# Re-entrant spin susceptibility of a superconducting grain

## Abstract

We study the spin susceptibility $`\chi `$ of a small, isolated superconducting grain. Due to the interplay between parity effects and pairing correlations, the dependence of $`\chi `$ on temperature $`T`$ is qualitatively different from the standard BCS result valid in the bulk limit. If the number of electrons on the grain is odd, $`\chi `$ shows a re-entrant behavior as a function of temperature. This behavior persists even in the case of ultrasmall grains where the mean level spacing is much larger than the BCS gap. If the number of electrons is even, $`\chi (T)`$ is exponentially small at low temperatures.

By now it is well-known that the properties of an isolated, mesoscopic superconducting grain are quite different from those of a bulk sample . First of all, since such a grain carries a fixed number, $`N`$, of electrons, its behavior depends strongly on whether $`N`$ is even or odd. Second, fluctuation effects become important as the size of the grain decreases. The interplay between parity and fluctuation effects crucially depends on the ratio $`\delta /\mathrm{\Delta }_0`$ of two characteristic energies: the mean level spacing $`\delta `$ and the bulk superconducting gap $`\mathrm{\Delta }_0`$. As long as the grain is not too small, $`\delta \mathrm{\Delta }_0`$, the fluctuation region $`\mathrm{\Delta }T`$ around the critical temperature $`T_c`$ is narrow, $`\mathrm{\Delta }T/T_c\sqrt{\delta /\mathrm{\Delta }_0}1`$, and the mean field description of superconductivity is appropriate. Parity effects  appear at temperatures lower than a crossover temperature $`T_{\mathrm{eff}}\mathrm{\Delta }_0/\mathrm{ln}\sqrt{8\pi \mathrm{\Delta }_0^2/\delta ^2}`$ which, in the experiments , is typically of the order of $`1030\%`$ of $`T_c`$. The dependence of $`T_{\mathrm{eff}}`$ on $`\mathrm{\Delta }_0`$ signals that the even-odd asymmetry is a collective effect due to pairing correlations. As the size of the grain is decreased, fluctuations start to smear the superconducting transition . The finite level spacing suppresses the BCS gap in a parity-dependent way . When $`\delta `$ becomes of the order of $`\mathrm{\Delta }_0`$, $`\mathrm{\Delta }TT_c`$ and the BCS description of superconductivity breaks down even at zero temperature . The regime $`\delta \mathrm{\Delta }_0`$ is dominated by strong pairing fluctuations .

The present-day interest in ultrasmall superconducting grains was triggered by the experiments of Ralph, Black and Tinkham , who were able to contact a single, nanometer-sized Al grain with current and voltage probes. They obtained tunneling spectra that revealed the presence of a parity-dependent spectroscopic gap, larger than the average level spacing, which could be driven to zero by an applied magnetic field. In this Letter we propose to measure the temperature dependence of a thermodynamic quantity – the spin susceptibility $`\chi `$ – as a means to detect both parity effects and pairing correlations. As we will show below, pairing correlations give rise to a specific temperature dependence of thermodynamic quantities. This enables a more quantitative investigation of fluctuation effects .

Spin paramagnetism of small particles has been considered in the past  and very recently parity effects in the susceptibility were measured for an ensemble of small, normal metallic grains . Spin susceptibility is very sensitive to BCS pairing as well. Yosida  showed that, due to the opening of the superconducting gap, $`\chi `$ vanishes at zero temperature . We will show that the combined effect of parity and pairing introduces qualitatively new features in the temperature dependence of $`\chi `$. Most interestingly, these effects might be observed even in the regime $`\delta \mathrm{\Delta }_0`$. The results of our work are summarized in Figs. 13, where we plot $`\chi `$ as a function of temperature $`T`$ for odd and even parity. In particular we want to emphasize that the odd susceptibility shows a re-entrant behavior as a function of $`T`$ for any value of the ratio $`\delta /\mathrm{\Delta }_0`$. This re-entrance is absent in normal metallic grains; it is a genuine feature of the interplay between pairing correlations and parity effects.

The BCS pairing Hamiltonian for a small grain can be written as 

$$=\underset{n,\sigma =\pm }{}(ϵ_n\sigma \mu _BH)c_{n,\sigma }^{}c_{n,\sigma }\lambda \delta \underset{m,n}{}B_m^{}B_n,$$
(1)   
where $`B_m^{}=c_{m,+}^{}c_{m,}^{}`$. The indices $`m`$, $`n`$ label the single particle energy levels with energy $`ϵ_m`$ and annihilation operator $`c_{m,\sigma }`$. The quantum number $`\sigma =\pm `$ labels time-reversed equally spaced states (with an average spacing $`\delta 1/\nu _0`$, where $`\nu _0`$ is the density of states at the Fermi energy). The external magnetic field $`H`$ couples to the electrons via the Zeeman term, $`\mu _B`$ is the Bohr magneton. We put the $`g`$-factor equal to two, ignoring any spin-orbit effects (see Ref. ). At the low magnetic fields of interest here, we can neglect the orbital contribution to magnetic energy, as it is smaller than the Zeeman energy by a factor $`(k_Fr)(Hr^2/\mathrm{\Phi }_0)`$ ($`r`$ is the size of the grain and $`\mathrm{\Phi }_0`$ the flux quantum). Finally $`\lambda `$ is the dimensionless BCS coupling constant. Since the Hamiltonian contains only pairing terms, an electron in a singly occupied level cannot interact with the other electrons.

The spin susceptibility of a grain with an even (e) or an odd (o) number $`N`$ of electrons is defined as

$$\chi _{e/o}(T)=\frac{^2_{e/o}(T,H)}{H^2}|_{H=0},$$
(2)   
where $`_{e/o}=T\mathrm{ln}Z_{e/o}`$ is the free energy of the grain and the partition function $`Z(T,N)`$ should be evaluated in the canonical ensemble. We will perform the calculation with the help of a parity projection technique  and by means of exact canonical methods based on Richardson’s solution . The grand partition function reads

$$Z_{e/o}(T,\mu )=(1/2)\underset{N=0}{\overset{\mathrm{}}{}}e^{\mu N/T}[1\pm e^{i\pi N}]Z(T,N)(1/2)\left(Z_+\pm Z_{}\right).$$
(3)   
The partition function $`Z_+`$ is the usual grand partition function at temperature $`T`$ and chemical potential $`\mu _+=\mu `$. The grand partition function $`Z_{}`$ describes an auxiliary ensemble at temperature $`T`$ and chemical potential $`\mu _{}=\mu +i\pi T`$; it is a formal tool, necessary to include parity effects. The chemical potential $`\mu `$ will be placed between the topmost occupied level and the lowest unoccupied level in the even case, while it will be at the singly occupied level in the odd case. Since we are interested in the evaluation of fluctuations effects, it is convenient to express the grand partition functions $`Z_\pm `$ using the path integral formulation of superconductivity ,

$$Z_\pm =Z_\pm ^0\frac{𝒟^2\mathrm{\Delta }\mathrm{exp}\left\{\underset{0}{\overset{\beta }{}}𝑑\tau \left[\mathrm{Tr}\mathrm{ln}(1\widehat{G}_\pm ^0\widehat{\mathrm{\Delta }})\frac{\mathrm{\Delta }^2}{\lambda \delta }\right]\right\}}{𝒟^2\mathrm{\Delta }\mathrm{exp}\left\{\underset{0}{\overset{\beta }{}}𝑑\tau \frac{\mathrm{\Delta }^2}{\lambda \delta }\right\}}.$$
(4)   
Here, $`\beta =1/T`$ and $`Z_\pm ^0`$ is the partition function for non-interacting electrons. The matrix Green function $`\widehat{G}_\pm ^0`$ is given by $`\widehat{G}_\pm ^{(0)}(ϵ_\nu )=\left[(i\omega _\nu +\mu _BH)\sigma ^{(0)}(ϵ_n\mu _\pm )\sigma ^{(z)}\right]^1,`$ where $`\omega _\nu `$ is a fermionic Matsubara frequency, $`\sigma ^{(i)}`$ ($`i=x,y,z`$) are the Pauli matrices, and $`\sigma ^{(0)}`$ is the identity. Finally, the matrix $`\widehat{\mathrm{\Delta }}`$ is given by $`\widehat{\mathrm{\Delta }}=(\mathrm{\Delta }/2)(\sigma ^x+i\sigma ^y)+\mathrm{h}.\mathrm{c}.`$ A direct calculation of the partition function (4) is impossible in general. Below, we first discuss two limiting cases which are tractable analytically: $`\delta /\mathrm{\Delta }_01`$ and $`\delta /\mathrm{\Delta }_01`$. Then we present the complete temperature dependence of the spin susceptibility evaluating Eq. (4) numerically for arbitrary values of $`\delta /\mathrm{\Delta }_0`$, with the help of the static path approximation .

Large grains ($`\mathrm{\Delta }_0\delta `$) . In this limit it is sufficient to evaluate the partition function in a saddle point approximation, since fluctuations will not contribute significantly . As a result we find

$$\chi _{e/o}=\frac{\mu _B^2}{2T}\underset{n}{}\frac{Z_+\mathrm{cosh}^2\frac{E_{+,n}}{2T}Z_{}\mathrm{sinh}^2\frac{E_{,n}}{2T}}{Z_+\pm Z_{}},$$
(5)   
where $`E_{\pm ,n}=\sqrt{ϵ_n^2+\mathrm{\Delta }_\pm }`$. The saddle point values of $`\mathrm{\Delta }_\pm `$ are found from the equations

$$\frac{1}{\lambda }=\underset{n,\sigma }{}\frac{\delta }{4E_{\pm ,n}}\text{th}^{\pm 1}\left(\frac{E_{\pm ,n}\sigma \mu _BH}{2T}\right).$$
(6)   
The partition functions for the two ensembles are

$`Z_\pm =\mathrm{exp}\left\{{\displaystyle \underset{n,\sigma }{}}\left[\mathrm{ln}2\left\{\begin{array}{c}\text{ch}\\ \text{sh}\end{array}\right\}{\displaystyle \frac{E_{\pm ,n}^\sigma }{2T}}{\displaystyle \frac{\xi _n}{2T}}\right]{\displaystyle \frac{\mathrm{\Delta }_\pm ^2}{\lambda \delta T}}\right\},`$ (9)   
where $`E_{\pm ,n}^\sigma =E_{\pm ,n}\sigma \mu _BH`$ and $`\xi _n=ϵ_n\mu `$.

At low temperatures $`T\mathrm{\Delta }_0`$, the ratio $`Z_{}/Z_+`$ can be calculated easily; one finds $`Z_{}/Z_+1\sqrt{8\pi T\mathrm{\Delta }_0/\delta ^2}\mathrm{exp}(\beta \mathrm{\Delta }_0)`$. Parity effects are important if this ratio is $`1`$, i.e. at temperatures $`T<T_{\mathrm{eff}}`$. At temperatures $`T_{\mathrm{eff}}T\mathrm{\Delta }_0`$, parity effects can be ignored and the spin susceptibility is found to decrease exponentially, as in the BCS case,

$$\chi _{e/o}\frac{2\mu _B^2}{\delta }\sqrt{\frac{2\pi \mathrm{\Delta }_0}{T}}e^{\beta \mathrm{\Delta }_0}.$$
(10)   
For $`TT_{\mathrm{eff}}`$, Eq. (5) can be approximated as

$$\chi _e\frac{8\pi \mu _B^2\mathrm{\Delta }_0}{\delta ^2}e^{2\beta \mathrm{\Delta }_0};\chi _o\frac{\mu _B^2}{T}.$$

We see that $`\chi _e`$ remains exponentially small, like in the BCS case (10), but with an exponent $`2\beta \mathrm{\Delta }_0`$ rather than $`\beta \mathrm{\Delta }_0`$. This reflects the fact that excitations are actually created in pairs. In odd grains, the unpaired spin gives rise to an extra paramagnetic (Curie-like) contribution to the spin susceptibility. As a result $`\chi _o`$ will show a re-entrant effect at low temperatures (see Fig. 1). Although the re-entrant behavior is essentially a single electron effect, we stress that it can be detected experimentally using granular systems with many well-separated grains (to avoid collective effects due to tunneling). Such systems contain even grains as well, but their susceptibility is exponentially small at the temperatures of interest; thus their contribution to the response of the system will be negligible.

Ultrasmall grains ($`\mathrm{\Delta }_0\delta `$) . A reduction of the grain size leads to a suppression of the gap $`\mathrm{\Delta }`$. For ultrasmall grains with $`\mathrm{\Delta }_0\delta `$, the mean field approximation gives $`\mathrm{\Delta }=0`$: the grain behaves as a normal metal. The non-interacting, parity-dependent spin susceptibility can be found from Eq. (5), see the topmost curves in Figs. 2 and 3. Note in particular the monotonous dependence of $`\chi _o`$ on $`T`$. The temperature scale at which parity effects appear is set by the average level spacing. If $`T\delta `$, parity effects are exponentially small and $`\chi _{e/o}(T)\chi _P[1(2T/\delta )\mathrm{exp}(\pi ^2T/\delta )]`$. In the opposite limit $`T\delta `$, $`\chi _e`$ is exponentially small, $`\chi _e(T)(8\mu _B^2/T)e^{\beta \delta }`$, as we need to excite an electron out of the topmost, doubly occupied single particle level to magnetize the grain. For an odd grain, $`\chi _o(T)\mu _B^2/T`$ at $`T\delta `$: the topmost level is occupied by a single electron that gives a Curie-like contribution.

The saddle point approach entirely ignores the fact that the fluctuation region $`\mathrm{\Delta }T`$ around $`T_c`$ grows as the size of the grains is reduced. Due to the presence of fluctuations, the behavior of small grains will be different in a distinct way from normal metallic grains. In the limit $`T\delta `$, both fluctuation and parity effects are small; it therefore suffices to consider the fluctuation correction $`\delta \chi _{\mathrm{fluc}}`$ to $`\chi _P`$, evaluating $`Z_+`$, Eq. (4), in Gaussian approximation. As a result, we find $`\delta \chi _{\mathrm{fluc}}/\chi _P\delta /2T\mathrm{ln}(T/\mathrm{\Delta }_0)`$; hence $`\chi _{e/o}(T)\chi _P[1(2T/\delta )\mathrm{exp}(\pi ^2T/\delta )\delta /2T\mathrm{ln}(T/\mathrm{\Delta }_0)]`$. Superconducting correlations suppress the susceptibility; due to its algebraic dependence on $`T`$ this suppression is stronger than the parity correction at temperatures $`T\delta \mathrm{ln}\mathrm{ln}\delta /\mathrm{\Delta }_0`$. In the opposite limit, $`T\delta `$, fluctuations are strong and the Gaussian approximation fails. However, the susceptibility can still be obtained analytically by considering a few levels close to the Fermi energy with a renormalized pairing interaction $`\stackrel{~}{\lambda }=1/\mathrm{ln}(\delta /\mathrm{\Delta }_0)`$ . Consider first a grain with an even number of electrons. It costs an energy $`\delta +\delta /\mathrm{ln}(\delta /\mathrm{\Delta }_0)`$ to excite an electron from the topmost, doubly occupied level to the lowest unoccupied level. Correspondingly, the leading temperature dependence of the spin susceptibility is

$$\chi _e(T)8\frac{\mu _B^2}{T}e^{\beta \delta (1+\mathrm{ln}^1(\delta /\mathrm{\Delta }_0))}+𝒪(e^{2\beta \delta }).$$
(11)   
The even susceptibility is exponentially small, like in the case of a normal metallic grain, but with an exponent $`\beta \delta (1+\stackrel{~}{\lambda })`$, rather than $`\beta \delta `$. Similarly, we find the spin susceptibility for a grain with an odd number of electrons

$$\chi _o(T)\frac{\mu _B^2}{T}[1+8e^{\beta \delta (2+\mathrm{ln}^1(\delta /\mathrm{\Delta }_0))}].$$
(12)   
The paramagnetic contribution from the single spin dominates at all temperatures below $`\delta `$. Compared to the case of a normal metallic grain, the odd susceptibility is non-monotonous: upon lowering temperature, $`\chi _o`$ first decreases due to superconducting fluctuations; at temperatures $`T\delta `$ a re-entrant behavior sets in which persists down to the lowest temperatures.

Reentrant susceptibility. The various limiting cases discussed so far provide evidence for the appearance of an anomaly in the spin susceptibility $`\chi _o`$. For large grains ($`\mathrm{\Delta }\delta `$) the mean field approximation, Eq.(5), leads to the re-entrant behaviour shown in Fig. 1. We will show that this is a unique signature of pairing correlations which is present even in ultrasmall grains. To this end we study the complete temperature dependence of $`\chi _{e/o}`$ for arbitrary values of the ratio $`\delta /\mathrm{\Delta }_0`$.

The physics of re-entrant susceptibility can be grasped by evaluating Eq. (4), in the static path approximation . This amounts in retaining only the static fluctuations (beyond the Gaussian approximation) in the path integral. In Figs. 2 and 3 we show the results of this calculation for the odd and the even cases respectively. The re-entrance in the odd case is visible even in systems with a ratio $`\delta /\mathrm{\Delta }_050`$ (!) and provides the signature of the existance of pairing correlations in the ultrasmall regime. Frequency dependent fluctuations will further enhance the size of the reentrant effect. The results are plotted for a system of $`N=200`$ electrons at half filling and the BCS coupling is chosen to fix the ratio $`\delta /\mathrm{\Delta }`$ ($`\lambda 0.10.2`$). The merit of the static path approximation combined with the analytic analysis in the limiting cases is that it allows to obtain a coherent quantitative physical picture in the whole temperature range.

As a final check of our results we computed $`\chi _o`$ using the exact solution of Ref. . The result is presented in Fig.2 (dashed lines). As expected, the re-entrant effect is slightly larger ($`15`$%). In order to obtain this result we considered all the different states with excitation energy up to a cutoff $`\mathrm{\Lambda }40\delta `$ for a system with $`N100`$ electrons. In the inset we show the scaling analysis for different $`N`$ and different energy cutoffs. This analysis becomes more and more difficult upon increasing temperature because of the exponential increase of the number of excited states needed.

In this Letter we proposed the study of the spin susceptibility of a metallic grain as a very sensitive probe to detect superconducting correlations. For grains in the nanometer size regime the odd spin susceptibility is a unique signature of pairing. In grains of dimensions of the order of few nanometers as those studied in Refs.  the reentrance should be of the order of $`1020`$% of the Pauli value and it could be measured using the techinque used in Ref. .

Acknowledgments We thank I. Aleiner, I. Beloborodov, A. Larkin, and B. Mühlschlegel for useful discussions. We acknowledge the financial support of European Community (Contract FMRX-CT-97-0143), SFB237 of the Deutsche Forschungsgemeinschaft and INFM-PRA-QTMD.