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# Finite-size and asymptotic behaviors of the gyration radius of knotted cylindrical self-avoiding polygons

## I Introduction

A ring polymer is one of the simplest systems that have the effect of topological entanglement. The topological state of a ring polymer is given by a knot, and it is fixed after the ring polymer is formed. The entropy of the ring polymer with the fixed knot is much smaller than that of no topological constraint. Thus, there should be several nontrivial properties in statistical mechanics of ring polymers with a fixed topology. Furthermore, some dynamical or thermodynamical properties of ring polymers under topological constraints could also be nontrivial. In fact, various computer simulations of ring polymers with fixed topology were performed by several groups Vologodskii1 ; desCloizeaux ; LeBret ; Chen ; Michels ; Klenin ; Janse1991 ; Koniaris ; DeguchiJKTR ; DeguchiRevE ; Orlandini ; Lai . However, there are still many unsolved problems related to the topological effect, such as the average size of a knotted ring polymer in solution.

In the paper, we discuss how the excluded volume controls the topological effect on the average size of ring polymers in good solution. As a model of ring polymers we employ a model of self-avoiding polygons consisting of cylindrical segments with radius $`r`$. Through numerical simulation, we investigate the mean square radius of gyration of cylindrical self-avoiding polygons with radius $`r`$ PLA ; JPSJ ; PRE . By changing the cylinder radius $`r`$, we modify the excluded volume effect. Thus, we can investigate the topological effect systematically through the simulation of cylindrical self-avoiding polygons for various values of cylinder radius $`r`$.

Let us consider the two cases when the radius $`r`$ is very large or very small. When the radius $`r`$ is very large, the simulation should be related to that of the self-avoiding polygons on the lattice Orlandini ; PRE . On the other hand, when the radius $`r`$ is very small, it is related to random polygons with a fixed topology, as we shall see explicitly through the data. In fact, there is quite an interesting suggestion desCloizeaux-Let ; Deutsch ; Grosberg  that under a topological constraint the average size of ring polymers with no excluded volume should be similar as that of ring polymers with the excluded volume, since nontrivial entropic repulsion should be derived from the topological constraint. According to the suggestion, the average size of random polygons with the trivial knot should be given by $`N^{\nu _{\mathrm{SAW}}}`$ with respect to the number $`N`$ of polygonal nodes, where $`\nu _{\mathrm{SAW}}`$ is the exponent of self-avoiding walks. Thus, the small $`r`$ case of the simulation in the paper should be important also in the study of the topological effect on random polygons.

The outline of the paper is given in the following. In Sec. II we explain self-avoiding polygons (SAPs) consisting of cylinder segments. We also discuss the effective exponent of the mean square radius of gyration under no topological constraint $`R^2`$. In Sec. III, we discuss various nontrivial finite-size properties of the mean square radius of gyration $`R_K^2`$ for cylindrical SAPs with a given knot type $`K`$. The ratio $`R_K^2/R^2`$ expresses the effective expansion due to the topological constraint. Through the simulation, we find that the topological effect is important particularly in the small $`r`$ case for cylindrical SAPs. Furthermore, the effective topological expansion is controlled by the parameter $`r`$. In Sec. IV, we discuss the asymptotic expansion of the ratio $`R_K^2/R^2`$ with respect to the number $`N`$. Finally, in Sec. V, we graphically explain the effective expansion of the cylindrical SAPs under the topological constraint, through the graphs in the $`Nr`$ plane.

## II Cylindrical self-avoiding polygons

### II.1 Cylindrical ring-dimerization algorithm and random knots

Let us introduce a model of ring polymers in good solution. We consider self-avoiding polygons consisting of $`N`$ rigid impenetrable cylinders of unit length and diameter $`r`$: there is no overlap allowed for any non-adjacent pairs of cylindrical segments, while next-neighboring cylinders may overlap each other. We call them cylindrical self-avoiding polygons or cylindrical SAPs, for short. The cylinder radius $`r`$ can be related to the stiffness of some stiff polymers such as DNAs Klenin ; JPSJ .

In the simulations of the paper, we have constructed a large number of cylindrical SAPs by the cylindrical ring-dimerization method PLA . The method is based on the algorithm of ring-dimerization Chen , and very useful for generating long self-avoiding polygons (for details, see Ref. JPSJ ). Here we note that another algorithm is discussed in Ref. Klenin  for the model of cylindrical SAPs, where self-avoiding polygons of impenetrable cylinders with $`N<100`$ are constructed in association with knotted DNAs Rybenkov ; Shaw .

In the cylindrical ring-dimerization method, a statistical weight is given to any self-avoiding polygon successfully concatenated. Thus, when we evaluate some quantity, we take the weighted average of it with respect to the statistical weight. Some details on the statistical weight of successful concatenation is given in Ref. JPSJ . Hereafter in the paper, however, we do not express the statistical weight, for simplicity.

Let us describe the processes of our numerical experiments. First, we construct $`M`$ samples of cylindrical SAPs with $`N`$ nodes by the cylindrical ring-dimerization method. We put $`M=10^4`$. Here we note that various knot types are included in the $`M`$ random samples. Second, we make knot diagrams for the three-dimensional configurations of cylindrical SAPs, by projecting them onto a plain. Then, we calculate two knot invariants $`\mathrm{\Delta }_K(1)`$ and $`v_2(K)`$ for the knot diagrams. Third, we select only such polygons that have the same set of values of the two knot invariants, and then evaluate physical quantities such as mean-squared gyration radius for the selected cylindrical SAPs.

The symbol $`\mathrm{\Delta }_K(1)`$ denotes the determinant of a knot $`K`$, which is given by the Alexander polynomial $`\mathrm{\Delta }(t)`$ evaluated at $`t=1`$. The symbol $`v_2(K)`$ is the Vassiliev invariant of the second degree DeguchiPLA ; Polyak . The two knot invariants are practically useful for computer simulation of random polygons with a large number of polygonal nodes. In fact, it has been demonstrated in Ref. DeguchiPLA  that the Vassiliev invariant $`v_2(K)`$ can be calculated not only in polynomial time but also without using large memory area.

### II.2 Characteristic length of random knotting $`N_c(r)`$

For a given knot $`K`$, we consider the probability $`P_K(N,r)`$ that the topology of an $`N`$-noded self-avoiding polygon with cylinder radius $`r`$ is given by the knot type $`K`$. We call it the knotting probability of the knot $`K`$. Let us assume that we have $`M_K`$ self-avoiding polygons with a given knot type $`K`$ among $`M`$ samples of cylindrical SAPs with radius $`r`$. Then, we evaluate the knotting probability $`P_K(N,r)`$ by $`P_K(N,r)=M_K/M`$.

For the trivial knot, the knotting probability $`P_{triv}(N,r)`$ for the cylindrical SAPs is given by

$$P_{triv}(N,r)=C_{triv}\mathrm{exp}(N/N_c(r)).$$
(1)
Here the estimate of the constant $`C_{triv}`$ is close to 1.0 PLA . We call $`N_c(r)`$ the characteristic length of random knotting. It is also shown in Ref. PLA  that $`N_c(r)`$ can be approximated by an exponential function of $`r`$:

$$N_c=N_c(0)\mathrm{exp}(\gamma r).$$
(2)
The best estimates of the two parameters $`N_c(0)`$ and $`\gamma `$ are given by $`N_c(0)=292\pm 5`$ and $`\gamma =43.5\pm 0.6`$ PLA .

For several knots, it is shown JPSJ  that the knotting probability $`P_K(N,r)`$ of a knot $`K`$ is given by

$$P_K(N,r)=C_K\left(\frac{N}{N_K(r)}\right)^{m(K)}\mathrm{exp}(N/N_K(r)).$$
(3)
It is numerically suggested in Ref. JPSJ  that $`N_K(r)`$ should be independent of $`K`$: $`N_K(r)N_c(r)`$, and also that the constant $`C_K`$ should be independent of the cylinder radius $`r`$.

### II.3 Mean-squared gyration radius with a topological constraint

The mean square radius of gyration $`R^2`$ of a self-avoiding polygon is defined by

$$R^2=\frac{1}{2N^2}\underset{n,m=1}{\overset{N}{}}<(\stackrel{}{R}_n\stackrel{}{R}_m)^2>.$$
(4)
Here $`\stackrel{}{R}_n`$ is the position vector of the $`n`$th segment (or the $`n`$th node) and $`<>`$ denotes the ensemble average, which is taken over all possible configurations of the self-avoiding polygon.

Suppose that we have $`M`$ self-avoiding polygons. Then, we evaluate the mean square radius of gyration $`R^2`$ by the sum: $`R^2=_{i=1}^MR_i^2/M`$, where $`R_i^2`$ denotes the gyration radius of the $`i`$th SAPs in the given $`M`$ SAPs.

Let us define the mean square radius of gyration $`R_K^2`$ for such self-avoiding polygons that have a given knot type $`K`$:

$$R_K^2=\frac{1}{M_K}\underset{i=1}{\overset{M_K}{}}R_{K,i}^2,$$
(5)
where $`R_{K,i}^2`$ denotes the gyration radius of the $`i`$th self-avoiding polygon that has the knot type $`K`$. In terms of $`R_K^2`$, $`R^2`$ is given by $`R^2=_KR_K^2M_K/M`$.

In Fig. 1, the estimates of the mean square radius of gyration $`R^2`$ are plotted against the number $`N`$ of nodes in a double-logarithmic scale, for the cylindrical SAPs with $`r=0.003`$ and $`r=0.03`$. We may confirm the standard asymptotic behaviors of the mean-squared gyration radius $`R^2`$ in Fig. 1. Here we remark on an effective exponent $`\nu _{\mathrm{eff}}`$, which is defined through the power-law approximation: $`RN^{\nu _{\mathrm{eff}}}`$. It is shown in PhD-Miyuki  that the estimate of the effective exponent $`\nu _{\mathrm{eff}}`$ for the cylindrical SAPs with radius $`r`$ is consistent with that of the cylindrical SAWs with radius $`r`$.

## III Finite-size behaviors of $`R_k^2`$ for some knots

Let us discuss simulation results on the mean square radius of gyration $`R_K^2`$ for the cylindrical SAPs with a knot $`K`$ and of radius $`r`$. For two prime knots (the trivial and trefoil knots) and a composite knot (the double-trefoil knot, $`3_1\mathrm{}3_1`$), we have investigated the mean-squared gyration radius $`R_K^2`$ under the topological constraint in the range of the number $`N`$ satisfying $`21N1001`$, and for 14 different values of cylinder radius $`r`$.

The gyration radius $`R_K^2`$ can approximately given by some power of $`N`$. In Fig. 2, double-logarithmic plots of $`R_K^2`$ versus $`N`$ are given for the trivial and trefoil knots, with two values of cylinder radius: $`r=0.003`$ and 0.03. We see that all the double-logarithmic plots of Fig. 2 fit to some straight lines. We note that for other values of cylinder radius $`r`$, several double-logarithmic plots of $`R_K^2`$ versus $`N`$ are explicitly shown in Ref. PhD-Miyuki .

With the number $`N`$ fixed, $`R_K^2`$ should increase with respect to the radius $`r`$ for any knot. In Fig. 2, closed squares for $`r=0.03`$ are located higher in the vertical direction than closed circles for $`r=0.003`$, through the whole range of $`N`$ both for the trivial and trefoil knots.

### III.1 Ratio $`R_K^2/R^2`$ and the effective expansion under the topological constraint

Let us now consider the ratio of $`R_K^2`$ to $`R^2`$ for a given knot $`K`$. If the ratio is larger (smaller) than 1.0, then the average size of SAPs with the knot $`K`$ is relatively larger (smaller) than that of no topological constraint. We say that the SAPs with the knot $`K`$ is effectively more (less) expanded. In Fig. 3, the ratio $`R_K^2/R^2`$ versus the number $`N`$ is plotted in a double-logarithmic scale for the trivial and trefoil knots. Here, we have depicted only the case of $`r=0.003`$ among many sets of the cylindrical SAPs with the 14 different values of cylindrical radius.

For the trivial knot, we see in Fig. 3 that the ratio $`R_{triv}^2/R^2`$ is greater than 1.0 when $`N>50`$. Thus, the average size of the ring polymers with the trivial knot enlarges under the topological constraint. It gives a typical example of effective expansion.

In Fig. 3, the graph of the trivial knot is convex downwards: the ratio $`R_{triv}^2/R^2`$ is almost constant with respect to $`N`$ for small $`N`$ such as $`N<100`$; for $`N>300`$ the ratio $`R_{triv}^2/R^2`$ increases with respect to $`N`$ with a larger gradient, and the graph can be approximated by a power law such as $`R_{triv}^2/R^2N^{\nu _{\mathrm{eff}}^{triv}}`$. Here the symbol $`\nu _{\mathrm{eff}}^{triv}`$ denotes the effective exponent for the trivial knot. We note that the characteristic length $`N_c(r)`$ is approximately given by 300 for $`r=0.003`$. Thus, we may say that the power law behavior is valid for $`N>N_c(r)`$.

For the trefoil knot, the graph can be approximated by a power of $`N`$ such as $`R_{tre}^2N^{\nu _{\mathrm{eff}}^{tre}}`$ through the range of $`100N1001`$. Here the symbol $`\nu _{\mathrm{eff}}^{tre}`$ denotes the effective exponent of the trefoil knot. In Fig. 3, we find that when $`N<100`$ the ratio $`R_{tre}^2/R^2`$ is smaller than 1.0, while it is larger than 1.0 when $`N>300`$. Thus, when $`N`$ is small, the topological constraint of the trefoil knot gives effective shrinking to ring polymers, while it does not when $`N`$ is large. For a nontrivial knot $`K`$, we expect that the ratio $`R_K^2/R^2`$ is less than 1.0 when $`N`$ is small, while it can be larger than 1.0 when $`N`$ is large.

The properties of the ratio $`R_K^2/R^2`$ discussed in the last three paragraphs are consistent with the simulation results of Gaussian random polygons Miyuki . We have found for the random polygons that the double-logarithmic graph of $`R_K^2/R^2`$ versus $`N`$ is given by a downward convex curve for the trivial knot, while it is given by a straight line for the trefoil knot and also for other several nontrivial knots; for the nontrivial knots investigated, the ratio $`R_K^2/R^2`$ is given by some power of $`N`$ such as $`N^{\nu _{\mathrm{eff}}^K}`$ . Thus, there are indeed many important properties valid both for the simulation of the Gaussian random polygons and that of the cylindrical SAPs with a small radius such as $`r=0.003`$.

The observations derived from Fig. 3 should be valid particularly for finite-size systems. Admitting that $`N`$ is finite, we can only understand that the Gaussian random polygons and the cylindrical SAPs have the similar topological properties in common. If we discuss asymptotic behaviors, SAPs and random polygons should be quite different. However, if we consider such properties that are valid for finite $`N`$, then they can hold both for SAPs with small excluded volume and random polygons that have no excluded volume.

Let us discuss again the convexity of the graph of the trivial knot, which has been observed in Fig. 3. We consider how the convexity depends on the radius $`r`$. In Fig. 4, the graphs of the ratio $`R_{triv}^2/R^2`$ versus $`N`$ are given in a double-logarithmic scale for four different values of cylinder radius $`r`$. Then, we see that the graph with $`r=0.05`$ is less convex than that of $`r=0.003`$. Thus, the convexity in the graphs of the effective expansion for the trivial knot should be valid only when cylinder radius $`r`$ is small.

Let us assume that the convexity of the graphs of $`R_{triv}^2/R^2`$ for the small $`r`$ case should correspond to a crossover behavior of $`R_{triv}^2/R^2`$ with respect to $`N`$. Then, the crossover behavior could be related to that of Gaussian random knots, which is recently discussed by Grosberg Grosberg  for Gaussian random polygons. We can discuss the convexity of the double-logarithmic graph of $`R_{triv}^2/R^2`$ versus $`N`$, taking an analogy with the crossover of the Gaussian random knots. Thus, we call the convexity of the trivial knot in Fig. 3 the crossover, hereafter in the paper.

For the non-trivial knots investigated, we do not see any crossover in the graph of $`R_K^2/R^2`$ versus $`N`$. For instance, for the $`4_1`$ and $`3_1\mathrm{}3_1`$ knots, the slope of the graph near $`NN_c(r)`$ is straight in the double-logarithmic scale. The crossover at $`NN_c(r)`$ should be valid only for the trivial knot.

### III.2 The plateau in the graph of $`R_K^2/R^2`$ versus $`N`$ for large $`N`$

We discuss how the ratio $`R_K^2/R^2`$ depends on the number $`N`$, considering both the excluded volume effect and the effective expansion due to the topological constraint. In Fig. 5, the graphs of the ratio $`R_K^2/R^2`$ versus $`N`$ for different values of cylinder radius $`r`$ are shown in linear scales: (a) for the trivial knot; (b) for the trefoil knot.

Let us first consider the large $`N`$ behaviors of the graphs shown in Fig. 5 for the trivial and trefoil knots. The graphs of $`R_K^2/R^2`$ versus $`N`$ have a common tendency that they become constant with respect to $`N`$ when $`N`$ is very large. It is particularly the case for the larger values of cylinder radius $`r`$ such as $`r=0.03`$ and 0.05. They approach horizontal lines at some large values of $`N`$. When $`r`$ is small such as $`r=0.003`$, the graph becomes flat only for large $`N`$, as shown in Fig. 5.

From the flatness of the graphs of $`R_K^2/R^2`$ for large $`N`$, it follows that the power law behavior: $`R_{tre}^2/R^2N^{\nu _{\mathrm{eff}}^{tre}}`$ does not hold when $`N`$ is very large. In Fig. 3, we have discussed that the ratio $`R_{tre}^2/R^2`$ versus the number $`N`$ can be approximated by the power law for $`r=0.003`$ through the range of $`100N1001`$. However, the power-law approximation should be valid only within some finite range of $`N`$.

Let us discuss other finite-$`N`$ behaviors of the ratio $`R_K^2/R^2`$. For the trefoil knot, the ratio $`R_{tre}^2/R^2`$ is less than 1.0 when $`N`$ is small; it approaches or becomes larger than 1.0 when $`N`$ is large enough. When cylinder radius $`r`$ is small such as $`r=0.003`$ and $`r=0.01`$, the ratio $`R_{tre}^2/R^2`$ is clearly greater than 1.0 when $`N`$ is large enough. When $`r`$ is small, there should be a critical value $`N_{critical}`$ such that $`R_{tre}^2/R^2<1.0`$ for $`N<N_{critical}`$, and $`R_{tre}^2/R^2>1.0`$ for $`N>N_{critical}`$. Furthermore, we have a conjecture that the critical value $`N_{critical}`$ should be roughly equal to the characteristic length $`N_c(r)`$ of random knotting. It seems that the conjecture is consistent with the graphs of Fig. 5 (b).

Let us discuss the conjecture on $`N_{critical}`$, explicitly. In Fig. 5 (b), we see that for $`r=0.003`$, the ratio $`R_{tre}^2/R^2`$ becomes 1.0 roughly at $`N=300`$, and also that for $`r=0.01`$, the ratio $`R_{tre}^2/R^2`$ is close to 1.0 roughly at $`N=400`$. The observations are consistent with the estimates of $`N_c(r)`$ in Ref. PLA : $`N_c(r)=(2.72\pm 0.06)\times 10^2`$ for $`r=0.0`$ and $`N_c(r)=(4.72\pm 0.14)\times 10^2`$ for $`r=0.01`$. Thus, the consistency supports the conjecture on $`N_{critical}`$.

### III.3 Decrease of the topological effect under the increase of the excluded volume

The effect of a topological constraint on the gyration radius decreases when the excluded volume increases. There are two examples: the decrease of ratio $`R_K^2/R^2`$ with respect to cylinder radius $`r`$ while $`N`$ being fixed, and the disappearance of the crossover for the trivial knot shown in Figs. 3 and 4.

Let us first discuss how the excluded-volume can modify the effective expansion due to the topological constraint. As we clearly see in Fig. 5, the ratio $`R_K^2/R^2`$ decreases as cylinder radius $`r`$ increases with $`N`$ fixed, both for the trivial and trefoil knots. Thus, the effective expansion of SAPs under the topological constraint becomes smaller when the excluded volume becomes larger.

It is quite nontrivial that the effective expansion given by the ratio $`R_K^2/R^2`$ decreases as cylinder radius $`r`$ increases. In fact, the value of $`R_K^2`$ itself increases with respect to $`r`$, as we have observed in Fig. 2. Furthermore, one might expect that the effective expansion due to a topological constraint should also increase with respect to cylinder radius $`r`$, simply because the average size of ring polymers with larger excluded volume becomes larger, as observed in Fig. 1. However, it is not the case for the ratio $`R_K^2/R^2`$.

Let us now discuss the crossover behavior of the trivial knot again, from the viewpoint of the competition between the topological effect and the excluded volume effect. Here we recall that the crossover has been discussed in §3.A with Figs. 3 and 4. Here we regard the crossover as a characteristic behavior derived from the topological constraint of being the trivial knot.

As a working hypothesis, let us assume that the crossover should occur at around the characteristic length $`N_c(r)`$. Recall that $`N_c(r)`$ is larger than 1000 for $`r=0.03`$ and 0.05, as we have estimated: $`N_c(r)1200`$ for $`r=0.03`$, and $`N_c(r)2600`$ for $`r=0.05`$. If the above hypothesis would be valid, then the graphs for $`r`$ = 0.03 and 0.05 should also be convex. In Fig. 4, however, we see no change in the gradient of the graph of $`R_{triv}^2/R^2`$ versus $`N`$ for $`r=0.03`$ or 0.05. The assumed crossover of the trivial knot does not appear for $`r`$ = 0.03 or 0.05. We may thus consider that the crossover as a topological effect is diminished by the excluded volume effect when $`r0.03`$.

### III.4 Characteristic length of random knotting $`N_c(r)`$ and the effective expansion

In terms of the characteristic length $`N_c(r)`$, we can explain some properties of the effective expansion of cylindrical SAPs under a topological constraint. Here we recall that the ratio $`R_K^2/R^2`$ describes the degree of the effective expansion under the topological constraint of a knot $`K`$.

We first consider the case when the characteristic length $`N_c(r)`$ is very large. Let us show that the ratio $`R_{triv}^2/R^2`$ should be close to 1.0 for $`NN_c(r)`$. First, we recall that the probability $`P_{triv}(N)`$ of the trivial knot decays exponentially with respect to the number $`N`$ of polygonal nodes: $`P_{triv}(N)=\mathrm{exp}(N/N_c(r))`$. If $`N/N_c(r)`$ is very small, the probability $`P_{triv}(N)`$ is close to 1.0, i.e., almost all SAPs have the trivial knot. Then, the mean-squared gyration radius with no topological constraint $`R^2`$ should be almost equal to that of the trivial knot $`R_{triv}^2`$. Consequently, the ratio $`R_{triv}^2/R^2`$ should be close to 1.0.

When $`r0.05`$, the characteristic length $`N_c(r)`$ is larger than $`2600`$. Then, the trivial knot is dominant among the possible knots generated in SAPs with $`N<1000`$. Thus, $`R_{triv}^2`$ should almost agree with $`R^2`$, which is the mean-squared gyration radius of SAPs under no topological constraint. There is no effective expansion under the topological constraint: the $`R_{triv}^2/R^2`$ is close to 1.0.

Let us next consider the case when the characteristic length $`N_c(r)`$ is small or not large. Then we show that the mean square radius of gyration of SAPs with the trivial knot $`R_{triv}^2`$ should be larger than that of no topological constraint $`R^2`$ for $`N>N_c(r)`$. In fact, various types of knots can appear in a given set of randomly generated SAPs of the cylinder radius $`r`$, since the probability of the trivial knot $`P_{triv}(N)`$ is exponentially small for $`N>N_c(r)`$ . We note that the fraction of nontrivial knots is given by $`1\mathrm{exp}(N/N_c(r))`$. Thus, it is not certain whether the ratio $`R_{triv}^2/R^2`$ is close to the value 1.0 or not. However, we may expect that the ratio $`R_{triv}^2/R^2`$ should be indeed larger than 1.0. Here we consider the following points: when $`N>N_c(r)`$, the majority of SAPs generated randomly should have much more complex knots than the trivial knot; the mean square radius of gyration of $`N`$-noded SAPs with a very complex knot should be much smaller than that of the trivial knot.

The explanation on the effective expansion discussed in the above is completely consistent with the simulation results, as having been discussed in §3, in particular, through Figs. 3, 4 and 5.

## IV Asymptotic behaviors of $`R_K^2`$

### IV.1 The exponent of $`R_K^2`$

Let us discuss an asymptotic expansion for the mean square radius of gyration of cylindrical SAPs with a given knot $`K`$. Here we assume that $`R_K^2`$ can be expanded in terms of $`1/N`$ consistently with renormalization group arguments. Then, the large $`N`$ dependence of $`R_K^2`$ is given by

$$R_K^2=A_KN^{2\nu _K}\left[1+B_KN^\mathrm{\Delta }+O(1/N)\right].$$
(6)
Here, the exponent $`\nu _K`$ should be given by that of self-avoiding walks: $`\nu _K=\nu _{\mathrm{SAW}}`$. In order to analyze the numerical data systematically, however, we have introduced $`\nu _K`$ as a fitting parameter. Thus, for the ratio $`R_K^2/R^2`$, we have the following expansion:

$$R_K^2/R^2=(A_K/A)N^{2\mathrm{\Delta }\nu _K}\left[1+(B_KB)N^\mathrm{\Delta }+O(1/N)\right].$$
(7)
Here we have put $`\mathrm{\Delta }\nu _K`$ as a fitting parameter.

We have analyzed the data for the three different knots: the trivial, trefoil and $`3_1\mathrm{}3_1`$ knots, applying the expansion (7) to the numerical data of $`R_K^2/R^2`$ for $`N300`$ . The best estimates of the three parameters are given in Tables 1, 2 and 3 for the trivial, trefoil and $`3_1\mathrm{}3_1`$ knots, respectively.

Let us discuss the best estimates of the difference of the exponents: $`\mathrm{\Delta }\nu _K`$. We see in Tables 1 , 2 and 3 that all the results of $`\mathrm{\Delta }\nu _K`$ suggest that they should be given by 0.0, with respect to the confidence interval. Let us examine the best estimates more precisely. It is rather clear from Tables 1, 2 and 3 that for a given cylinder radius $`r`$, the best estimates of $`\mathrm{\Delta }\nu _K`$ are independent of the knot type.

There is another evidence supporting that $`\mathrm{\Delta }\nu _K=0.0`$ for the trivial and trefoil knots. Let us consider the plots of the ratio $`R_K^2/R^2`$ versus $`N`$ in Fig. 5 for the trivial and trefoil knots. We recall that the graphs are likely to approach some horizontal lines at some large $`N`$. The tendency of the graphs becoming flat for large $`N`$ suggests that $`R_K^2`$ and $`R^2`$ should have the same exponent, i.e., $`\nu _{\mathrm{SAW}}`$.

From the two observations, we conclude that the difference of the exponents is given by 0.0: $`\mathrm{\Delta }\nu _K=0.0`$ for any value of $`r`$. There is thus no topological effect on the scaling exponent defined in the asymptotic expansion of $`R_K^2`$.

### IV.2 Amplitude ratio $`A_K/A`$

Let us now consider the amplitude $`A_K`$ of the asymptotic expansion (7). In Tables 1, 2 and 3, the best estimates of the ratio $`A_K/A`$ are larger than 1.0 for the three knots, when $`r`$ is small. The observation must be important. In fact, if the amplitude ratio $`A_K/A`$ is larger than 1.0 in the asymptotic expansion (7), then $`R_K^2`$ is larger than $`R^2`$ for any large value of $`N`$. It might seem that the consequence is against the standard thermodynamic limit of statistical mechanics.

However, there is a clear evidence for the observation that $`A_K/A>1.0`$ for some small values of cylinder radius $`r`$. In fact, the graphs of the ratio $`R_K^2/R^2`$ versus $`N`$ are monotonically increasing with respect to $`N`$, as we see in Figs. 3, 4 and 5. It is clear that the graphs with the smaller values of cylinder radius $`r`$ are larger than 1.0 when $`N`$ is large. This observations of Figs. 3, 4 and 5 confirm that $`A_K/A>1.0`$ when cylinder radius $`r`$ is small. Thus, we may conclude that the topological constraint gives an effective expansion also to asymptotically large cylindrical SAPs when the radius $`r`$ is small.

The value of $`A_K/A`$ decreases with respect to the radius $`r`$ for the three knots. We see it in Tables 1 to 3, where the best estimates of $`A_K/A`$ are listed. It is also consistent with the fact that the ratio $`R_K^2/R^2`$ decreases with respect to $`r`$, which we have discussed in §3.C. However, the decrease of $`A_K/A`$ is quite nontrivial, since the mean-squared gyration radius $`R_K^2`$ itself increases with respect to $`r`$, for the trivial and trefoil knots, as shown in Fig. 2. Here we recall in Fig. 1 that the gyration radius under no topological constraint $`R^2`$ increases with respect to $`r`$.

From the viewpoint of asymptotic behaviors, we have shown that the effective expansion derived from the topological repulsion decreases with respect to cylinder radius $`r`$. We have also discussed that $`R_K^2`$ is larger than $`R^2`$ for any large value of $`N`$, when cylinder radius $`r`$ is small.

### IV.3 The $`r`$-dependence of the amplitude ratio

Let us discuss the $`r`$ dependence of the amplitude ratio $`A_K/A`$, more quantitatively. For this purpose, we analyze the data of $`R_K^2/R^2`$ versus $`N`$ again, assuming $`\nu _K=\nu `$ in eq. (7). We evaluate the amplitude ratio $`A_K/A`$ by the following formula:

$$R_K^2/R^2=\alpha _K(1+\beta _KN^\mathrm{\Delta }+O(1/N)).$$
(8)
Here we have replaced with $`\alpha _K`$ and $`\beta _K`$, $`A_K/A`$ and $`B_KB`$ in (7), respectively. Here we have also introduced a technical assumption: $`\mathrm{\Delta }=\mathrm{\Delta }_K`$=0.5 in (7).

We have obtained the numerical estimates of $`\alpha _K`$, applying the fitting formula (8) to the data of $`R_K^2/R^2`$ with $`N300`$ . The estimates of $`\alpha _K`$ versus $`r`$ are shown in Fig. 6 in the double-logarithmic scale for the trivial, trefoil, and $`3_1\mathrm{}3_1`$ knots. To be precise, the values of $`\alpha _K`$ are a little larger than those of $`A_K/A`$ given in Tables 1 , 2 and 3.

The estimate of the parameter $`\alpha _K`$ becomes close to the value 1.0 when cylinder radius $`r`$ is large enough. Furthermore, it is suggested from Fig. 6 that $`\alpha _K`$ should be independent of the knot type. In fact, the data points for the trivial, trefoil and the double-trefoil ($`3_1\mathrm{\#}3_1`$) knots overlap each other. These two observations are consistent with the simulation result of the self-avoiding polygons on the lattice Orlandini ; Janse1991 .

Interestingly, we see in Fig. 6 that the ratio $`\alpha _K`$ decreases monotonically with respect to the cylinder radius $`r`$. For the data with $`0.001r0.01`$, we find that $`\alpha _K`$ is roughly approximated by a decreasing function of $`r`$ such as $`\alpha _K=\alpha _0r^\varphi \mathrm{exp}(\psi r)`$, with $`\alpha _0`$=1.00$`\pm `$0.12, $`\varphi `$=-0.05$`\pm `$0.02 and $`\psi `$=5.78$`\pm `$4.79. The $`\chi ^2`$ value is given by 1.

## V Discussion

With some graphs in the $`Nr`$ plane, we can illustrate the finite-size behaviors of the ratio $`R_K^2/R^2`$ discussed in §3. We recall that the topological effect has played a central role as well as the excluded-volume effect. Thus, we consider two lengths with respect to the number $`N`$ of polygonal nodes: the characteristic length of random knotting $`N_c(r)`$ and the “excluded-volume length” $`N_{ex}(r)`$. When $`N>N_{ex}(r)`$, the excluded-volume effect should be important to any $`N`$-noded SAP with radius $`r`$ .

We define $`N_{ex}(r)`$ by $`N_{ex}(r)=1/r^2`$. The derivation is given in the following. We first note that the parameter $`z`$ of the excluded-volume is given by $`z=\mathrm{Const}.\sqrt{N}B/\mathrm{}^3N^{1/2}r`$, where the cylindrical segments have the diameter $`d`$ and the length $`\mathrm{}`$, and the second virial coefficient $`B`$ of a polymer chain is given by $`\mathrm{}^2d`$ Grosberg-book . Here we also note that the ratio $`d/\mathrm{}`$ corresponds to the radius $`r`$ of the cylindrical SAPs. We may consider that when $`z1`$, the excluded volume can not be neglected. Thus we have the number $`N_{ex}(r)`$ from the condition: $`\sqrt{N_{ex}(r)}r=1`$.

We consider two graphical lines in the $`Nr`$ plane: $`N=N_{ex}(r)`$ and $`N=N_c(r)`$. In Fig. 7, the vertical line of the diagram expresses the $`r`$-axis and the horizontal one the $`N`$-axis. The graph $`N_c(r)=N`$ reaches the $`N`$ axis at $`N=N_c(0)300`$. Here we recall that the function $`N_c(r)`$ is given by eq. (2): $`N_c(r)=N_c(0)\mathrm{exp}\left(\gamma r\right)`$. There is a crossing point for the two curved lines. The coordinates of the crossing point is approximately given by $`N^{}=1300`$ and $`r^{}=0.03`$. For a given simulation of the ratio $`R_K^2/R^2`$ with a fixed radius $`r`$, we have a series of data points located on a straight line parallel to the $`N`$ axis.

Let us first consider the case of small values of $`r`$ such as $`r=0.003`$ and $`r=0.01`$. From the simulation of §3, it is shown that the effective expansion due to the topological constraint is large. This is consistent with the following interpretation of the $`Nr`$ diagram: if we start from the region near the $`r`$ axis and move in the direction of the $`N`$ axis, then we cross the line $`N=N_c(r)`$ before reaching another one $`\sqrt{N}r=1`$; thus, we expect that the excluded-volume remains small when the topological effect becomes significant.

The above explanation should be consistent with the observation that the crossover of the trivial knot occurs near $`N=N_c(r)`$ for small values of $`r`$. Here we recall Figs. 3 and 4. When $`r`$ is very small, then we cross the line of $`N_c(r)=N`$ almost at $`N_c(0)300`$.

When radius $`r`$ is large such as $`r=0.03`$ and 0.05, it is shown in §3 through simulation that the effective expansion is small: the ratio $`R_K^2/R^2`$ is close to 1.0. In the $`Nr`$ diagram, when we move rightwards from the region near the $`r`$ axis with $`r`$ fixed, we cross the line $`\sqrt{N}r=1`$ before reaching another line $`N_c(r)=N`$. Thus, the effective expansion as the topological effect should be small.

Finally, we should remark that some important properties of $`R_K^2`$ of cylindrical SAPs with radius $`r`$ have been discussed systematically through scaling arguments with the blob picture by Grosberg Grosberg2 . In the note Grosberg2 , the characteristic length $`N_c(r)`$ and the excluded-volume parameter $`z`$ are explicitly discussed in the $`Nr`$ diagrams. It would thus be an interesting future problem to investigate how far the predicted properties of $`R_K^2`$ are consistent with simulation results.

###### Acknowledgements.

We would like to thank Prof. K. Ito for helpful discussions. We would also like to thank Prof. A.Yu. Grosberg for his helpful discussion and sending the unpublished note on $`R_K^2`$ Grosberg2 .


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# Reciprocal and Variational Principles in Micropolar Thermoelasticity Work performed in the context of a fellowship of Italian Research Council (C.N.R.).

( Dipartimento di Ingegneria dell’Informazione e Matematica Applicata
Universitá di Salerno - via Ponte don Melillo - I–84084 Fisciano (SA) )


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# Impurity-induced transition and impurity-enhanced thermopower in the thermoelectric oxide NaCo2-xCuxO4

## I Introduction

Recently layered cobalt oxides have been extensively investigated as a promising candidate for a thermoelectric material. The thermoelectric material is a material that shows large thermopower ($`S`$), low resistivity ($`\rho `$) and low thermal conductivity ($`\kappa `$) mahan , and a quantity of $`ZS^2/\rho \kappa `$ called the figure of merit characterizes the thermoelectric conversion efficiency. Thermoelectric device can generate electric power from heat through the Seebeck effect, and can pump heat through the Peltier effect. Thus far oxides have been regarded as unsuitable for thermoelectric application because of their poor mobility, but some years ago Terasaki et al. found that a single crystal of the layered oxide NaCo2O4 exhibits good thermoelectric performance terra . Fujita et al. showed that the dimensionless figure of merit $`ZT`$ of a NaCo2O4 single crystal exceeds unity at $`T=`$1000 K fujita , Ohtaki et al. ohtaki  measured $`ZT0.8`$ at 1000 K even in the polycrystalline samples of NaCo2O4. Thus this compound is quite promising for thermoelectric power generation at high temperature.

Following NaCo2O4, other layered cobalt oxides, Ca-Co-O li ; miyazaki ; masset ; funahashi , Bi-Sr-Co-O itoh ; itoh2 ; funahashi2 , Tl-Sr-Co-O hebert  have been found to show good thermoelectric performance. In particular, Funahashi et al. funahashi  showed $`ZT>1`$ at 1000 K for Ca-Co-O. The most important feature is that the CdI2 type triangular CoO2 block is common to the layered cobalt oxides. We have proposed that the high thermoelectric performance of the layered cobalt oxides cannot be explained by a conventional band picture based on the one-electron approximation, but is understood in terms of the strong electron-electron correlation effects, similarly to the case of heavy-fermion compounds. In fact the material dependence of the thermopower quite resembles that of Ce$`M_2X_2`$ terra2 .

A prime example for the difficulties of the one-electron picture is observed in the Cu substitution effects in NaCo2O4 terra3 . The thermopower of NaCo2-xCuxO4 is significantly enhanced, while the resistivity is nearly independent of $`x`$. This is quite surprising in comparison with normal impurity effects in a metal. The doped impurity acts as a scattering center in usual cases, and does not make a significant change in thermopower, because it is a quantity of the zero-th order of scattering time. Indeed this is what was observed in high-temperature superconductors tallon . Importantly, correlation effects can explain the large impurity effect on the thermopower, similarly to the case of dilute magnetic alloys fischer . In this paper, we report on measurement of specific heat, susceptibility, Hall coefficient, and transverse magnetoresistance for NaCo2-xCuxO4 polycrystalline samples, and discuss the Cu substitution effects quantitatively.

## II Experimental

Polycrystalline samples of Na1.2Co2-xCuxO4 ($`x`$=0, 0.1, 0.2 and 0.3) were prepared through a solid-state reaction. A stoichiometric amount of Na2CO3, Co3O4 and CuO was mixed and calcined at 860C for 12 h in air. The product was finely ground, pressed into a pellet, and sintered at 920C for 12 h in air. Since Na tends to evaporate during calcination, we added 20 % excess Na. Namely we expected samples of the nominal composition of Na1.2Co2-xCuxO4 to be NaCo2-xCuxO4.

The x-ray diffraction (XRD) was measured using a standard diffractometer with Fe Kα radiation as an x-ray source in the $`\theta 2\theta `$ scan mode. The resistivity was measured through a four-terminal method, and the thermopower was measured using a steady-state technique with a typical temperature gradient of 0.5 K/cm. The Hall coefficient ($`R_H`$) and the transverse magnetoresistance were measured from 15 to 100 K in a closed refrigerator inserted into a room temperature bore of a liquid-He free superconducting magnet. To eliminate the unwanted voltage arising from the misalignment of the voltage pads, the magnetic field was swept from -7 to 7 T with a typical period of 20 min at constant temperatures with a stability of 10 mK. The specific heat was measured using a standard relaxation method with a mechanical heat switch. The mass of the samples used for the measurement is typically 1000 mg and the heat capacity of the samples is always more than two orders of magnitude larger than the addenda heat capacity. The susceptibility was measured with a SQUID susceptometer in a magnetic field of 1 T.

## III Results

Figure 1(a) shows the x-ray diffraction patterns of the prepared samples of NaCo2-xCuxO4. Almost all the peaks are indexed as the $`\gamma `$ phase JH ; fouassier , though a small amount (approximately less than 5%) of unreacted Co3O4 is observed. With increasing Cu content $`x`$, no additional peak appears, with the patterns unchanged, which shows that Cu is substituted for Co. However, the sample of $`x`$=0.3 shows a higher background noise, indicating that the crystal quality becomes worse, possibly owing to the limit of solid solution with Cu.

Figure 2(a) shows the temperature dependence of the resistivity for NaCo2-xCuxO4. All the samples are metallic down to 4.2 K without any indication of localization. It should be noted that the increased resistance due to the substituted Cu is of the order of 10$`\mu \mathrm{\Omega }`$cm for 1 at.% Cu, which is anomalously small in the layered transition-metal oxides fukuzumi . Another important feature is that the resistivity for the Cu substituted samples show a kink near 22 K as indicated by the dotted line. Since the temperature dependence is steeper below 22 K, the density of states (or the carrier concentration) decreases below 22 K.

Figure 2(b) shows the temperature dependence of the thermopower for NaCo2-xCuxO4. Thermopower increases with increasing $`x`$ with a dip near 22 K and a peak near 10-15 K. As we previously shown in the analysis for Bi-Sr-Co-O itoh2 , a low-temperature thermopower ($`S`$) of the layered Co oxides is determined by the diffusive term that is proportional to temperature ($`T`$). Accordingly $`S/T`$ is an essential parameter similarly to the electron specific-heat coefficient. Thus, the dip, rather than the peak, is a meaningful temperature, which corresponds to the onset of the enhancement in $`S/T`$ at low temperatures. It should be emphasized that the dip temperature is nearly the same as the kink temperature for the resistivity, which strongly suggests that this temperature is related to a kind of phase transition.

Figure 3(a) shows the specific heat $`C`$ for NaCo2-xCuxO4. In order to emphasize the $`T`$-linear electron specific heat, we plot $`C/T`$ as a function of temperature. As shown in Fig. 3(a), the $`C/T`$ value at 2 K decreases with increasing the Cu content from 0 to 0.2, which means the decrease of the electron specific heat coefficient $`\gamma `$ with $`x`$. (For the sample of $`x`$=0.3, the $`C/T`$ value increases again, which might be due to an extrinsic origin such as the solid-solution limit of Cu.) Since $`\gamma `$ is proportional to the density of states and the mass-enhancement factor, the present results indicate that the either or both decrease with the Cu substitution. As for high temperatures, all the data show a peak near 30 K which is the antiferromagnetic transition of the unreacted Co3O4, as shown by the solid curve LB1 . As mentioned above, the x-ray diffraction patterns reveal less than 5 at.% of unreacted Co3O4, which is consistent with the peak height of the specific heat at 30 K. We should emphasize here that the existence of Co3O4 does not seriously affect the estimation of $`\gamma `$, because the $`C/T`$ value for Co3O4 is negligibly small at low temperatures. For $`x=`$0.2 and 0.3, another peak appears in the specific heat near 22 K, which is close to the kink temperature in $`\rho `$, and the dip temperature in $`S`$. We thus conclude that the 22-K anomaly comes from a (2nd order) phase transition.

Figure 3(b) shows the susceptibility ($`\chi `$) of NaCo2-xCuxO4. The substituted Cu also decreases the susceptibility, indicating the decrease of the density of states and/or the mass-enhancement factor. A broad hump near 30 K is due to the antiferromagnetic transition of the unreacted Co3O4, as shown by the solid curve LB2 . Interestingly, there is no anomaly near 22 K in the susceptibility, suggesting that the transition at 22 K is not the magnetic transition of impurity phases. We further note that the Curie-like contribution is absent in the susceptibility at low temperatures, which shows that magnetic impurities are unlikely to exist other than Co3O4. Quantitatively, the decrease of $`\chi `$ by Cu is more moderate than that of $`C/T`$. $`C/T`$ decreases by a factor of ten from $`x=0`$ to 0.2, whereas $`\chi `$ decreases only by a factor of two. This implies that the 22-K transition causes a dramatic reduction of the electron entropy possibly owing to a (pseudo)gap formation, while it does not alter the magnetic excitation at $`k=0`$. The nature of the 22-K transition will be discussed in the next section.

Figure 4(a) shows the Hall coefficient ($`R_H`$) of NaCo2-xCuxO4. The sign is negative below 100 K, and the magnitude is as small as 4-6$`\times `$10-4 cm3/C. The Cu substitution does not change the magnitude so much, indicating that the carrier concentration is nearly unchanged. By contrast, it changes the temperature dependence in a complicated way, which implies that plural kinds of carriers are responsible for the electric conduction. The band calculation by Singh singh  reveals that the two bands of different symmetries cross the Fermi level for NaCo2O4. (See the next section)

Contrary to the Hall effect, the magnetoresistance is weakly dependent on the Cu substitution, as shown in Fig. 4(b). By taking a closer look at the $`x`$ dependence, one can see that the negative magnetoresistance is gradually suppressed by the substituted Cu. This implies that the kink of the resistivity is more or less smeared against magnetic field, which suggests that the magnetic field suppresses the 22-K transition.

## IV Discussion

Before going into details, we will begin with a brief review on the electronic states of NaCo2O4. As is well known, the five-fold degenerate $`d`$ orbitals split into two-fold ($`e_g`$) and three-fold ($`t_{2g}`$) degenerate levels in an oxygen octahedron. In the real triangular CoO2 block, the octahedron is compressed along the $`c`$ direction, and the degeneracy is further quenched, where the lower $`t_{2g}`$ levels split into $`e_g`$ and $`a_{1g}`$ levels. The lower $`e_g`$ levels correspond to the orbital spread along the CoO2 block to make a relatively broad band, whilst the $`a_{1g}`$ orbital is spread along the $`c`$ direction to make a nearly localized narrow band. Since each Co ion is 3.5+ with $`(3d)^{5.5}`$, the highest occupied orbital is $`a_{1g}`$ in the atomic limit, and the main part of the Fermi surface consists of the narrow $`a_{1g}`$ band. In the real band calculation, however, there is significant hybridization between the $`a_{1g}`$ and $`e_g`$ levels, and the broader $`e_g+a_{1g}`$ band touches the Fermi level to make small Fermi surfaces singh .

We have proposed that the electronic structure of NaCo2O4 is similar to that of the Ce-based intermetallics, a prime example of valence-fluctuation/heavy-fermion compounds terra2 . $`\gamma `$ and $`\chi `$ of NaCo2O4 are as large as those of CePd3. In this context, the large thermopower of NaCo2O4 is explained in terms of a diffusive contribution of a metal with a heavily enhanced effective mass, and is roughly proportional to $`\gamma `$. In the heavy fermion compounds, the broad conduction band crosses the Fermi energy, and the narrow (localized) f band is located below the Fermi energy. For NaCo2O4, the broad $`e_g+a_{1g}`$ band and the narrow $`a_{1g}`$ band do exist, but both of which cross the Fermi energy to form two kinds of the Fermi surfaces. Thus it is not trivial whether or not the two Fermi surfaces behave heavy-fermion-like in the charge transport. At least we can say that the two Fermi surfaces play different roles, where the Cu substitution induces different effects: $`\rho `$ is weakly dependent on the Cu content $`x`$, whereas $`S`$, $`\chi `$ and $`\gamma `$ are strongly dependent on $`x`$. $`S`$, $`\chi `$ and $`\gamma `$ are basically proportional to the density of states in the lowest order, which are determined by the large Fermi surface of the $`a_{1g}`$ symmetry. In contrast, the carriers on the $`e_g+a_{1g}`$ band can be highly mobile, because it is spread along the in-plane direction. In short, the $`a_{1g}`$ and $`e_g+a_{1g}`$ bands are responsible for the large thermopower and a good electric conduction, respectively.

Existence of the $`a_{1g}`$ and $`e_g+a_{1g}`$ bands was suggested from the angular dependence of the X-ray absorption spectroscopy experiment mizokawa ; mizokawa2 , where the valence bands of NaCo2O4 consist of the $`a_{1g}`$ and $`e_g+a_{1g}`$ bands. The valence band of the less conductive Bi-Sr-Co-O is mainly composed only of the $`a_{1g}`$ band, which is consistent with our speculation that the $`e_g+a_{1g}`$ band is responsible for the metallic nature of NaCo2O4. The large Fermi surface suggested by the band calculation was not seen in the angle photoemission spectra for Bi-Sr-Co-O, which indicates that the band calculation should be modified by additional effects such as the electron-electron or electron-phonon effects.

### IV.1 Phase Transition at 22 K

As shown in the previous section, the Cu substitution causes the phase transition at 22 K, which is probed by the jump of the specific heat, the dip in the thermopower, and the kink in the resistivity. Figure 5(a) shows the specific heat for the $`x=0.2`$ sample (the same data in Fig. 3(a)) as a function of temperature in linear scale in order to see the 22-K anomaly clearly. One thing to point out is that the entropy change of this transition is surprisingly small. As shown in Fig. 5(a), we estimated the entropy change by the area surrounded with $`C/T`$ and the dotted line, which is approximately 77 mJ/Kmol, corresponding to 0.01$`k_B`$ per Co. Actually only 5% of Co3O4 impurity exhibits a specific heat jump of the same order at 30 K.

There are two possibilities for the origin of the small entropy change. One is that the 22-K transition is something related to the impurity phase of the order of 1%. Although we cannot exclude this possibility completely, we will take the other possibility that the small entropy change is an intrinsic nature in bulk, because (i) the field dependence of $`C/T`$ is different between the 22-K transition and the magnetic transition in Co3O4 at 30 K as shown in Fig. 5(b), (ii) a possible impurity phase is a Cu-based magnetic material, which is inconsistent with no anomaly in $`\chi `$ at 22 K, and (iii) the thermopower and the resistivity systematically change at the same temperature. The most familiar phase transition accompanied by a small entropy change is perhaps superconducting transition. More generally, off-diagonal long range order induces a small entropy change of the order of $`Nk_BT/E_F`$.

Figure 5(c) shows the $`T`$-linear term of the thermopower ($`S/T`$) and the temperature derivative of the resistivity $`d\rho /dT`$, both of which are inversely proportional to the Drude weight comment . Their temperature dependences are quite similar to each other, where the magnitude increases up to almost twice below 22 K. This indicates that the Drude weight decreases by 50% at low temperatures, implying the existence of a (pseudo)gap. As an off-diagonal long-range order with a gapped state, one would think of charge density wave (CDW) or spin density wave (SDW). The calculated Fermi surface singh  of the $`a_{1g}`$ band is hexagon-like, which is unstable against CDW or SDW formation with the nesting vector along the $`\mathrm{\Gamma }`$-K direction. We think that the 22-K transition is SDW-like, because CDW is insensitive to magnetic field coleman . Actually we can find many similarities between the 22-K transition and SDW transition: The entropy change is observed to be quite small in Cr CrReview , YbBiPt fisk  and (TMTSF)2PF6 coroneus . The resistivity shows a hump CrReview ; fisk , and the thermopower shows a dip at the transitionchoi .

It is not surprising that the 22-K transition has little effects on the magnetic susceptibility. Since an SDW state is an antiferromagnetically ordered state, the magnetic excitation is gapless in principle. In fact, the SDW state of Cr exhibits a very tiny (1-2%) change in the susceptibility at the transition temperature CrReview , while it causes a clear hump in the resistivity adachi . The metallic conduction below 22 K, implies that a part (approximately 50%) of the Fermi surface remains, which could smears the SDW transition. To clarify the nature of the transition, a local magnetic probe such as NMR or $`\mu `$SR should be employed.

### IV.2 Effects on the Hall coefficient and thermopower

Next we will discuss how we can understand the Cu substitution effects on $`R_H`$ and $`S`$. We should note here that the sum rules of transport parameters for a multiband system are expressed in the form of conductivities, not in the form of $`R_H`$ or $`S`$. Let us denote the conductivities for the $`a_{1g}`$ and $`e_g+a_{1g}`$ bands as $`\sigma ^a`$ and $`\sigma ^e`$, respectively. The total conductivity $`\sigma `$ is then written as

$$\sigma =\sigma ^e+\sigma ^a$$
(1)
Similarly, the total Hall conductivity $`\sigma _{xy}`$ and the total Peltier conductivity $`\sigma _P`$ are written as

$`\sigma _{xy}`$ $`=`$ $`\sigma _{xy}^e+\sigma _{xy}^a`$ (2)
$`\sigma _P`$ $`=`$ $`\sigma _P^e+\sigma _P^a`$ (3)
where the Peltier conductivity ong  is defined as $`\sigma _PS\sigma =S/\rho `$.

Figure 6(a) shows the temperature dependence of $`\sigma _P=S/\rho `$ for $`x=`$0 and 0.2. The Cu substitution enhances the Peltier conductivity over the measured temperature range from 4 to 100 K, indicating that the mobility is enhanced by Cu. The enhancement below 22 K is more remarkable in $`\sigma _P`$ than in $`S`$, which indicates the mobility is rapidly enhanced below the 22-K transition. Figure 6(b) shows the temperature dependence of $`\sigma _{xy}=HR_H/\rho ^2`$ for $`x=`$0 and 0.2. The complicated change seen in $`R_H`$ is converted into a simpler change in $`\sigma _{xy}`$. Although the Cu substitution effects in $`\rho `$ is quite small, $`1/\rho ^2`$ term moderates the difference in $`R_H`$. One can see that $`\sigma _{xy}`$ is also increased by Cu over the temperature range from 15 to 100 K, as is similar to the case of $`\sigma _P`$.

Let us assume that the substituted Cu affects only the $`a_{1g}`$ band. Then a difference between $`x=0`$ and 0.2 is reduced to a change in $`\sigma _P^a`$ and $`\sigma _{xy}^a`$. Figure 6(c) shows $`\mathrm{\Delta }\sigma _P=\sigma _P(x=0.2)\sigma _P(x=0)`$ $`\mathrm{\Delta }\sigma _{xy}=\sigma _{xy}(x=0.2)\sigma _{xy}(x=0)`$. Most unexpectedly, the change in the Peltier conductivity $`\mathrm{\Delta }\sigma _P`$ and the change in the Hall conductivity $`\mathrm{\Delta }\sigma _{xy}`$ show nearly the same temperature dependence. In particular, a clear enhancement below 22 K indicates that the phase transition causes an equal impact on $`S`$ and $`R_H`$ in the form of the Peltier and Hall conductivities.

On the assumption that only the $`a_{1g}`$ band is modified by Cu, we will consider the change in the $`a_{1g}`$ band in terms of the carrier concentration $`n`$, the effective mass $`m`$, and the scattering time $`\tau `$. Then $`\sigma _P^a`$ and $`\sigma _{xy}^a`$ are roughly expressed as $`\sigma _P^an/m^{}`$ and $`\sigma _{xy}^a\tau /m^{}`$, where the average of $`\mathrm{}`$ is defined as $`(4\pi ^3)^1(v_F)^2\tau \mathrm{}d^3k`$. A close similarity between $`\mathrm{\Delta }\sigma _P`$ and $`\mathrm{\Delta }\sigma _{xy}`$ implies that $`\mathrm{\Delta }\tau `$ and $`\mathrm{\Delta }n`$ are nearly independent of temperature. The $`T`$-independent $`\mathrm{\Delta }\tau `$ means the scattering time averaged in the $`a_{1g}`$ Fermi surface is dominated by impurity scattering, which is consistent with the localized picture of the $`a_{1g}`$ band. The positive values of $`\mathrm{\Delta }\sigma _{xy}`$ and $`\mathrm{\Delta }\sigma _P`$ suggests that the increase of $`1/m^{}`$. This indicates that the mass enhancement is suppressed (the mobility is enhanced) by Cu over the measured temperature range, regardless of the 22-K transition, which is consistent with the decrease in $`\gamma `$ and $`\chi `$ by Cu.

### IV.3 Comparison with Ce based compounds

Based on the heavy-fermion scenario, it seems inconsistent that the substituted Cu causes the decrease in $`\gamma `$ (Fig. 3) together with the increase in $`S`$ (Fig. 2). As shown in Fig. 7(a), $`\gamma `$, $`\chi `$ and $`S`$ are plotted as a function of the Cu content $`x`$. (Note that $`\gamma `$ was estimated as $`C/T`$ at 2 K, and $`\chi `$ was estimated as the raw value of $`\chi `$ at 2 K.) Although $`\gamma `$ and $`\chi `$ decreases with $`x`$, $`S`$ significantly increases with $`x`$, where $`S\gamma `$ is no longer valid.

We should emphasize that the relationship between $`\gamma `$ and $`S`$ is complicated also in the Ce-based compounds. Figure 7(b) shows $`\gamma `$, $`\chi `$ lin  and $`S`$ sakurai  for Ce(Pb1-ySny)3 as a function of the Sn content $`y`$. CePb3 is in the heavy fermion regime (low Kondo temperature) and CeSn3 is in the valence fluctuation regime (high Kondo temperature). Thus the solid solution between Pb and Sn changes the material from the heavy-fermion to the valence-fluctuation compound, which is evidenced by the fact that $`\chi `$ and $`\gamma `$ monotonically decrease with $`y`$. On the other hand, $`S`$ exhibits complicated $`y`$ dependence. $`S`$ is negative for $`y=0`$, increases with $`y`$ up to 0.4, and eventually decreases from $`y`$=0.6 to 1.0.

This is intuitively understood as follows. When the Kondo temperature is sufficiently low as in the case of CePb3, the RKKY interaction survives at low temperatures, and often causes a magnetic transition. Since the magnetic transition release the entropy of the spin sector, the entropy per carrier (equivalently the diffusive term of the thermopower) would be suppressed against the fluctuation of the magnetic transition. On the other hand, when the Kondo temperature is high enough, the mass enhancement is severely suppressed to give a small thermopower again. Thus the thermopower would take a maximum at an intermediate value of the Kondo temperature. This is indeed what we see in Fig. 7(b), and similar to the general trend of the 20-K thermopower of Ce$`M_2X_2`$ found by Jaccard et al.jaccard

In this context, the NaCo2O4 is located near the heavy-fermion regime, and the substituted Cu caused the decrease in the mass enhancement accompanied by the increase in $`S`$, which is consistent with the increase in the Peltier and Hall conductivities seen in the previous subsection. Although there is no microscopic relationship between NaCo2-xCuxO4 and Ce(Pb1-ySny)3, a close resemblance in Fig. 7 suggests that the unsubstituted NaCo2O4 corresponds to $`y0.2`$, while NaCo1.8Cu0.2O4 corresponds to $`y0.40.6`$. We further note that the Pd substituted NaCo2O4 shows negative thermopower below 50 K, which might correspond to $`y<0.2`$ kitawaki .

### IV.4 Order from disorder

Although the microscopic theory for the high thermoelectric performance of NaCo2O4 is still lacking, the following features are established. (1) The mixture of Co3+ and Co4+ in the low spin state can carry a large entropy of $`k_B`$log6 koshibae . (2) NaCo2O4 shows no structural, electric, and magnetic transitions from 2 to 1000 K ohtaki ; fujita . (3) From (1)(2), the large entropy cannot be released through phase transitions, and inevitably adhere to the conducting carriers to form a “heavy-fermion”-like electron.

In this respect, NaCo2O4 is very close to the instability for various phase transitions arising from the large entropy per site. The Cu substitution enhances the instability, and eventually causes the SDW-like transition at 22 K. This type of transition is called “order from disorder” tsvelik , which has been extensively investigated experimentally as well as theoretically. In other words, instabilities against various phases are competing or disordering in NaCo2O4, and any phase transitions are prohibited down to low temperatures. This does not mean that NaCo2O4 is far from the instability of phase transitions, but rather, is very susceptible to various transitions against various perturbations. In fact, Na1.5Co2O4 exhibits a glassy behavior at 3 K due to structure instability of the $`\gamma `$ phase takeuchi , and (Bi,Pb)-Sr-Co-O shows a ferromagnetic transition at 4 K due to the lattice misfit tsukada .

Among various possible transitions, it is not trivial whether an SDW-like state is favored by impurities or not. As an SDW-formation mechanism, we should note here that SDW and CDW are closely related to the nesting of the and the topology of the Fermi surface. They are a property for a metal, and occur when the correlation effect is weak enough to hold one-electron picture based on the band calculation. As often mentioned in the present paper, the experimental results consistently suggest that Cu suppresses the mass enhancement without significant change in the carrier concentration. If so, the decrease in $`\chi `$ implies that the substituted Cu enhances the screening of the magnetic fluctuation, which might recover the band picture to cause the CDW/SDW instability of the $`a_{1g}`$ Fermi surface.

## V Summary and Future issues

In this article, we have discussed the Cu substitution effects on the thermoelectric and thermodynamic properties of NaCo2-xCuxO4. The substituted Cu induces a phase transition at 22 K, which is characterized by the kink in the resistivity, the hump in the thermopower, and the jump in the specific heat. We have analysed the nature of the transition, and finally proposed a spin-density-wave-like state as a possible origin, because (i) it accompanies a small entropy change of the order of 10$`{}_{}{}^{2}k_{B}^{}`$ per Co, (ii) the transition is sensitive to the magnetic field, (iii) the large Fermi surface of the $`a_{1g}`$ character is gapped. The impurity induced transition is often called “order from disorder”, which implies that phase transitions are somehow suppressed in the unsubstituted NaCo2O4.

Above the transition temperature, the thermoelectric properties are at least qualitatively compared with those of heavy-fermions valence-fluctuation compounds, where mobile holes on the $`e_g+a_{1g}`$ band and the nearly localized holes of the $`a_{1g}`$ band correspond to the carrier and the $`f`$ electrons. In this analogy, the substituted Cu increase the interaction between the $`e_g+a_{1g}`$ and $`a_{1g}`$ bands to decrease the effective-mass enhancement.

In this article we have reviewed the phenomenology of the Cu substitution effects, but failed to address the microscopic origin and/or the electronic states of the substituted Cu. This is because our experiments were concerned only with the thermodynamic and transport properties of bulk materials. Nonetheless we can say that the scattering cross section will be small for the $`d_{x^2y^2}`$ and $`d_{z^2}`$ levels of the impurity in NaCo2O4, because the valence bands of NaCo2O4 consist of $`t_{2g}`$. Thus the substituted Cu (possibly divalent anno ) will not increase $`\rho `$ seriously, because Cu2+ has the highest occupied orbital of $`d_{x^2y^2}`$ that is orthogonal to $`t_{2g}`$. In addition, strong Jahn-Teller effects of Cu2+ may cause local distortion of the CoO2 block, which serves as a kind of chemical pressure to increase $`S`$ terra2 . To proceed further, site-selective probes such as NMR, photoemission, and STM/STS should be employed.

## Acknowledgments

The authors would like to thank T. Motohashi, H. Yamauchi, N. Murayama, K. Koumoto, and T. Mizokawa for fruitful discussion.


text:
# A multi-epoch spectrophotometric atlas of symbiotic starsBased on observations collected with the telescopes of the European Southern Observatory (ESO, Chile) and of the Padova & Asiago Astronomical Observatories (Italy),Figures 4–256 are only available in electronic form (𝑎) at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/Abstract.html, and (𝑏) from the personal home page http://ulisse.pd.astro.it/symbio-atlas/

## 1 Introduction

Allen’s (1984) atlas offered the first comprehensive spectroscopic view of symbiotic stars. It included spectra covering the 3400-7500 Å range for 114 objects (validated and possible, corresponding to 72% of the total number known at the time), which however were not fluxed, of low resolution and low dynamic range. Nevertheless, Allen’s catalogue has been extensively used in all studies of symbiotic stars, even in those concerning single objects, because its single-epoch spectra could be compared with later observations in order to study the marked spectral variability of these binaries.

Other compilations of symbiotic star optical spectra are available. The larger ones since Allen’s atlas are Blair et al. (1983; 16 objects, absolute fluxes), Ipatov & Yudin (1986; 14, absolute), Kenyon & Fernandez-Castro (1987; 11, absolute), Acker et al. (1988; 10, relative) Múrset et al. (1996; 12, absolute), Gutierrez-Moreno et al. (1999; 14, absolute) and Medina Tanco & Steiner (1995; 45, relative). Meier et al. (1994) assembled an atlas of ultraviolet IUE spectra for 32 symbiotic stars, Schulte-Ladbeck (1988) of 16 objects in the near-IR and Schild et al. (1992) of 8 objects in the IR. Van Winckel et al. (1993) surveyed emission line profiles for 59 objects and Ivison et al. (1994) for 35. Pereira et al. (1999) presented Bowen-fluorescence dominated blue spectra for 8 symbiotic stars and Schmid and Schild (1994) surveyed Raman-scatter dominated red spectra for 15 objects.

Here we present the largest optical spectroscopic atlas of symbiotic stars since Allen’s one. Compared to Allen’s atlas, our spectra cover a comparable number of objects (130 in all, 75 observed from ESO, 40 from Asiago, and 15 from both places) but are better resolved , extend over a wider wavelength range, offer a higher dynamical range, are absolutely fluxed, are multi-epoch (half of the targets re-observed one or more times over a three year period), and are available in electronic form (from the authors upon request).

The spectra presented in this atlas are planned to become the input data for future follow-up studies:
$``$ given the high accuracy of the absolute fluxes and the wide wavelength range covered, optical magnitudes will be derived from the spectra and combined into a unique multi-epoch UBV(RI)C photometric catalogue with the results of CCD photometry of 60 symbiotic stars obtained by Henden and Munari (2000, 2001a, 2001b) while calibrating their comparison sequences;
$``$ the rich emission line spectrum of symbiotic stars will be studied in a global approach;
$``$ properties of the cool giants will be derived from the absorption spectrum in the red region.

## 2 The data

The list of program stars and the journal of observations is given in Table 1. The number of symbiotic stars (validated and

probable) observed for this atlas is 130, with a total of 213 spectra presented in Figures 4–216. Spectra of 40 reference stars are given in Figures 217–256, with Table 2 listing their relevant properties. Figure 1 gives an example of Figures 4–256 available electronically only. Of the 90 symbiotic stars observed from ESO, 22 have been re-observed about one year later. Fifty-five are instead the symbiotics observed from Asiago, 21 of which were re-observed once, 9 twice and 1 three times over a two and a half year period. For some systems our observations document the spectral changes induced by an outburst state, as for CL Sco (during the 1995 quiescence in Fig. 49, and at 1996 outburst in Fig. 50), or their interplay with the pulsation activity of the cool giant, as for the carbon symbiotic Mira UV Aur (at Mira’s minimum in Fig. 124, and at Mira’s maximum in Fig. 125).

The program stars have been selected among those listed in Allen’s (1984) catalogue and those discovered later (and summarized in the new catalogue of symbiotic stars by Belczynski et al. 2000), including objects from the Meyssonnier & Azzopardi (1993) survey of SMC.

The object names (as given in Table 1 and the first column of Table 3) are sometimes different from those used in the literature, because either (i) a variable star name has been assigned since (for example V1413 Aql for AS 338), or (ii) there have been re-organizations in the name coding within SIMBAD (for example, He 2-468 was replaced by Hen 2-468, or Hen 1591 is now Hen 3-1591). A list of correspondences is given in Table 3, where column 2 contains Allen (1984) names for the systems renamed subsequently.

The spectrophotometric observations have been performed with B&C + CCD spectrographs at ESO and Asiago. All spectra have been reduced with the IRAF software package. Standard procedures (including bias and flat field correction, wavelength and flux calibration) have been applied. Cosmic rays on the stellar tracing were cleaned manually on the extracted spectrum after inspection of the original two dimensional frames. For the vast majority of the program stars we have obtained more than one spectrum per night (with the aim of appropriately exposing the continuum as well as avoiding saturation of the strongest emission lines), and their inter-comparison greatly assisted during the manual cleaning of cosmic-rays.

### 2.1 Astrometry

Historically inaccurate or erroneous coordinates of several symbiotic stars are still present in the current literature. Moreover, correspondence between symbiotic stars and entries in astrometric catalogues has not been systematically explored yet. The latter is an important task because, once the correspondence is established, coordinates of symbiotic stars will be automatically improved every time the catalogues are re-calibrated (like USNO-A1 that has been recalibrated into USNO-A2 when the Hipparcos/Tycho reference stars have become available) or cross-referenced toward newer and higher precision catalogues.

Correspondence with sources in astrometric catalogues is established in Table 3 (last column) for all the program stars. Help has been provided by the Aladin graphical interface at CDS (http://aladin.u-strasbg.fr/aladin.gml) that allows overplotting of astrometric catalogues over the digitized DSS-I and DSS-II plates. The astrometric identification has been searched for and taken from the following catalogues, in order of preference: Hipparcos, Tycho-2, USNO-A2.0, GSC-1, 2MASS. Only 6 objects lack any astrometric identification, while 14 and 24 objects are included in the Hipparcos and Tycho-2 catalogues, respectively.

Coordinates of program stars in Table 1 have not been adapted or re-processed from the existing literature, but re-compiled from scratch. Hender and Munari (2000, 2001a) give astrometrically measured accurate positions for 40 of our program stars (linked to the USNO-A2.0 reference system). For the remaining targets the positions as given in the appropriate astrometric catalogues (following identifications in Table 3) have been adopted. For the 6 objects without an entry in the surveyed astrometric catalogues, coordinates have been measured by us on the digitized DSS-II plates (or, if not available, on the DSS-I ones). All coordinates are on J2000.0 equinox, but epochs are those of the corresponding catalogues (this should not be a major concern given the minimal proper motions typical for most symbiotic stars).

### 2.2 ESO observations

The ESO observations have been performed with the B&C + CCD spectrograph at the 1.5 m telescope under photometric conditions (sparse data from non optimal nights have not been used in the present atlas). We used a 400 l/mm grating (# 25) and a 2 arcsec slit, always aligned along the parallactic angle for pointings at zenital distances larger than 35. The CCD was a 2048$`\times `$2048, 15 $`\mu `$m size, thinned and back-illuminated to enhance UV sensitivity. The dispersion was $``$2.5 Å/pix, with a FWHM(PSF)$``$2 pixels. The covered spectral range changes somewhat from one observing run to another, with the extremes of 3200–8900 and 3400–9100 Å. The seeing during the observing nights was always smaller than the slit width (as can be derived from the simultaneous absolute measurements with the La Silla Meteo Monitor and from the measured FWHM perpendicular to the dispersion on the recorded stellar spectra). For a non–marginal part of the time the seeing was better than 1 arcsec. Several spectrophotometric standards were observed each night in order to achieve absolute flux calibration and monitor stable transparency conditions.

### 2.3 Asiago observations

The Asiago observations were secured with the Boller & Chivens spectrograph attached to the 1.82 m telescope operated by Osservatorio Astronomico di Padova atop of Mount Ekar (Asiago, Italy), during nights of suitable photometric conditions. The detector was a Thompson TH7882 UV-coated CCD, 580x388 pixels of 23$`\mu `$m size. We used a 150 ln/mm grating giving a dispersion of 7.5 Å/pixel, generally covering the wavelengths 3350-7550 Å (exact limits variable according to the observing runs). The slit width was $``$2.0 arcsec, giving a FHWM(PSF)$``$2 pixels. When the object’s zenith distance exceeded 45, the slit was aligned along the parallactic angle. Each night at least four spectrophotometric standard stars were observed more than once at different airmasses for flux calibration.

### 2.4 Reference objects

A number of spectra of reference objects have been secured with the same instrumentation during symbiotic star observing runs. The reference objects include MKK cool giant standards, Miras, planetary nebulae, Wolf Rayet stars, white dwarfs, hot sub-dwarf, classical novae, and are intended to assist inspection and interpretation of symbiotic star spectra. They are listed in Table 2 and their spectra are presented in Figures 217–256.

### 2.5 Flux accuracy

It appears appropriate to quantify the accuracy of absolute fluxes in this atlas. For symbiotic stars no optical photometry was carried out simultaneously with the spectroscopic observations. However, a number of program symbiotic stars are regularly observed by several organizations of amateur astronomers. We have consulted the on-line databases of VSNET, VSOLJ and AFOEV and found useful data to support comparison with 70 of the spectra presented in this atlas (49 Asiago spectra and 21 ESO spectra, reflecting the predominance of amateurs in the northern hemisphere and higher brightness of average symbiotic stars known in the northern hemisphere). When possible the amateurs’ lightcurves have been interpolated/extrapolated to derive the visual magnitude for the date of the given spectral observation. In a few cases an estimate was found in the amateurs’ archives for the exact date of the spectral observations. Such estimates have been adopted unless an eye inspection of the whole light-curve rendered them unreliable.

The $`V`$ magnitude was derived from our spectra by convolving them with the $`V`$ band-pass profile (taken from Ažusienis & Straižys 1969). The comparison between the spectroscopic and amateurs’ $`V`$ magnitudes is presented in Figure 2 separately for the Asiago and ESO data. The comparison gives for the ESO spectra:

$$V_{spectrum}V_{amateurs}=0.06;\sigma =0.21$$
(1)
and similarly for the Asiago spectra:

$$V_{spectrum}V_{amateurs}=0.05;\sigma =0.19$$
(2)
The offset is small and can be easily accounted for by a number of possibilities, the first and the most obvious one being the difference between the eye response and the $`V`$ band profile.

ESO and Asiago observations appear equally accurate, as seen in Figures 2 and 3, with an average 0.20 mag scatter that deserves some comment. Several mechanisms contribute to it, including \[$`a`$\] errors in the comparison sequences used by amateurs ($`\sigma _{cs}`$), \[$`b`$\] errors in estimating the magnitude by the amateurs and uncertainties in interpolating/extrapolating their lightcurve to the desired date ($`\sigma _{est}`$), \[$`c`$\] day-by-day random variability of symbiotic stars ($`\sigma _{var}`$), and obviously \[$`d`$\] the errors in fluxing our spectra ($`\sigma _{flux}`$). Because these errors are unrelated and follow normal distributions we write

$$\sigma ^2=(0.20)^2=\sigma _{cs}^2+\sigma _{est}^2+\sigma _{var}^2+\sigma _{flux}^2$$
(3)
Based on common experience it may be assumed that $`\sigma _{cs}`$0.05, $`\sigma _{est}`$0.15, and $`\sigma _{var}`$0.1 ($`\sigma _{cs}=`$0.05 is obviously an underestimate, at least because magnitudes of comparison stars on amateur finding charts are given to one decimal figure only). So $`\sigma _{flux}`$ 6%, i.e. the fluxes of each individual spectrum are on the average accurate better than 6%. This is in fair agreement with results of inter-calibrations of spectrophotometric standard stars observed every night that suggest an accuracy of 5% or better.

Certain points in Figure 3 are marked with open circles and triangles. The open circles refer to HM Sge and V1016 Cyg that have spectra resembling planetary nebulae. Minimal differences between the $`V`$ band and eye response curves around the immensely strong H$`\alpha `$ and \[OIII\] lines fully account for the $``$0.7 mag systematic difference of both Asiago and ESO spectra versus amateurs’ estimates. The open triangles refer to V1413 Aql that shows the same $``$0.8 mag systematic difference between the Asiago and ESO spectra vs. amateurs’ estimates: the reason may be an error in the comparison sequence around V1413 Aql used by the amateurs.

Another independent way to estimate the flux accuracy is offered by the spectra of the reference objects listed in Table 2. Selecting those not carrying a variable star name among those observed by Hipparcos/Tycho, we found

$$V_T^{spectra}V_T^{Tycho}=0.06;\sigma =0.08$$
(4)
$$(BV)_T^{spectra}(BV)_T^{Tycho}=+0.03;\sigma =0.03$$
(5)
Here the spectra were convolved with the $`B_T`$ and $`V_T`$ band profiles as given in the Hipparcos Catalogue (ESA SP-1200, June 1997, pag 42; slightly modified transmission profiles are suggested by Bessell 2000). The uncertainties in the shutter aperture time ($``$0.1 sec in both Asiago and ESO observations) become notable in the observations of the bright template stars in Table 2 with an average exposure time of only 2.5 sec. Also, non-perfect placement of such bright objets on the slit, which is compensated for faint objects by guiding, may contribute to the scatter in Eq.(5). Finally, it is worth remembering that Tycho data for bright stars are accurate to 0.012 mag in $`V_T`$ and 0.02 mag in $`(BV)_T`$.

In light of these considerations it seems safe to argue that the fluxes in this atlas are generally correct within

$$\sigma _{flux}\stackrel{<}{}5\%$$
(6)
at least for the $`B`$, $`V`$ and $`R`$ band wavelength ranges. A lower accuracy is probable for faint red objects at $`\lambda `$3800 Å or for pure emission line spectra at $`\lambda `$8700 Å.

## 3 The atlas

Each spectral observation listed in Tables 1 and 2 is presented by a separate figure. The format of the figures is identical to Figure 1. UT dates are in the DD.dd/MM/YY format.

At upper right a full-scale, compressed view of the whole recorded spectrum is given, and the units for absolute fluxes are indicated. The same units are valid for the other panels that present zoomed-in portions of the spectrum.

For ESO spectra the first zoomed-in panel always runs from 3200 to 5250 Å, the second from 5150 to 7200 Å, and the third from 7100 to 9150 Å. For Asiago spectra, given the shorter wavelength range covered, two zoomed-in panels suffice, the first from 3250 to 5600 Å, the second from 5350 to 7600 Å.

Stronger emission lines are generally truncated in the zoomed-in panels to emphasize the visibility of finer details. The full height of emission lines can be read from the compressed view of the whole spectrum at the upper right.


text:
# Thermoelectric properties of the brownmillerite oxide Ca2-yLayCo2-xAlxO5

## I Introduction

Thermoelectric materials, which convert heat into electricity and vice versa through the thermoelectric phenomena in solids, have recently attracted a renewed interest as a promising energy-conversion technology that is friendly to the environment. The conversion efficiency of a thermoelectric material is characterized by the figure of merit $`Z=S^2/\rho \kappa `$, where $`S`$, $`\rho `$ and $`\kappa `$ are the thermopower, the resistivity, and the thermal conductivity, respectively.

Recently Terasaki et al.terasaki  found that a layered cobalt oxide NaCo2O4 shows a large thermopower of 100 $`\mu `$V/K and a low resistivity of 200 $`\mu \mathrm{\Omega }`$cm at room temperature, and they proposed that the strong correlation plays an important role in the enhancement of the thermoelectric properties. Based on this proposal, other layered cobalt oxides Bi-Sr-Co-Oitoh ; funahashi  and Ca-Co-Oco349 ; miyazaki ; co225  have been studied, and they are found to be potential thermoelectric materials as well as NaCo2O4. In particular, Funahashi et al.co225  reported the maximum of $`ZT`$ is larger than 1.2 for Ca-Co-O, which means that the layered cobalt oxides might be the best group among all the thermoelectric materials.

These layered cobalt oxides are, however, all p-type materials, and an n-type cobalt oxide has not been found yet. Thermoelectric devices are made from a pair of p and n-type thermoelectric materials, and we tried to find an n-type cobalt oxide. The Co ion in NaCo2O4 is at the center of an oxygen octahedron, and its average valence is +3.5 with the electron configuration of $`(3d)^{5.5}`$, which corresponds to 0.5 hole in the $`t_{2g}`$ bands per Co site. In NaCo2O4, the octahedron is edge-shared, where the $`t_{2g}`$ bands of Co 3$`d`$ directly overlap each other. By contrast, electrons doped in an insulating cobalt oxide made of Co3+ will be in the $`e_g`$ bands. Since the $`e_g`$ bands are strongly hybridized with O $`2p`$, the conduction-band width is largest when the bonding angle of Co-O-Co is 180. Thus a cobalt oxide in a corner-shared oxygen octahedron will be a good n-type conductor.

Accordingly we searched for a cobalt oxide in a corner-shared oxygen octahedron, and eventually found Ca2(Co,Al)2O5kouzou , which has a brownmillerite structure with Co3+. The brownmillerite structure is schematically shown in Fig. 1. Big white circles represent Ca and La, black circles Co, shaded circles Al and Co. This structure is composed of an alternate stack of the CoO2 square lattice and the (Co,Al)O chain along the $`c`$ direction, and can be regarded as an oxide-deficient perovskite structure. In this paper we report on preparation of polycrystalline and single-crystal samples, and on measurements and analyses of their thermoelectric properties.

## II Experimental

Polycrystalline samples of Ca2-yLayCoAlO5 ($`y=`$0, 0.05, 0.1 and 0.15) and Ca1.95La0.05Co2-xAlxO5 ($`x=`$0.4, 0.5, 0.6, and 0.7) were prepared by a solid-state reaction. Stoichiometric amounts of CaCO3, La2O3, Co3O4 and Al2O3 were mixed, and the mixture was calcined at 900C for 12h in air. The product was finely ground, pressed into a pellet, and sintered at 960C for 12h in air.

Single-crystal samples were prepared by a Bi2O3/PbO flux method. Bi2O3, PbO, CaCO3 and Co3O4 powders were mixed with a cationic composition of Bi:Pb:Ca:Co=1.3:0.7:3:2, and was heated at 1100C for 5h, and then slowly cooled down to 700C at a rate of 8C/h in air using an Al2O3 crucible (Al was supplied from the crucible). The composition ratio of a single-crystal sample measured by energy dispersive X-ray analysis (EDX) is Ca:Co:Al$`=`$2:1.3:0.7.

The X-ray diffraction (XRD) of the sample was measured using a standard diffractometer with Fe Kα radiation as an X-ray source in the $`\theta 2\theta `$ scan mode. The resistivity was measured using a four-probe method, below room temperature in a liquid He cryostat, and above room temperature in an electric furnace. The thermopower was measured using a steady-state technique, below room temperature in a liquid He cryostat, and above room temperature in an electric furnace. A temperature gradient of 1 K/cm was generated by a small resistive heater pasted on one edge of a sample, and was monitored by a differential thermocouple made of copper-constantan below room temperature, and by that of platinum-rhodium above room temperature. The thermopower of the voltage leads was carefully subtracted. The thermal conductivity was measured from 30 to 280 K using a steady-state technique in a closed refrigerator pumped down to 10-6 Torr. The temperature gradient was monitored using a differential thermocouple made of chromel-constantan.

## III Results and Discussion

Figure 2 shows an XRD pattern of a polycrystalline sample Ca1.95La0.05Co1.3Al0.7O5 A small amount (at most 7%)of impurity phase (mainly Ca3Co4O9)co349  is seen, but almost all the peaks are indexed as the brownmillerite phase. The lattice parameters were obtained to be $`a=`$5.28 Å, $`b=`$5.52 Å, and $`c=`$14.66 Å, which is consistent with a 4-cycle X-ray diffraction of a single crystal. We will use the composition as the nominal composition in the present paper, though the real composition is different from the nominal composition. However, the difference is small within less than 10% accuracy: for example a nominal La \[Al\] content of 0.05 \[0.5\] corresponds to 0.053 \[0.54\] for the real composition at most. We further note that the impurity phase of Ca3Co4O9 shows positive and nearly temperature-independent thermopower above 100 K co349 , which would not seriously affect the temperature and the composition dependences of $`\rho `$ and $`S`$, or the discussion in the present paper.

Figure 3(a) shows $`\rho `$ and $`S`$ of polycrystalline Ca2-yLayCoAlO5 at room temperature. With increasing La content $`y`$, $`\rho `$ decreases systematically, and the sign of $`S`$ changes from positive to negative. This indicates that the substitution of La3+ for Ca2+ supplies an electron. Figure 3(b) shows the power factor $`S^2/\rho `$ corresponding to the data in Fig 2(a). The power factor takes a maximum at $`y`$=0.05, and accordingly we fix $`y`$ to be 0.05 to see the Al-content dependence.

Figure 4(a) shows $`\rho `$ of polycrystalline samples of Ca1.95La0.05Co2-xAlxO5, together with the in-plane (parallel to the $`ab`$ direction) and the out-of-plane (parallel to the $`c`$ direction) resistivity of a single-crystal sample of Ca2Co1.3Al0.7Oy. At 750 K, the magnitude of resistivity decreases down to 10-20 m$`\mathrm{\Omega }`$cm for polycrystalline samples and the in-plane direction of the single crystals. This magnitude of resistivity is the lowest, to our knowledge, in brownmillerite oxides brown1 ; brown2 . The temperature dependence is described by an activation-type conduction, where the activation energy for resistivity (Eρ) is approximately 0.2 eV for all the samples. As for anisotropy, the out-of-plane resistivity is 100 times higher than that for the in-plane resistivity, implying that the layered structure is realized, as is expected from the brownmillerite phase. This means that the conduction path of a single crystal sample is two-dimensional, and the conduction path of the polycrystalline samples is mainly determined by the in-plane conduction paths. Then the resistivity of the polycrystalline samples is higher than the in-plane resistivity of the single crystal sample, while the temperature dependences are similar, as is also seen in the resistivity of high-temperature superconductors. The resistivity increases with increasing Al content $`x`$, which indicates that a Co ion is responsible for the electric conduction and an Al ion acts as an impurity. We should note that the brownmillerite structure was not synthesized for $`x0.4`$, which means that an Al ion is essential to stabilizing the brownmillerite structure at ambient pressure.

Figure 4(b) shows the thermopower of the prepared samples. The in-plane thermopower of the single-crystal sample is $``$150 $`\mu `$V/K, and that of polycrystalline samples is about $``$100 $`\mu `$V/K at 300 K. This means that the carrier concentration of the single-crystal sample is smaller than that of the polycrystalline samples, because no donor ion such as La is included in the single crystal. The source of the carrier is not clear at present, and the oxygen deficiency or a small inclusion of Bi3+ are possible candidates.

It should be emphasized that the magnitude and the temperature dependence of the thermopower of polycrystalline samples are nearly independent of $`x`$. Considering the $`x`$ dependence of $`\rho `$ and $`S`$, we can conclude that an Al ion acts as a scattering center (disorder) for electric conduction, although it stabilizes the brownmillerite structure at ambient pressure kouzou . Consequently carriers are likely to conduct on CoO2 square lattice, not on the (Co,Al)O chain. Below 350 K, the temperature dependence of the thermopower is described by an activation-type conduction with the activation energy for thermopower ($`E_s`$) of 0.01 eV for the polycrystalline samples, and 0.04 eV for the single-crystal sample. $`E_\rho (=0.2\mathrm{eV})E_s(=0.010.04\mathrm{eV})`$ implies a polaron conduction, where $`E_\rho `$ and $`E_s`$ are described as $`E_\rho =E_FE_c+W_H`$ and $`E_s=E_FE_c`$ ($`E_c`$: the energy of bottom of conduction band, $`E_F`$: Fermi energy, $`W_H`$: hopping energy that contributes to the change of mobility by temperature)mott . Such a material is useful for the high-temperature thermoelectric application wood , because a rapid decrease in $`\rho `$ and a gradual decrease in $`S`$ will occur with increasing temperature.

For the present material, however, the high temperature thermopower is quite small. Above 350 K it deviates from the activation type, and the sign of the thermopower of the polycrystalline samples changes from negative to positive at 500 K. A similar tendency was observed for the single-crystal sample, though a sign change was not yet seen below 550 K. As a result the thermoelectric performance rapidly decreases above 450 K. Very recently Ueno et al. have found a similar sign change of the thermopower in the brownmillerite Ca-Co-Al-O thin film ueno .

Figure 5 shows the thermal conductivity of polycrystalline samples. The magnitude is about 20 mW/cmK, which is relatively low, possibly due to a solid solution of Co and Al. Using $`\kappa `$=20 mW/cmK, the figure of merit for $`x=0.4`$ is estimated to be of the order of 10-6 K-1 at 300 K, which is three orders of magnitude smaller than that of the conventional thermoelectric materials. By examining $`\rho `$, $`S`$ and $`\kappa `$ individually, we find $`\rho `$ is hopelessly high, while $`S`$ and $`\kappa `$ are comparable. This is due to the polaron conduction where the mobility is exponentially lowered with decreasing temperature.

Let us discuss the sign change of the thermopower at 500 K. We should note that the electronic states (and the crystal structure) of Ca2(Co,Al)2O5 resemble those of the cubic perovskite LaCoO3, which is a p-type conductor at all temperatureslaco . Thus it is very likely that holes are thermally excited also in Ca2(Co,Al)2O5 at high temperature, which will compensate the doped electrons to decrease the magnitude of the thermopower. In general, the square lattice as seen in the brownmillerite is often symmetric to electron and hole doping (which is exact in the tight-binding approximation) mao ; mackenzie . This means that electrons and holes are equally excited at high temperature to give zero thermopower. Thus the electron-hole symmetry is unsuitable for good thermoelectrics, which might be the reason most of the perovskite related oxides are not good thermoelectric materials.

## IV Summary

We successfully prepared an n-type Co oxide material for the first time, although the thermoelectric properties are not satisfactory. The figure of merit at 300 K is of the order of $`10^6`$ K-1, the low value of which comes from the high resistivity. The high resistivity is ascribed to the polaron conduction suggested by the fact that $`E_\rho `$ is one order of magnitude larger than $`E_s`$. The sign change of the thermopower represents thermal excitation of holes at high temperatures. Thus it would be less advantageous to design an n-type thermoelectric material by using Co oxides with a corner-shared oxygen octahedron network.

## V Acknowledgements

The authors appreciate K. Takahata for fruitful discussions and valuable comments. We would also like to thank R. Kitawaki and T. Itoh for collaboration.