task, it is intriguing to find an example where the effect of varying $`\delta `$ is huge. Finally, the flavor ratios are sensitive only to the “Dirac” phase $`\delta `$, and not the “Majorana” phases; Majorana phases are relative phases between mass eigenstates, and the beam consists of the single mass eigenstate $`\nu _1`$.

Variation of the atmospheric mixing angle $`\theta _{23}`$ away from $`45^{}`$ also breaks the $`\nu _\mu \nu _\tau `$ symmetry, as shown in Eq. (3), and has a similar effect on the flavor ratios. Variation of the solar mixing angle changes the $`\varphi _e/\varphi _\mu `$ ratio as it alters the $`\nu _e`$ fraction of $`\nu _1`$. In Fig. 3, we show how the variations of these angles within their one-sigma allowed ranges affects $`\varphi _e/\varphi _\mu `$. Note that the size of the variation due to uncertainties in the solar and atmospheric angles are quite similar. These uncertainties will be reduced by existing or planned solar and long-baseline experiments. The angle $`\theta _{13}`$ may be measured by future long baseline LB  or reactor reactor13  experiments, and measuring $`\delta `$ may require a neutrino factory.

To conclude, IceCube and other detectors have an excellent chance of detecting astrophysical neutrinos and measuring their flavor ratios in the next several years. If neutrinos decay, the flavor ratio $`\varphi _e/\varphi _\mu `$ will be much larger than its no-decay value of 1, and this effect is significantly enhanced by nonzero $`\theta _{13}`$ and $`\delta `$. Thus there may be a new opportunity to measure the last unknown values in the neutrino mixing matrix.

Acknowledgments.— We thank Stephen Parke for illuminating discussions. J.F.B. and N.F.B. were supported by Fermilab (operated by URA under DOE contract DE-AC02-76CH03000) and NASA grant NAG5-10842; S.P. by DOE grant DE-FG03-94ER40833; and T.J.W. by DOE grant DE-FG05-85ER40226, NASA grant NAG5-13399, and a Vanderbilt Discovery Award. T.J.W. also thanks the U. Wisconsin Phenomenology Group for hospitality.