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# Orbital effect of Cooper pairs on Kondo effect in unconventional superconductors

## I introduction

The search for variety in the Kondo effect was stimulated by the discovery of the non-Fermi liquid behavior in heavy fermion materials and by the observation of the two-level system character in metallic glasses and nanoscale devices. In these cases, orbital degrees of freedom are very important as well as spin.  Due to incomplete compensation of a local moment, it displays singular behavior in physical quantities, differing from the ordinary single-channel Kondo effect. This Kondo problem has been investigated mainly for metallic systems with no gap in the density of states.

For a gapped system, the problem of a magnetic impurity in a $`s`$-wave superconductor has been investigated for a long time.  Since the $`s`$-wave property is described by a single channel, the Kondo effect itself is understood in the framework of the conventional theory based on the single-channel Kondo model. On the other hand, no one has paid attention to multichannel properties of $`p`$-wave and $`d`$-wave superconductors derived from angular momenta of their Cooper pairs. They can exhibit a new type of Kondo effect peculiar to the unconventional superconductivity.

The unconventional superconductivity is very sensitive to impurities and surface boundaries. It displays peculiar phenomena not observed in the $`s`$-wave superconductivity. It is known that scattering objects destroy the unconventional superconductivity and induce bound states.  The nuclear magnetic resonance (NMR) $`T_1^1`$ measurement performed in Zn-doped YBa2Cu3O7-δ showed a constant $`T_1T`$ at low temperatures  reflecting finite density of states at lower energies. As shown by the low temperature scanning tunnel microscope (STM), a single Zn atom actually generates the low energy bound state.  For the $`d_{x^2y^2}`$-wave, the (1,1,0) surface is regarded as the pair-breaking boundary.  A very recent experiment showed a zero energy peak in the tunneling conductance between the (1,1,0) boundary of YBa2Cu3O7-δ and a normal metal.  Thus much attention has been paid to the effects of non-magnetic impurities and static boundaries in the last decade.

Recently the effect of magnetic impurities in unconventional superconductors has attracted attention gradually with the development of experimental studies. According to the NMR experiments,  a local moment is induced around a Zn site substituted for a Cu site in YBa2Cu3O7-δ. It is expected that the observed Kondo behavior is due to this moment.  Similar behavior is also observed in Li-substituted YBa2Cu3O7-δ.  In this case, the local magnetic susceptibility of the Li induced moment shows strong reduction of the Kondo screening below the superconducting transition temperature. At present the search for the influence of unconventional superconductivity on the Kondo effect is still in progress. We are also interested in the Kondo effect for different types of superconductors other than such high-$`T_\mathrm{c}`$ cuprates.

Several studies of a magnetic impurity in a conventional ($`s`$-wave) superconductor clarified how a bound state generated around the impurity depends on the Kondo temperature $`T_\mathrm{K}`$ and the superconducting energy gap $`\mathrm{\Delta }`$.  The numerical renormalization group (NRG) study by Satori et al.  showed that the bound state energy is scaled by $`T_\mathrm{K}/\mathrm{\Delta }`$ and the interchange of singlet and doublet ground states occurs smoothly. Even if an energy gap exists in the density of quasiparticle states, a local spin couples with the quasiparticles antiferromagnetically to form a spin singlet (Kondo singlet) for $`T_\mathrm{K}/\mathrm{\Delta }>0.3`$. A similar competition was discussed in gapless $`d_{x^2y^2}`$-wave superconductors such as high $`T_\mathrm{c}`$ cuprates.  In this case, the gapless density of states stabilizes the Kondo singlet more favorably than in the gapped $`s`$-wave case. However, it is not certain that a singlet ground state is always realized in all types of superconductors when the Kondo effect is strong enough. A Cooper pair in the unconventional superconductivity has an angular momentum and can produce multichannel scattering of quasiparticles at an impurity. As well as for metals, a difference between single channel and multichannel properties in the Kondo effect can be expected for superconductors.

In order to elucidate the multichannel property, we study the Kondo effect due to a local spin coupled to a $`p_x+ip_y`$ (or $`d_{x^2y^2}+id_{xy}`$)-wave superconducting state. The $`𝒅`$-vector for the $`p_x+ip_y`$-wave is given by $`𝒅_𝒌=\widehat{z}(k_x+ik_y)`$ where $`\widehat{z}`$ is a unit vector in the z axis. Since the density of states has a full gap like the $`s`$-wave case, we can find the peculiarity of the unconventional superconductivity in comparison with the $`s`$-wave. The property of the $`p_x+ip_y`$ superconductivity is analogous to that of the A phase found in the superfluid 3He. A lot of attention has been paid to this superconductivity since the discovery of the spin triplet superconductor Sr2RuO4.  The recent theoretical studies proposed a number of unique physics associated with the broken time reversal symmetry observed by the $`\mu `$SR experiment.  In the $`p_x+ip_y`$-wave superconductor, spontaneous current appears close to the scattering objects and it induces a finite magnetic field.  This argument explains the $`\mu `$SR data well.  If the system induces the spontaneous magnetic field by itself, a spontaneous Hall effect can be expected.  A vortex charging effect is also interesting, peculiar to the rotating Cooper pairs.

The most important point in this paper is that for the $`p_x+ip_y`$-wave case one of the Cooper pairing electrons is coupled to a local spin and the other has no direct coupling with the local spin. As we will discuss later, the latter can interact with the local spin through the superconducting order parameter. We use the NRG method  to study this new type of two-channel Kondo effect. As for the $`s`$-wave case, we discretize the bare conduction band logarithmically and apply the Bogoliubov transformation to obtain a diagonal form of NRG Hamiltonian for the superconductivity. In the NRG Hamiltonian, the two independent channels consisting of the $`l=0`$ and $`l=1`$ orbitals are coupled to each other at the impurity. The NRG result shows that the ground state is a spin doublet over all the $`T_\mathrm{K}/\mathrm{\Delta }`$ region and $`T_\mathrm{K}/\mathrm{\Delta }`$ dependence of a bound state expresses a competition between the Kondo effect and the superconducting energy gap. The solution of the strong coupling limit ($`T_\mathrm{K}/\mathrm{\Delta }\mathrm{}`$) shows that the ground state is a spin doublet due to dynamical coupling between the $`l=0`$ and $`l=1`$ electrons, while the local spin is almost quenched by the $`l=0`$ electrons.

This paper is organized as follows. In Sec. II we derive the NRG Hamiltonian to investigate the two-channel Kondo effect specific to the $`p_x+ip_y`$ (or $`d_{x^2y^2}+id_{xy}`$)-wave superconductivity. Here the origin of the two channels is explained thoroughly. In Sec. III we show the NRG results in comparison with the $`s`$-wave case. We also calculate a local spin susceptibility and discuss the Ising case. It is very useful to understand the quantum effect of the magnetic impurity in the gapped electron system. This paper is closed with concluding remarks in Sec. IV.

## II Formulation

In this section we derive the NRG Hamiltonian for the Kondo effect in the $`p_x+ip_y`$-wave ($`d_{x^2y^2}+id_{xy}`$-wave) superconductor. Here we study a single magnetic impurity at the center in two-dimensional superconducting systems.

### A Model Hamiltonian

Let us begin with the following Hamiltonian:

$`H=H_{\mathrm{kin}}+H_\mathrm{\Delta }+H_{\mathrm{imp}},`$ (2)
$`H_{\mathrm{kin}}={\displaystyle \underset{𝒌\sigma }{}}\epsilon _𝒌a_{𝒌\sigma }^{}a_{𝒌\sigma },`$ (3)
$`H_\mathrm{\Delta }={\displaystyle \underset{𝒌}{}}(\mathrm{\Delta }_𝒌a_𝒌^{}a_𝒌^{}+\mathrm{H}.\mathrm{c}.),`$ (4)
$`H_{\mathrm{imp}}={\displaystyle \frac{1}{2}}{\displaystyle \underset{𝒌𝒌^{}\sigma \sigma ^{}}{}}\left(J𝑺𝝈_{\sigma \sigma ^{}}+V\delta _{\sigma ,\sigma ^{}}\right)a_{𝒌\sigma }^{}a_{𝒌^{}\sigma ^{}}.`$ (5)
Here $`𝒌`$ and $`\sigma `$ represent the wave vector and spin of the conduction electrons, respectively. $`a_{𝒌\sigma }`$ is the annihilation operator of the conduction electron, $`ϵ_𝒌`$ is the kinetic energy of the conduction electron, and $`\mathrm{\Delta }_𝒌`$ is the momentum dependent order parameter. $`𝑺`$ expresses the $`S=1/2`$ spin operator for the magnetic impurity, and $`𝝈`$ is the Pauli matrix for the conduction electrons. $`J(<0)`$ and $`V`$ are the antiferromagnetic and non-magnetic couplings, respectively. Here we have assumed a short-range ($`s`$-wave) scattering impurity. For the $`p_x+ip_y`$-wave pairing state, the order parameter has a form of $`\mathrm{\Delta }_𝒌=\mathrm{\Delta }e^{i\varphi _k}`$. Here $`\mathrm{\Delta }`$ is the order parameter which we assume a real number, and $`\varphi _k`$ is the angle of the wave vector measured from the $`k_x`$ axis. Since the orbital angular momentum is a good quantum number for the $`p_x+ip_y`$-wave, it is convenient to transform the wave vector representation into the following two-dimensional polar coordinate representation:

$$a_{𝒌\sigma }=\underset{l}{}(i)^l|J_{l+1}(kR)|e^{il\varphi _k}a_{kl\sigma },$$
(6)
where $`J_l`$ is the $`l`$-th Bessel function, and $`R`$ is the radius of the two-dimensional system. $`l`$ is the $`z`$-component of the orbital angular momentum of the conduction electron. Substituting Eq. (6) into Eq. (II A), we obtain

$`H=B\left(\overline{H}_{\mathrm{kin}}+\overline{H}_\mathrm{\Delta }+\overline{H}_{\mathrm{imp}}\right),`$ (8)
$`\overline{H}_{\mathrm{kin}}={\displaystyle _1^1}𝑑kk{\displaystyle \underset{l\sigma }{}}a_{kl\sigma }^{}a_{kl\sigma },`$ (9)
$`\overline{H}_\mathrm{\Delta }={\displaystyle _1^1}dk{\displaystyle \underset{l}{}}(1)^{1l}(i\overline{\mathrm{\Delta }}a_{kl}^{}a_{k,l+1,}^{}+\mathrm{H}.\mathrm{c}.),`$ (10)
$`\overline{H}_{\mathrm{imp}}={\displaystyle \underset{\sigma \sigma ^{}}{}}\left(\overline{J}𝑺𝝈_{\sigma \sigma ^{}}+\overline{V}\delta _{\sigma ,\sigma ^{}}\right)f_{00\sigma }^{}f_{00\sigma ^{}},`$ (11)
$`f_{00\sigma }={\displaystyle \frac{1}{\sqrt{2}}}{\displaystyle _1^1}𝑑ka_{k,l=0,\sigma },`$ (12)
where $`B=k_\mathrm{F}^3R/(\pi m)=2k_\mathrm{F}RE_\mathrm{F}/\pi `$, $`\overline{\mathrm{\Delta }}=\mathrm{\Delta }/(2E_\mathrm{F})`$, $`\overline{J}=J\rho `$, $`\overline{V}=V\rho `$. Here $`E_\mathrm{F}=k_\mathrm{F}^2/(2m)`$ is the Fermi energy, and $`\rho =mR^2/2=(k_\mathrm{F}R)^2/(4E_\mathrm{F})`$ is the density of states at the Fermi energy for the two-dimensional conduction band. In Eq. (II A) we have used the following asymptotic form of the Bessel function: $`J_l(kR)\sqrt{2/(\pi kR)}`$ (for a large $`kR`$). The wave number $`k`$ in Eq. (II A) is normalized by $`k_\mathrm{F}`$. The kinetic energy of the conduction electron is linearized near the Fermi energy. For simplicity, we have used the same values for both the superconducting cutoff energy and the band width $`k_\mathrm{F}`$, since it is assured that this does not alter the results.  The fermion represented by the operator $`f_{00\sigma }`$ corresponds to a fermion localized at the impurity. The first subscript $`0`$ of $`f_{00\sigma }`$ represents the 0-th shell of the NRG Hamiltonian which will be derived later (see Appendix). The second zero means the $`l=0`$ orbital. Notice that the angular momentum of the $`p_x+ip_y`$-wave Cooper pair equals to one (see $`\overline{H}_\mathrm{\Delta }`$), and that the $`l=0`$ and $`l=1`$ orbitals are coupled. Since the angular momentum is a good quantum number for the $`p_x+ip_y`$-wave, both orbitals are decoupled from the other orbitals. Due to the short-range ($`s`$-wave) scattering, the electrons only in the $`l=0`$ orbital couple with the impurity. The electrons in the $`l=1`$ orbital can also interact with the impurity via the $`p_x+ip_y`$-wave order parameter. It is sufficient to choose only the $`l=0`$ and $`l=1`$ orbitals in Eq. (II A) to study the Kondo effect for the $`p_x+ip_y`$-wave state. Therefore we can apply the NRG method to this Kondo problem as we do to the two-channel Kondo problem.  We rewrite then $`\overline{H}_{\mathrm{kin}}`$ and $`\overline{H}_\mathrm{\Delta }`$ as

$`\overline{H}_{\mathrm{kin}}={\displaystyle _1^1}𝑑kk{\displaystyle \underset{\sigma }{}}\left(a_{k0\sigma }^{}a_{k0\sigma }+a_{k1\sigma }^{}a_{k1\sigma }\right),`$ (14)
$`\overline{H}_\mathrm{\Delta }={\displaystyle _1^1}dk{\displaystyle \underset{\sigma }{}}(i\overline{\mathrm{\Delta }}a_{k1\sigma }^{}a_{k0,\sigma }^{}+\mathrm{H}.\mathrm{c}.).`$ (15)
We can obtain a similar $`\overline{H}_\mathrm{\Delta }`$ for a $`d_{x^2y^2}+id_{xy}`$-wave if we replace $`i\overline{\mathrm{\Delta }}`$ by $`\sigma \overline{\mathrm{\Delta }}`$ and $`l=1`$ by $`l=2`$, since the order parameter for the $`d_{x^2y^2}+id_{xy}`$-wave has a form of $`\mathrm{\Delta }_𝒌=\mathrm{\Delta }e^{i2\varphi _k}`$.

### B Transformation of the Hamiltonian

In our formulation we follow the procedure by Sakai et al.  and derive a NRG Hamiltonian. There is another way to derive the Hamiltonian,  which we describe in Appendix. First we diagonalize the conduction electron part by introducing the following Bogoliubov transformation:

$`a_{k0\sigma }=u_k\alpha _{k,+,\sigma }v_k^{}\alpha _{k,,\sigma }^{},`$ (17)
$`a_{k1\sigma }=u_k\alpha _{k,,\sigma }+v_k^{}\alpha _{k,+,\sigma }^{}.`$ (18)
Here $`\alpha _{k,\tau =\pm ,\sigma }`$ is the annihilation operator for the superconducting quasiparticle with $`\sigma `$ spin in $`\tau `$ channel. The coefficients $`u_k`$ and $`v_k`$ are defined by

$`u_k=\sqrt{{\displaystyle \frac{1}{2}}(1+{\displaystyle \frac{|k|}{E_k}})},`$ (20)
$`v_k=i\sqrt{{\displaystyle \frac{1}{2}}(1{\displaystyle \frac{|k|}{E_k}})}\mathrm{sgn}(k),`$ (21)
where $`E_k=(k^2+\overline{\mathrm{\Delta }}^2)^{1/2}`$ is the energy of the quasiparticles. The $`p_x+ip_y`$-wave Hamiltonian is then expressed in terms of the superconducting quasiparticle as

$`\overline{H}_{p_x+ip_y}=\overline{H}_{\mathrm{kin}}+\overline{H}_\mathrm{\Delta }`$ (22)
$`={\displaystyle _1^1}𝑑kE_k\mathrm{sgn}(k){\displaystyle \underset{\tau =\pm ,\sigma }{}}\alpha _{k\tau \sigma }^{}\alpha _{k\tau \sigma }.`$ (23)
For the later convenience, we introduce the following transformations:

$`\beta _{|k|,\tau ,\sigma }^{}=\alpha _{|k|,\tau ,\sigma },`$ (25)
$`A_{k\tau \sigma }={\displaystyle \frac{1}{\sqrt{2}}}\left(\alpha _{k\tau \sigma }i\tau \beta _{k\tau \sigma }\right),`$ (26)
$`B_{k\tau \sigma }={\displaystyle \frac{1}{\sqrt{2}}}\left(\alpha _{k\tau \sigma }+i\tau \beta _{k\tau \sigma }\right),`$ (27)
$`C_{+,\sigma }(k)=A_{k,+,\sigma },`$ (28)
$`C_{+,\sigma }(k)=iB_{k,,\sigma }^{},`$ (29)
$`C_{,\sigma }(k)=iA_{k,,\sigma }^{},`$ (30)
$`C_{,\sigma }(k)=B_{k,+,\sigma }.`$ (31)
The Hamiltonian (23) can be expressed by the above $`C`$ operators as

$$\overline{H}_{p_x+ip_y}=_0^1𝑑kE_k\underset{s=\pm ,\tau ,\sigma }{}\tau sC_{\tau \sigma }^{}(sk)C_{\tau \sigma }(sk).$$
(32)
For the impurity part, the operator $`f_{00\sigma }`$ is also expressed in terms of the superconducting quasiparticle as

$`f_{00\sigma }={\displaystyle \frac{1}{\sqrt{2}}}{\displaystyle _0^1}dk[u_k(\alpha _{k+\sigma }+\beta _{k,\sigma }^{})`$ (34)
$`v_k^{}(\alpha _{k,\sigma }^{}\beta _{k+,\sigma })]`$ (35)
$`={\displaystyle \frac{1}{\sqrt{2}}}{\displaystyle _0^1}dk[w_{k+}(A_{k+\sigma }+iA_{k,\sigma }^{})`$ (36)
$`+w_k(B_{k+\sigma }iB_{k,\sigma }^{})],`$ (37)
$`w_{k,\pm }=\sqrt{{\displaystyle \frac{1}{2}}\left(1\pm {\displaystyle \frac{|\overline{\mathrm{\Delta }}|}{E_k}}\right)}.`$ (38)
By introducing the following operators

$`a_{\tau ,\sigma }=N_+^1{\displaystyle _0^1}𝑑kw_{k+}A_{k,\tau ,\sigma },`$ (40)
$`b_{\tau ,\sigma }=N_{}^1{\displaystyle _0^1}𝑑kw_kB_{k,\tau ,\sigma },`$ (41)
$`N_\pm =\left({\displaystyle _0^1}𝑑kw_{k\pm }^2\right)^{1/2},`$ (42)
$`f_{00\sigma }`$ is expressed as

$`f_{00\sigma }={\displaystyle \frac{1}{\sqrt{2}}}[N_+a_{+,\sigma }iN_{}b_{,\sigma }^{}`$ (43)
$`+i(N_+a_{,\sigma }^{}iN_{}b_{+,\sigma }^{})]`$ (44)
$`={\displaystyle \frac{1}{\sqrt{2}}}\left(c_{0,+,\sigma }+c_{0,,\sigma }\right),`$ (45)
where $`c_{0,\tau ,\sigma }`$ is defined by

$`c_{0,+,\sigma }=N_+a_{+,\sigma }iN_{}b_{,\sigma }^{}`$ (47)
$`={\displaystyle _0^1}𝑑k\left(w_{k+}A_{k,+,\sigma }iw_kB_{k,,\sigma }^{}\right)`$ (48)
$`={\displaystyle _0^1}𝑑k{\displaystyle \underset{s=\pm }{}}w_{k,s}C_{+,\sigma }(sk),`$ (49)
$`c_{0,,\sigma }=i\left(N_+a_{,\sigma }^{}iN_{}b_{+,\sigma }\right)`$ (50)
$`={\displaystyle _0^1}𝑑k\left(w_{k+}iA_{k,,\sigma }^{}+w_kB_{k,+,\sigma }\right)`$ (51)
$`={\displaystyle _0^1}𝑑k{\displaystyle \underset{s=\pm }{}}w_{k,s}C_{,\sigma }(sk).`$ (52)
The exchange Hamiltonian $`\overline{H}_{\mathrm{imp}}`$ is then written as

$$\overline{H}_{\mathrm{imp}}=\frac{1}{2}\underset{\tau \tau ^{}\sigma \sigma ^{}}{}\left(\overline{J}𝑺𝝈_{\sigma \sigma ^{}}+\overline{V}\delta _{\sigma ,\sigma ^{}}\right)c_{0\tau \sigma }^{}c_{0\tau ^{}\sigma ^{}}.$$
(53)
In Eq. (53), the subscript $`\tau =\pm `$ represents the two channels, both of which consists of the $`l=0`$ and $`l=1`$ orbitals. While the impurity interacts with only the $`l=0`$ electron, Eq. (53) contains the channel-flip ($`_{\tau \tau ^{}}`$) terms. This is because the operator $`f_{00\sigma }`$ is expressed as Eq. (45). The two-channel property in Eq. (53) originates from the angular momentum of the $`p_x+ip_y`$-wave Cooper pair. In order to treat the Kondo problem in the superconducting state, first we have diagonalized the Hamiltonian of the conduction electron part. The diagonalized representation ($`\tau `$ representation) in this Hamiltonian is given by the linear combination of the $`l=0`$ and $`l=1`$ orbitals, since the $`p_x+ip_y`$-wave mixes the two orbitals. It is natural that the impurity part of the Hamiltonian contains the channel-flip part in the $`\tau `$ representation.

In contrast to the present $`p_x+ip_y`$-wave case, the standard two-channel Kondo model was derived from the internal degrees of freedom of the impurity atom.  In our model, the impurity does not have such internal degrees of freedom except for the $`S=1/2`$ spin. However, we can obtain the two-channel property due to the orbital effect of the Cooper pairs. Therefore the present two-channel property for the $`p_x+ip_y`$-wave can provide new Kondo physics peculiar to the unconventional superconductors.

### C Discretization

Following Wilson’s procedure, we discretize the conduction band with a logarithmic mesh in the $`k`$ space. The Hamiltonian for the discretized conduction band is written as

$`\overline{H}_{p_x+ip_y}={\displaystyle \underset{m=0}{\overset{\mathrm{}}{}}}{\displaystyle \underset{\tau \sigma s}{}}\tau sE_mC_{\tau \sigma }^{}(sm)C_{\tau \sigma }(sm),`$ (55)
$`E_m=\sqrt{k_m^2+\overline{\mathrm{\Delta }}^2},`$ (56)
$`k_m=(1+\mathrm{\Lambda }^1)\mathrm{\Lambda }^m/2,`$ (57)
where $`\mathrm{\Lambda }>1`$ is the discretization parameter. The above $`C`$ operators satisfies the Fermion commutation relation:

$$\{C_{\tau \sigma }(sm),C_{\tau ^{}\sigma ^{}}^{}(s^{}m^{})\}=\delta _{\tau ,\tau ^{}}\delta _{\sigma ,\sigma ^{}}\delta _{s,s^{}}\delta _{m,m^{}}.$$
(58)
The fermion operator for the localized orbit (the 0-th shell orbit) $`c_{0\tau \sigma }`$ is also expressed with the $`C`$ operators as

$`c_{0\tau \sigma }=(1\mathrm{\Lambda }^1)^{1/2}{\displaystyle \underset{sm}{}}w_{ms}\mathrm{\Lambda }^{m/2}C_{\tau \sigma }(sm),`$ (60)
$`w_{ms}=\sqrt{(1+s{\displaystyle \frac{\overline{\mathrm{\Delta }}}{E_m}})/2}.`$ (61)
We define $`c_{n\tau \sigma }`$ for the n-th shell orbit and satisfies the following commutation relation:

$`[c_{n\tau \sigma },\overline{H}_{p_x+ip_y}]`$ $`=`$ $`t_{n1}c_{n1,\tau \sigma }+\tau \eta _nc_{n\tau \sigma }`$ (62)
$`+`$ $`t_nc_{n+1,\tau \sigma }.`$ (63)
For $`n=0`$ we have

$`[c_{0\tau \sigma },\overline{H}_{p_x+ip_y}]`$ $`=`$ $`(1\mathrm{\Lambda }^1)^{1/2}`$ (65)
$`\times {\displaystyle \underset{sm}{}}w_{ms}\mathrm{\Lambda }^{m/2}\tau sE_mC_{\tau \sigma }(sm)`$
$`=`$ $`\tau \eta _0c_{0\tau \sigma }+t_0c_{1\tau \sigma },`$ (66)
where $`\eta _0`$, $`t_0`$, and $`c_{1\tau \sigma }`$ are defined by

$`\eta _0=(1\mathrm{\Lambda }^1){\displaystyle \underset{sm}{}}w_{ms}^2\mathrm{\Lambda }^msE_m,`$ (68)
$`t_0=\left[(1\mathrm{\Lambda }^1){\displaystyle \underset{sm}{}}w_{sm}^2\mathrm{\Lambda }^m(sE_m\eta _0)^2\right]^{1/2},`$ (69)
$`c_{1\tau \sigma }=\tau {\displaystyle \frac{(1\mathrm{\Lambda }^1)^{1/2}}{t_0}}`$ (70)
$`\times {\displaystyle \underset{sm}{}}w_{sm}\mathrm{\Lambda }^{m/2}(sE_m\eta _0)C_{\tau \sigma }(sm).`$ (71)
Repeating this procedure, we obtain the total Hamiltonian which has the following hopping type with staggered potentials:

$`\overline{H}=\overline{H}_{p_x+ip_y}+\overline{H}_{\mathrm{imp}},`$ (73)
$`\overline{H}_{p_x+ip_y}={\displaystyle \underset{n\tau \sigma }{}}[\tau \eta _nc_{n\tau \sigma }^{}c_{n\tau \sigma }`$ (74)
$`+t_n(c_{n+1,\tau \sigma }^{}c_{n\tau \sigma }+c_{n,\tau \sigma }^{}c_{n+1,\tau \sigma })],`$ (75)
$`\overline{H}_{\mathrm{imp}}={\displaystyle \frac{1}{2}}{\displaystyle \underset{\tau \tau ^{}\sigma \sigma ^{}}{}}\left(\overline{J}𝑺𝝈_{\sigma \sigma ^{}}+\overline{V}\delta _{\sigma ,\sigma ^{}}\right)c_{0\tau \sigma }^{}c_{0\tau ^{}\sigma ^{}}.`$ (76)
Here $`\eta _n`$ and $`t_n`$ are given by

$`\eta _n=(1)^n\overline{\mathrm{\Delta }},`$ (78)
$`t_n={\displaystyle \frac{(1+\mathrm{\Lambda }^1)}{2}}\epsilon _n\mathrm{\Lambda }^{n/2},`$ (79)
$`\epsilon _n=\left[1\mathrm{\Lambda }^{(n+1)}\right]\left[1\mathrm{\Lambda }^{(2n+1)}\right]^{1/2}`$ (80)
$`\times \left[1\mathrm{\Lambda }^{(2n+3)}\right]^{1/2}.`$ (81)
In the practical calculation, we use the following scaled Hamiltonian in a recursion relation given by

$`H_{N+1}=\mathrm{\Lambda }^{1/2}H_N+{\displaystyle \underset{\tau \sigma }{}}[\epsilon _N(c_{N+1,\tau \sigma }^{}c_{N\tau \sigma }+\mathrm{H}.\mathrm{c}.)`$ (83)
$`+(1)^N\mathrm{\Lambda }^{N/2}\tau \stackrel{~}{\mathrm{\Delta }}c_{N+1,\tau \sigma }^{}c_{N+1,\tau \sigma }],`$ (84)
$`H_0=[{\displaystyle \frac{1}{2}}{\displaystyle \underset{\tau \tau ^{}\sigma \sigma ^{}}{}}(\stackrel{~}{J}𝑺𝝈_{\sigma \sigma ^{}}+\stackrel{~}{V}\delta _{\sigma ,\sigma ^{}})c_{0\tau \sigma }^{}c_{0\tau ^{}\sigma ^{}}`$ (85)
$`{\displaystyle \underset{\tau \sigma }{}}\tau \stackrel{~}{\mathrm{\Delta }}c_{0\tau \sigma }^{}c_{0\tau \sigma }]\mathrm{\Lambda }^{1/2}.`$ (86)
Here the parameters are defined by

$`\stackrel{~}{\mathrm{\Delta }}={\displaystyle \frac{\overline{\mathrm{\Delta }}}{(1+\mathrm{\Lambda }^1)/2}},`$ (87)
$`\stackrel{~}{J}={\displaystyle \frac{\overline{J}}{(1+\mathrm{\Lambda }^1)/2}},`$ (88)
$`\stackrel{~}{V}={\displaystyle \frac{\overline{V}}{(1+\mathrm{\Lambda }^1)/2}}.`$ (89)
The Hamiltonian (II C) is related to $`H_N`$ and is given by

$$\overline{H}=\frac{1+\mathrm{\Lambda }^1}{2}\underset{N\mathrm{}}{lim}\mathrm{\Lambda }^{(N1)/2}H_N.$$
(90)
In Eq. (II C), $`c_{N\tau \sigma }`$ is an operator of the NRG fermion quasiparticle in the $`N`$-th shell. The subscript $`\tau =\pm `$ represents the two channels which are constructed by the $`l=0`$ and $`l=1`$ orbitals as discussed in the last part of the previous subsection. We can obtain the same NRG Hamiltonian for a $`d_{x2y^2}+id_{xy}`$-wave. In order to check reliability of numerical results, we compare different data by changing cutoff of the eigenstates and the discretization parameter $`\mathrm{\Lambda }`$. In the NRG results we show throughout this paper, we keep the lowest-lying $`500`$ states at each renormalization step and take $`\mathrm{\Lambda }=3`$. For calculating a local spin susceptibility, we keep $`1200`$ states to reduce the cutoff dependence.

## III Kondo Effect in $`p`$-wave Superconductor

In this section we present our results for the Kondo effect in the $`p_x+ip_y`$-wave superconducting state. We show numerical results and then discuss the strong coupling limit to see how the orbital dynamics of the Cooper pairs affects the Kondo singlet.

### A Numerical results

First we discuss a $`\stackrel{~}{\mathrm{\Delta }}=0`$ case where the only $`l=0`$ electrons couple with the local spin and the $`l=1`$ electrons are free from the impurity. The NRG result shows that the Kondo singlet is realized by the relevant $`l=0`$ electrons at the stable fixed point. This fixed point is of strong coupling type ($`|\stackrel{~}{J}|\mathrm{}`$) and the fixed-point NRG energy levels is reproduced by truncating the $`N=0`$ site (impurity site) from the $`l=0`$ chain of the conduction electrons.  On the other hand, the fixed point for $`l=1`$ is of free-electron type ($`\stackrel{~}{J}=0`$). One of the two chains produces a zero energy state in one-particle energy levels at the fixed point. We can fill at most two particles (spin up and down) into the zero energy state and we have quartet ground state for $`\stackrel{~}{\mathrm{\Delta }}=0`$.

Next we discuss a $`\stackrel{~}{J}=\stackrel{~}{V}=0`$ case with finite $`\stackrel{~}{\mathrm{\Delta }}`$. In this case, the NRG Hamiltonian (II C) consists of the two independent $`\tau =\pm `$ channels related to the superconducting state. The Hamiltonian of each channel is same as that of the free $`s`$-wave superconductivity.  At the odd renormalization steps, one-particle energy level for the free $`s`$-wave is particle-hole symmetric. At the even steps, there is an additional one-particle energy level which is hole-like (particle-like) for a positive (negative) $`\stackrel{~}{\mathrm{\Delta }}`$. In the present $`p_x+ip_y`$-wave case, one particle energy level is symmetric at all the renormalization steps, since the signs of $`\stackrel{~}{\mathrm{\Delta }}`$ for the $`\tau =\pm `$ channels are different each other. In one-particle energy levels, there is no zero energy state due to the finite $`\stackrel{~}{\mathrm{\Delta }}`$. The ground state is obtained by filling particles into the energy levels and we have a single ground state.

Let us turn to the Kondo problem in the $`p_x+ip_y`$-wave state. In this case both $`\stackrel{~}{\mathrm{\Delta }}`$ and $`\stackrel{~}{J}`$ are finite. Since $`\stackrel{~}{J}`$ grows up as $`\mathrm{\Lambda }^{N/2}`$ with increasing $`N`$, it is relevant in the Kondo effect. In addition, $`\stackrel{~}{\mathrm{\Delta }}`$ is also relevant since it grows as in Eq. (II C). Therefore we can expect a competition between the Kondo effect and the superconductivity.  As the renormalization step increases, the excited state energies increase with $`\stackrel{~}{\mathrm{\Delta }}_N\mathrm{\Lambda }^{N/2}`$, which is the energy gap at the $`N`$-th renormalization step. Since the magnetic impurity can destroy the superconductivity, we have bound states below $`\stackrel{~}{\mathrm{\Delta }}_N`$. The ratio of the bound state energy and $`\stackrel{~}{\mathrm{\Delta }}_N`$ approaches a constant value with the increase of the renormalization step. We express the convergent value of the ratio by $`(E_\mathrm{B}/\mathrm{\Delta })^{}`$. Figure 1 shows the $`T_\mathrm{K}/\mathrm{\Delta }`$ dependence of the first excited state (bound state) for $`\stackrel{~}{V}=0`$, where the Kondo temperature is defined by

$$T_\mathrm{K}=\sqrt{|\overline{J}|}\mathrm{exp}(1/|\overline{J}|).$$
(91)
Here, a unit of the energy is taken to be the band width $`2E_\mathrm{F}`$. We find that the bound state energy level is scaled by $`T_\mathrm{K}/\mathrm{\Delta }`$ as in the $`s`$-wave case. In a small $`T_\mathrm{K}/\mathrm{\Delta }`$ region, the ground state is a spin doublet as expected, and the first excited state is a particle-hole doublet with no spin. With the increase of $`T_\mathrm{K}/\mathrm{\Delta }`$, the energy level of the bound state (the first excited state) decreases (see Fig. 1). As $`T_\mathrm{K}/\mathrm{\Delta }\mathrm{}`$, it approaches the ground state energy and the ground state is four-fold degenerate. The result for $`T_\mathrm{K}/\mathrm{\Delta }\mathrm{}`$ is connected smoothly to that for $`\mathrm{\Delta }=0`$.

The most important point in Fig. 1 is that the ground state is always a spin doublet. This means that the spin of the ground state survives even in the strong coupling limit for the $`p_x+ip_y`$-wave superconductivity. In the $`s`$-wave case, the Kondo singlet is realized in the large $`T_\mathrm{K}/\mathrm{\Delta }`$ region , resulting in a spin singlet ground state. Thus the Kondo effect for the $`p_x+ip_y`$-wave is quite different from that for the conventional $`s`$-wave.

While the ground state is always a spin doublet for the $`p_x+ip_y`$-wave, we find that the $`T_\mathrm{K}/\mathrm{\Delta }`$ dependence of the bound state energy level is very similar to that of the $`s`$-wave. For the $`s`$-wave, the Kondo singlet is realized in $`T_\mathrm{K}/\mathrm{\Delta }>0.3`$ region against the superconducting energy gap.  In Fig. 1, the curvature of the $`(E_\mathrm{B}/\mathrm{\Delta })^{}`$ curve found around $`(E_\mathrm{B}/\mathrm{\Delta })^{}=0.5`$ is very similar to that of the $`s`$-wave case found with the interchange of the ground state. This represents a crossover from the $`\mathrm{\Delta }`$ dominant region to the $`T_\mathrm{K}`$ dominant region. It occurs around $`T_\mathrm{K}/\mathrm{\Delta }=0.3`$ as in the $`s`$-wave case. Thus the Kondo effect can overcome the energy gap also in the $`p_x+ip_y`$-wave case, although the ground state is still a spin doublet. This means that the competition between the Kondo effect and the energy gap is characterized by such $`T_\mathrm{K}/\mathrm{\Delta }`$ dependence. All the above results hold for the $`d_{x^2y^2}+id_{xy}`$-wave as well, since we can obtain the same NRG Hamiltonian.

Finally, we mention the effect of the potential scattering $`\stackrel{~}{V}`$ in Eq. (II C). It is well known that a single non-magnetic impurity destroys the unconventional superconductivity. It can generate a bound state locally around the impurity. If we treat the magnetic impurity realistically, we have to start from the Anderson model. Since the generalized Kondo model consists of both magnetic and non-magnetic interactions, we have to take both couplings into account. Since the effect of $`\stackrel{~}{V}`$ breaks the particle-hole symmetry, it lifts the degeneracy of the first excited particle-hole doublet. However, the ground state is still a spin doublet and $`\stackrel{~}{V}`$ is irrelevant even if it is large enough.

### B Strong coupling limit

Here we study the mechanism of the spin doublet ground state for the $`p_x+ip_y`$-wave. Let us discuss the strong coupling limit ($`|\stackrel{~}{J}|\mathrm{}`$) case. The Hamiltonian $`H_0`$ in Eq. (II C) can exhibit the solution in this limit. Returning the channel ($`\tau `$) representation to the angular momentum ($`l`$) one, we can rewrite the $`H_0`$ for $`\stackrel{~}{V}=0`$ as

$`H_0=H_{0J}+H_{0\mathrm{\Delta }},`$ (92)
$`H_{0J}=\stackrel{~}{J}{\displaystyle \underset{\sigma \sigma ^{}}{}}𝑺𝝈_{\sigma \sigma ^{}}g_{0\sigma }^{}g_{0\sigma ^{}},`$ (93)
$`H_{0\mathrm{\Delta }}=\stackrel{~}{\mathrm{\Delta }}{\displaystyle \underset{\sigma }{}}(g_{0\sigma }^{}g_{1\sigma }+g_{1\sigma }^{}g_{0\sigma }),`$ (94)
where the following transformation has been used:

$$c_{N=0,\tau ,\sigma }=\frac{1}{\sqrt{2}}\left(g_{l=0,\sigma }+\tau g_{l=1,\sigma }\right).$$
(95)
Here $`g_{l=0,\sigma }`$ and $`g_{l=1,\sigma }`$ correspond to $`f_{00\sigma }`$ and $`f_{01\sigma }^{}`$, respectively. Notice that the order parameter corresponds to the hopping parameter between the $`l=0`$ and $`l=1`$ local orbital sites, since the $`p_x+ip_y`$-wave Cooper pair consists of the $`l=0`$ and $`l=1`$ particles. When $`|\stackrel{~}{J}|\mathrm{}`$, the $`l=0`$ particle couples with the local spin strongly to form a spin singlet $`|s`$:

$$|\mathrm{s}=\frac{1}{\sqrt{2}}\left(g_0^{}|g_0^{}|\right),$$
(96)
where $`|`$ and $`|`$ represent the local spin states. Since the hopping is forbidden, the ground states are 4-fold degenerate for $`|J|\mathrm{}`$:

$`|\mathrm{s}=g_1^{}|\mathrm{s},`$ (97)
$`|\mathrm{s}=g_1^{}|\mathrm{s},`$ (98)
$`|\mathrm{p1}=|s,`$ (99)
$`|\mathrm{p2}=g_1^{}g_1^{}|s,`$ (100)
where $`|\mathrm{s}\sigma `$ ($`\sigma =,`$) and $`|\mathrm{p}i`$ ($`i=1,2`$) are the spin doublet and particle-hole doublet, respectively. At a finite $`|\stackrel{~}{J}|`$, $`\stackrel{~}{\mathrm{\Delta }}`$ in Eq. (94) lifts the degeneracy. The perturbation (the $`\stackrel{~}{\mathrm{\Delta }}`$ term) generates excited states from the ground states in Eq. (100). We show the connection among these states in Fig. 2. One of the particle-hole doublet states is connected to a single excited state. For $`|\mathrm{p1}`$, the excited state is given by \[see Fig. 2 (a)\]:

$$|\mathrm{p1}^{}=\frac{1}{\sqrt{2}}\left(g_1^{}|g_1^{}|\right).$$
(101)
The similar argument holds for $`|\mathrm{p2}`$. We can obtain the following eigenvalue for the particle-hole doublet up to the fourth order of the perturbation:

$$E_{S=0}=\left[\frac{3}{2}\frac{2}{3}\left(\frac{\stackrel{~}{\mathrm{\Delta }}}{|\stackrel{~}{J}|}\right)^2+\frac{8}{27}\left(\frac{\stackrel{~}{\mathrm{\Delta }}}{|\stackrel{~}{J}|}\right)^4\right]|\stackrel{~}{J}|.$$
(102)
For one of the spin doublet states, it is connected to four excited states by the perturbation up to the fourth order. For $`|\mathrm{s}`$, these excited states are given as follows \[see Fig. 2 (b)\]:

$`|0=g_0^{}g_0^{}|,`$ (103)
$`|1=g_1^{}g_1^{}|,`$ (104)
$`|\mathrm{t1}=g_1^{}g_0^{}|,`$ (105)
$`|\mathrm{t2}={\displaystyle \frac{1}{\sqrt{2}}}g_1^{}\left[g_0^{}|+g_0^{}|\right],`$ (106)
and the similar connection is obtained for $`|\mathrm{s}`$ as well. The energy eigenvalue can be obtained from the following equation:

$`e(e1/2)\left[e^3+e^2(4x^2+3/4)e4x^2\right]=0,`$ (107)
$`e=E/|\stackrel{~}{J}|,x=|\stackrel{~}{\mathrm{\Delta }}|/|\stackrel{~}{J}|.`$ (108)
After expanding the lowest $`e`$ in $`x`$ up to the fourth order, we obtain the energy for the spin doublet as

$$E_{S=1/2}=\left[\frac{3}{2}\frac{2}{3}\left(\frac{\stackrel{~}{\mathrm{\Delta }}}{|\stackrel{~}{J}|}\right)^2\frac{10}{27}\left(\frac{\stackrel{~}{\mathrm{\Delta }}}{|\stackrel{~}{J}|}\right)^4\right]|\stackrel{~}{J}|.$$
(109)
The energy difference between the two doublets is given by

$$E_{S=0}E_{S=1/2}=\frac{2}{3}|\stackrel{~}{J}|\left(\frac{\stackrel{~}{\mathrm{\Delta }}}{\stackrel{~}{J}}\right)^4.$$
(110)
Thus, the order parameter $`\stackrel{~}{\mathrm{\Delta }}`$ stabilizes the spin doublet even if it is very small.

In the $`s`$-wave case, the superconducting part of $`H_0`$ is given by

$$H_{0\mathrm{\Delta }}=\stackrel{~}{\mathrm{\Delta }}\left(g_0^{}g_0+g_0^{}g_01\right).$$
(111)
We notice that it is not given by hopping between the sites but is given by a potential on the $`l=0`$ site. This is because the $`s`$-wave Cooper pair is formed by only the $`l=0`$ quasiparticles. In the $`|\stackrel{~}{J}|\mathrm{}`$ limit, we have a Kondo singlet ground state as expected.

Comparing the $`p_x+ip_y`$-wave result with the $`s`$-wave one, we conclude that the spin of the ground state is realized by the orbital dynamics of the $`p_x+ip_y`$-wave Cooper pairs. This point is illustrated by Fig. 3. In a weak coupling region, the spin of the ground state is mainly produced by the local spin itself \[see Fig. 3(a)\]. In the strong coupling limit, however, a Kondo singlet is formed by the $`l=0`$ conduction electrons. Therefore the local spin is almost quenched by the $`l=0`$ electrons. In this limit, one of the paired electrons having $`l=1`$ angular momentum is connected weakly with the Kondo singlet to gain the superconducting condensation energy. The latter electrons generate the ground state spin as shown in Fig. 3(b).

### C Impurity susceptibility

Next we see how the spin of the magnetic impurity is screened by the Kondo effect. For this purpose we calculate a local spin susceptibility which is defined by

$`\chi _{\mathrm{local}}(T)`$ $`=`$ $`g\mu _\mathrm{B}{\displaystyle \frac{S_z}{h}}|_{h0},`$ (113)
$`S_z`$ $`=`$ $`{\displaystyle \frac{\mathrm{Tr}\left[S_z\mathrm{exp}(\overline{\beta }H_N)\right]}{\mathrm{Tr}\left[\mathrm{exp}(\overline{\beta }H_N)\right]}}.`$ (114)
Here $`S_z`$ is the local spin operator, and $`\overline{\beta }1`$ is taken in the calculation. The temperature $`T`$ is given by

$$T=\frac{1}{2}(1+\mathrm{\Lambda }^1)\mathrm{\Lambda }^{(N1)/2}/\overline{\beta }.$$
(115)
A small magnetic field $`h`$ is applied only at the local spin site. The impurity part of the Hamiltonian $`H_0`$ in Eq. (II Cb) is replaced as

$$H_0H_0g\mu _\mathrm{B}S_zh\mathrm{\Lambda }^{1/2}.$$
(116)
Therefore $`\chi _{\mathrm{local}}`$ represents magnetic response of the local spin. In Fig. 4(a) we show the temperature dependence of $`\chi _{\mathrm{local}}`$ for various $`\mathrm{\Delta }`$ with a fixed exchange coupling $`\stackrel{~}{J}`$. We can see that $`T\chi _{\mathrm{local}}`$ decreases monotonically as we decrease temperature (increase the renormalization step) for each $`\mathrm{\Delta }`$, and that it becomes constant at low temperatures, indicating the Curie law. However, the effective $`g`$-factor of the local spin depends on both $`\stackrel{~}{J}`$ and $`\mathrm{\Delta }`$ shown in Fig. 4(b). We can see that $`g`$ is scaled by $`T_\mathrm{K}/\mathrm{\Delta }`$ as in the case of the energy of the first excited state \[see Fig. 1\]. This result indicates that the local spin is actually screened by the Kondo effect, although the ground state is a spin doublet.

In order to see the quantum effect (Kondo effect) of the local spin, we compare the result of the bound state energy for a Ising (classical) spin \[see Fig. 5\]. The bound state energy position is given by

$`E_\mathrm{B}`$ $`=`$ $`{\displaystyle \frac{\mathrm{\Delta }}{\sqrt{1+\gamma ^2}}},`$ (118)
$`\gamma `$ $`=`$ $`{\displaystyle \frac{\pi N_0}{4\mathrm{\Omega }}}|J_z|,`$ (119)
which is essentially same as in the non-magnetic impurity case.  Here $`N_0`$ is the density of state at the Fermi energy in the normal state. $`\mathrm{\Omega }`$ is the volume of the system. The bound state energy decreases as we increase the Ising coupling $`|\stackrel{~}{J}_z|`$. This point is similar to the result of the quantum spin case shown in Fig. 1. However, the bound state energy is independent of $`\mathrm{\Delta }`$ for the Ising spin, while it is a function of $`T_\mathrm{K}/\mathrm{\Delta }`$ for the quantum spin. In addition, we have to use an extremely larger $`|\stackrel{~}{J}_z|`$ value ($`|\stackrel{~}{J}_z|1`$) for the Ising spin to obtain a small $`(E_\mathrm{B}/\mathrm{\Delta })^{}`$. This indicates that the spin-flip effect (quantum effect) is essential to our result, and that the Kondo effect actually occurs in the $`p_x+ip_y`$-wave superconductor.

## IV Conclusion and Discussion

We have studied the novel Kondo effect due to the orbital effect of the Cooper pairs of unconventional superconductors. In particular, we have focused on the $`p_x+ip_y`$-wave ($`d_{x^2y^2}+id_{xy}`$-wave) pairing state. Regarding the magnetic impurity, we have assumed an $`s`$-wave (short-range type) impurity scattering, which is the simplest but is primarily important in real materials. The characteristic point of the unconventional superconductor is that the Cooer pair has orbital degrees of freedom. Therefore the superconducting quasiparticles consist of electrons with various angular momenta. The object of this paper is to clarify how the orbital dynamics of the Cooper pairs affects the Kondo effect in unconventional superconductors. The followings are our main results.

(1) $`p_x+ip_y`$-wave

In the superconducting state, the low-energy excitations are moved out of the superconducting energy gap. The $`p_x+ip_y`$-wave superconductor is a fully gapped system. Unlike the $`s`$-wave superconductor, the $`p_x+ip_y`$-wave Cooper pairs have the orbital degrees of freedom. The local spin couples with only $`l=0`$ electrons which are paired with the $`l=1`$ ones. However, the $`l=1`$ electrons can interact with the local spin via the superconducting order parameter. We note that there is no direct coupling between the local spin and the $`l=1`$ electrons. In contrast to the two-channel Kondo effect derived from the atomic structure of the impurity,  the present two-channel property is the consequence of the internal degrees of freedom of the conduction electron system. Our NRG result shows that the ground state is a spin doublet over all the $`T_\mathrm{K}/\mathrm{\Delta }`$ region. This is completely different from the result of the $`s`$-wave superconductor in which the Kondo singlet is realized in a large $`T_\mathrm{K}/\mathrm{\Delta }`$ region. We also find that the first excited energies are scaled by $`T_\mathrm{K}/\mathrm{\Delta }`$. In the strong coupling limit ($`T_\mathrm{K}/\mathrm{\Delta }\mathrm{}`$), it is found that the effective $`g`$-factor of the local spin is strongly reduced by the Kondo effect, while the $`p_x+ip_y`$-wave Cooper pair couples with the Kondo singlet, generating the spin of the ground state. Thus the orbital effect of the Cooper pair is important in the Kondo effect we have discussed here.

(2) Origins of the multichannel property

Generally, there are two origins of the multichannel property in the Kondo effect. The first one is the internal degrees of freedom of the impurity atom as pointed out by Nozi$`\stackrel{`}{\mathrm{e}}`$res and Blandin.  In this case, the channels of the conduction electron system is controlled by the atomic structure of the impurity atom.

The second one is related to the conduction electron systems. In this paper we have investigated the Kondo effect in the unconventional superconductors. As shown in the $`p_x+ip_y`$-wave case, the multichannel property comes from the angular momenta of the Cooper pairs. The independent channels of the superconducting quasiparticles couple with each other at the impurity even if there is no internal degrees of freedom in the impurity atom (just a local spin). This is because the symmetry of the conduction electron system is different from that of the impurity scattering. As a different variety besides the superconducting systems, we can introduce strong momentum dependence into the bare conduction band. For example, a singular pseudo-gap in the vicinity of the Fermi energy produces unusual Kondo behavior.  Thus the internal degrees of freedom of both the impurity and the conduction electron system are important for the Kondo effect in real materials.

###### Acknowledgements.

We are grateful to S. Curnoe, H. Kusunose, O. Sakai, H. Shiba, R. Shiina, and K. Ueda for helpful discussions and comments.

## A Another Derivation of the NRG Hamiltonian

In Appendix, we present another derivation of the NRG Hamiltonian (II C), following Satori et al..  First, we apply the logarithmic discretization to the conduction band. Then we obtain the hopping type of Hamiltonian,

$`\overline{H}_{\mathrm{kin}}`$ $`=`$ $`{\displaystyle \frac{1+\mathrm{\Lambda }^1}{2}}`$ (A1)
$`\times `$ $`{\displaystyle \underset{n=0}{\overset{\mathrm{}}{}}}{\displaystyle \underset{l\sigma }{}}\mathrm{\Lambda }^{n/2}\epsilon _n(f_{nl\sigma }^{}f_{n+1,l\sigma }+f_{n+1,l\sigma }^{}f_{nl\sigma }),`$ (A2)
for the free electrons. Here $`f_{nl\sigma }^{}`$ and $`f_{nl\sigma }`$ are fermion operators corresponding to the conduction electrons with angular momentum $`l`$. For the BCS pairing interaction in the $`p_x+ip_y`$-wave superconductors, we can also obtain the following Hamiltonian:

$`\overline{H}_\mathrm{\Delta }={\displaystyle \underset{n=0}{\overset{\mathrm{}}{}}}{\displaystyle \underset{\sigma }{}}(i\overline{\mathrm{\Delta }})(f_{n,0,\sigma }^{}f_{n,1,\sigma }^{}f_{n,1,\sigma }f_{n,0,\sigma }).`$ (A3)
To diagonalize $`\overline{H}_\mathrm{\Delta }`$, we use the following Bogoliubov transformation:

$`b_{n,+,\sigma }^{}={\displaystyle \frac{1}{\sqrt{2}}}(f_{n,0,\sigma }^{}if_{n,1,\sigma }),`$ (A5)
$`b_{n,,\sigma }={\displaystyle \frac{1}{\sqrt{2}}}(f_{n,1,\sigma }if_{n,0,\sigma }^{}),`$ (A6)
and we obtain

$`\overline{H}_\mathrm{\Delta }=\overline{\mathrm{\Delta }}{\displaystyle \underset{n=0}{\overset{\mathrm{}}{}}}\left({\displaystyle \underset{\tau \sigma }{}}b_{n\tau \sigma }^{}b_{n\tau \sigma }2\right).`$ (A7)
The impurity Hamiltonian is expressed by the Bogoliubov operators $`b_{n\tau \sigma }^{}`$ and $`b_{n\tau \sigma }`$ as

$`\overline{H}_{\mathrm{imp}}=\overline{J}{\displaystyle \underset{\sigma \sigma ^{}}{}}𝑺𝝈_{\sigma \sigma ^{}}f_{00\sigma }^{}f_{00\sigma ^{}}`$ (A8)
$`={\displaystyle \frac{\overline{J}}{2}}{\displaystyle \underset{\sigma \sigma ^{}}{}}𝑺𝝈_{\sigma \sigma ^{}}(b_{0,+,\sigma }^{}+ib_{0,,\sigma })`$ (A9)
$`\times (b_{0,+,\sigma ^{}}ib_{0,,\sigma ^{}}^{}).`$ (A10)
The Hamiltonian for the conduction electrons is given by

$`\overline{H}_{\mathrm{kin}}`$ $`=`$ $`{\displaystyle \frac{1+\mathrm{\Lambda }^1}{2}}{\displaystyle \underset{n=0}{\overset{\mathrm{}}{}}}{\displaystyle \underset{\sigma }{}}\mathrm{\Lambda }^{n/2}\epsilon _n(i)`$ (A11)
$`\times `$ $`(b_{n,+,\sigma }b_{n+1,,\sigma }+b_{n,+,\sigma }^{}b_{n+1,,\sigma }^{}`$ (A13)
$`+b_{n+1,+,\sigma }b_{n,,\sigma }+b_{n+1,+,\sigma }^{}b_{n,,\sigma }^{}).`$
Next we apply the following particle-hole transformation:

$`c_{2n,+,\sigma }^{}=b_{2n,+,\sigma }^{},c_{2n,,\sigma }^{}=ib_{2n,,\sigma },`$ (A14)
$`c_{2n1,+,\sigma }^{}=ib_{2n1,,\sigma },c_{2n1,,\sigma }^{}=b_{2n1,+,\sigma }^{}.`$ (A15)
In this manner we can exchange the roles of particles and holes to keep the number of fermion quasiparticles. Then we obtain the same form of the Hamiltonian given in (II C). The above argument can be applied to the case of $`d_{x^2y^2}+id_{xy}`$-wave superconductors by replacing $`i\mathrm{\Delta }`$ to $`\sigma \mathrm{\Delta }`$. In this case, the Bogoliubov transformation is given by

$`b_{n,+,\sigma }^{}={\displaystyle \frac{1}{\sqrt{2}}}(f_{n,0,\sigma }^{}+\sigma f_{n,2,\sigma }),`$ (A17)
$`b_{n,,\sigma }={\displaystyle \frac{1}{\sqrt{2}}}(f_{n,2,\sigma }\sigma f_{n,0,\sigma }^{}),`$ (A18)
and the roles of particles and holes are exchanged by the following transformation:

$`c_{2n,+,\sigma }^{}=b_{2n,+,\sigma }^{},c_{2n,,\sigma }^{}=\sigma b_{2n,,\sigma },`$ (A19)
$`c_{2n1,+,\sigma }^{}=\sigma b_{2n1,,\sigma },c_{2n1,,\sigma }^{}=b_{2n1,+,\sigma }^{}.`$ (A20)


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# Superconducting 2D system with lifted spin degeneracy: Mixed singlet-triplet state

## Abstract

Motivated by recent experimental findings, we have developed a theory of the superconducting state for 2D metals without inversion symmetry modeling the geometry of a surface superconducting layer in a field-effect-transistor or near the boundary doped by adsorbed ions. In such systems the two-fold spin degeneracy is lifted by spin-orbit interaction, and singlet and triplet pairings are mixed in the wave function of the Cooper pairs. As a result, spin magnetic susceptibility becomes anisotropic and Knight shift retains finite and rather high value at $`T=0`$.

In this presentation we consider the energy spectrum and some other properties of the superconducting state for a two-dimensional (2D) system without inversion symmetry when the two-fold degeneracy of the electron energy spectrum is lifted by spin-orbit (SO) interaction. We have been motivated by several recent experimental discoveries. Superconductivity (SC) with critical temperature $`T_c=91`$ K was observed in insulating WO3 when its surface was doped by Na+ ions . According to Refs. , SC in the material is a surface effect which comes to the existence in a narrow layer with a composition of $`\mathrm{Na}_{0.05}\mathrm{WO}_3`$. We speculate that strong near-surface electric fields should be present in the SC layer of these crystals quite similar to the 2D superconducting fullerene and polyacene crystals in the field-effect transistor geometry . The two-fold degeneracy of the electron energy spectrum in the bulk characteristic of crystals with 3D inversion symmetry should be broken in the surface layer because of SO coupling. This effect is known and well documented experimentally  in physics of semiconductor microstructures, and has been recently discovered in surface states of metallic Au  and also of (Li covered) Mo and W . In what follows, therefore, we discuss general properties of 2D superconductors with lifted spin degeneracy.

Ideal boundary being a strong “defect” for the crystal’s bulk, it is known that split-off 2D electron bands may form at the surface (Tamm levels). Besides, near the surface the space inversion (the 3D inversion which ensures two-fold degeneracy of the bands throughout the Brillouin zone) is automatically broken, resulting in a new SO invariant of the group C∞v (and its discrete sub-groups) in the free electron Hamiltonian

$$H_{\mathrm{so}}=\alpha (𝝈\times 𝐩)𝐧$$
(1)
dubbed in the literature as Rashba term. Here $`𝐩`$ is a 2D quasimomentum, $`𝝈`$ are Pauli matrices, and $`𝐧`$ is a unit vector normal to the surface ($`\mathrm{}=1`$). Despite the fact that $`𝐩`$ is two-dimensional, the 3D group controls the symmetry of the system since $`𝐧`$ determines the prefered direction of the normal to the plane and spins are always 3D. Total single electron Hamiltonian, $`H=H_0+H_{\mathrm{so}}`$, diagonalizes in eigenfunctions $`\eta _\lambda (𝐩)`$ and eigenvalues $`\epsilon _\lambda (p)`$

$`\eta _\lambda (𝐩)`$ $`=`$ $`{\displaystyle \frac{1}{\sqrt{2}}}\left(\begin{array}{c}1\\ i\lambda \mathrm{exp}(i\phi _𝐩)\end{array}\right),`$ (4)
$`\epsilon _\lambda (p)=\epsilon _0(p)`$ $`+`$ $`\epsilon _\lambda ^{\mathrm{so}}(p),\epsilon _\lambda ^{\mathrm{so}}(p)=\alpha \lambda p,`$ (5)
$`\lambda =\pm 1`$, and the Fermi surface splits into two sheets. SO interaction $`H_{\mathrm{so}}`$ puts electron spins into the plane, ($`𝐧`$), where they are aligned perpendicular to the quasimomentum $`𝐩`$. The magnitude of the coefficient $`\alpha `$ depends on the electric field, presence of adatoms at the boundary, atomic weight, and atomic shells involved. Angle resolved photoemission spectroscopy (ARPES) data on the s-p surface band of Au are in excellent agreement with Eq. (1). They result in a nearly isotropic spectrum with $`\alpha 5\times 10^9\mathrm{eV}\mathrm{cm}`$ (that is somewhat larger than in typical semiconductor systems) and in the SO splitting at the Fermi level $`2|\alpha |p_F=0.11`$ eV. Anisotropic $`d`$-derived bands of Mo and W show even larger SO splittings up to 0.13 eV and 0.5 eV, respectively, depending on the surface concentration of adsorbed Li+ ions.

Returning back to the surface SC reported in Refs.  for doped tungsten bronzes, we expect, therefore, that the SO interaction of Eq. (1) should play essential role in the surface properties both of the normal and SC phases. In what follows we address changes in properties of the BCS-type 2D superconductivity caused by lifting the electron spin degeneracy in the presence of the SO interaction.

For the simplicity sake we consider a two-particle interaction $`U(|𝐫𝐫^{}|)`$ (here and below all vectors lie in the plane). Retardation effects such as due to the phonon mediated attraction are known to be of no importance for a weak coupling scheme. To put it briefly, we do not address at all the issue of the mechanism responsible for pairing, and restrict ourselves by features pertaining to the reduced dimensionality (for the proper symmetry at the surface) and spin-split isotropic electron spectrum. The SO splitting at the Fermi level, $`2\alpha p_F`$, (here and below $`\alpha >0`$) can be comparable to, or exceed, the SC characteristic scale, the critical temperature $`T_c`$. However, it is assumed to be small compared to the Fermi energy, $`2\alpha p_F\epsilon _F`$, and $`p_+p_{}p_F`$, where $`p_\lambda =p_\pm `$ are Fermi momenta for the two SO split sheets of the Fermi surface. Therefore, near the Fermi energy the electron dispersion is taken linear:

$$\xi _\lambda (p)=v_F(pp_\lambda ),p_\lambda =(1+\alpha \lambda /v_F)p_F.$$
(6)
The total electron Hamiltonian $`H=H_0+H_{\mathrm{so}}+H_{\mathrm{int}}`$ includes the interaction Hamiltonian

$`H_{\mathrm{int}}`$ $`=`$ $`{\displaystyle \frac{1}{/}}2{\displaystyle \underset{\lambda \mu \nu \rho }{}}{\displaystyle \underset{\mathrm{𝐩𝐩}^{}𝐪}{}}U_{\lambda \mu \nu \rho }(𝐩,𝐩^{},𝐪)`$ (7)
$`\times `$ $`a_\lambda ^+(𝐩)a_\mu ^+(𝐩𝐪)a_\nu (𝐩^{}𝐪)a_\rho (𝐩^{}).`$ (8)
Here $`a_\lambda (𝐩)`$ are Fermi electronic operators, and $`U_{\lambda \mu \nu \rho }(𝐩,𝐩^{},𝐪)`$ is the interaction potential written in the representation of the spinors $`\eta _\lambda (𝐩)`$

$`U_{\lambda \mu \nu \rho }(𝐩`$ , $`𝐩^{},𝐪)=U(|𝐩𝐩^{}|)`$ (9)
$`\times `$ $`(\eta _\lambda (𝐩),\eta _\rho (𝐩^{}))(\eta _\mu (𝐩𝐪),\eta _\nu (𝐩^{}𝐪)),`$ (10)
$`U(|𝐩|)`$ is the Fourier image of the interaction potential, and scalar products of spinors are equal to

$$(\eta _\lambda (𝐩),\eta _\lambda ^{}(𝐩^{}))=\frac{1}{/}2\{1+\lambda \lambda ^{}\mathrm{exp}[i(\phi _𝐩\phi _𝐩)]\}.$$
(11)
In what follows we employ the method of thermodynamic (Matsubara) Green functions. Onset of the SC state manifests itself as the appearance, side by side with the regular Green functions

$$g_\lambda (𝐩,\tau \tau ^{})=T\{\stackrel{~}{a}_\lambda (𝐩,\tau )\stackrel{~}{a}_\lambda ^+(𝐩,\tau ^{})\},$$
(12)
also of the non-zero anomalous (Gor’kov) averages

$$f_\lambda (𝐩,\tau \tau ^{})=\lambda T\{\stackrel{~}{a}_\lambda (𝐩,\tau )\stackrel{~}{a}_\lambda (𝐩,\tau ^{})\},$$
(13)
$$f_\lambda ^+(𝐩,\tau \tau ^{})=\lambda T\{\stackrel{~}{a}_\lambda ^+(𝐩,\tau )\stackrel{~}{a}_\lambda ^+(𝐩,\tau ^{})\},$$
(14)
where operators $`\stackrel{~}{a}_\lambda (𝐩,\tau )`$ are in the Heisenberg representation. Functions $`f_\lambda (𝐩)f_\lambda (𝐩,0+)`$ that obey the relation

$$f_\lambda ^{}(𝐩)=f_\lambda ^+(𝐩)$$
(15)
are components of the wave functions of Cooper pairs at each spectrum branch. Fermionic commutation relations result in

$$f_\lambda (𝐩)=f_\lambda (𝐩).$$
(16)
From equations of motion for the operators $`\stackrel{~}{a}_\lambda (𝐩,\tau )`$, $`_\tau \stackrel{~}{a}_\lambda (𝐩,\tau )=[H,\stackrel{~}{a}_\lambda (𝐩,\tau )]`$, equations of motion for $`g_\lambda (𝐩,\tau \tau ^{})`$ and $`f_\lambda (𝐩,\tau \tau ^{})`$ follow in the usual way. They include 4-fermion $`T`$-products, the standard decoupling of which results in

$$(_\tau +\epsilon _\lambda (p))g_\lambda (𝐩,\tau \tau ^{})\lambda \underset{\mu 𝐩^{}}{}\mu U_{\lambda \lambda \mu \mu }(𝐩,𝐩^{},0)f_\mu (𝐩^{})f_\lambda ^+(𝐩,\tau \tau ^{})=\delta (\tau \tau ^{}),$$
(17)
$$(_\tau \epsilon _\lambda (p))f_\lambda ^+(𝐩,\tau \tau ^{})+\lambda \underset{\mu 𝐩^{}}{}\mu U_{\mu \mu \lambda \lambda }(𝐩^{},𝐩,0)f_\mu ^+(𝐩^{})g_\lambda (𝐩,\tau \tau ^{})=0.$$
(18)
For the Cooper pairs with the zero total momentum forming the condensate, $`𝐪=0`$ in $`U_{\lambda \lambda \mu \mu }(𝐩,𝐩^{},𝐪)`$. Next simplification in the potential comes from the fact that it enters in Eqs. (17,18) only in the combination with the functions $`f_\mu (𝐩)`$, hence, because of Eq. (16), $`U_{\lambda \lambda \mu \mu }(𝐩,𝐩^{},0)`$ should be antisymmetrisized. Simple algebra shows

$`U_{\lambda \mu }(𝐩,𝐩^{})`$ $``$ $`{\displaystyle \frac{1}{/}}2[U_{\lambda \lambda \mu \mu }(𝐩,𝐩^{},0)U_{\lambda \lambda \mu \mu }(𝐩,𝐩^{},0)]`$ (19)
$``$ $`{\displaystyle \frac{1}{/}}2\lambda \mu U(0)\mathrm{exp}[i(\phi _𝐩^{}\phi _𝐩)].`$ (20)
Having in mind $`s`$-pairing we neglected the momentum dependence of the potential in the right hand side of Eq. (20). Making Fourier transformation of Eqs. (17,18) to the Matsubara frequencies $`i\omega _n`$, we find the final form of Gor’kov equations

$$[i\omega _n\epsilon _\lambda (𝐩)]g_\lambda (𝐩,\omega _n)+\mathrm{\Delta }(𝐩)f_\lambda ^+(𝐩,\omega _n)=1,$$
(21)
$$\mathrm{\Delta }^+(𝐩)g_\lambda (𝐩,\omega _n)+[i\omega _n+\epsilon _\lambda (𝐩)]f_\lambda ^+(𝐩,\omega _n)=0,$$
(22)
where the “gap” $`\mathrm{\Delta }(𝐩)`$ is

$`\mathrm{\Delta }(𝐩)=\mathrm{exp}(i\phi _𝐩)\mathrm{\Delta }_0,`$ $`\mathrm{\Delta }_0={\displaystyle \frac{1}{/}}2U(0){\displaystyle \underset{\lambda 𝐩}{}}\mathrm{exp}(i\phi _𝐩)f_\lambda (𝐩),`$ (23)
$`\mathrm{\Delta }^+(𝐩)`$ $`=`$ $`\mathrm{\Delta }^{}(𝐩).`$ (24)
Before turn to the discussion of the nature of the order parameter in the new SC state, let us make one preliminary comment. The “gap function” $`\mathrm{\Delta }(𝐩)`$ depends on $`𝐩`$ through its phase. This dependence is inherent in the non-perturbative character of the spinor basis functions of Eq. (5) after spin degeneracy is lifted. It cannot be fully eliminated, however, it can be changed by a different choice of phase factors in Eq. (5). Green functions diagonal in branch indices  are

$`g_\lambda (𝐩,\omega _n)`$ $`=`$ $`[i\omega _n+\xi _\lambda (𝐩)]/D_{n\lambda }(𝐩),`$ (25)
$`f_\lambda ^+(𝐩,\omega _n)`$ $`=`$ $`\mathrm{\Delta }^+(𝐩)/D_{n\lambda }(𝐩),`$ (26)
$`D_{n\lambda }(𝐩)`$ $`=`$ $`\omega _n^2+\xi _\lambda ^2(𝐩)+|\mathrm{\Delta }|^2.`$ (27)
The self-consistency condition for $`|\mathrm{\Delta }(𝐩)|\mathrm{\Delta }(T)`$ is

$$\frac{1}{/}2TU(0)\underset{n\lambda 𝐩}{}D_{n\lambda }^1(𝐩)=1.$$
(28)
In the approximation $`2\alpha p_F\epsilon _F`$, left hand side of Eq. (28) does not depend on $`\alpha `$ and coincides with the BCS equation for $`\alpha =0`$. The energy spectrum found from the poles of $`g_\lambda (𝐩,\omega _n)`$ and $`f_\lambda (𝐩,\omega _n)`$ with the proper account of Eq. (6) is

$$E_\lambda (p)=\pm [v_F^2(pp_\lambda )^2+\mathrm{\Delta }^2(T)]^{1/2},$$
(29)
i.e., it consists of two gapped branches. One sees that weak SO coupling makes no changes in thermodynamical properties of the new BCS like state. In particular, the relation $`\mathrm{\Delta }(0)=(\pi /\gamma )T_c1.76T_c`$ holds in this case.

Green function were found above in the representation of energy branches indices $`\lambda `$. To get insight on the symmetry of the new SC state we rewrite them as matrices $`\widehat{G}(𝐩,\omega _n)`$ and $`\widehat{F}(𝐩,\omega _n)`$ in the basis of the components $`\eta _\lambda ^\alpha (𝐩)`$ of the spinors $`\eta _\lambda (𝐩)`$

$`G_{\alpha \beta }(𝐩,\omega _n)`$ $`=`$ $`{\displaystyle \underset{\lambda }{}}\eta _\lambda ^\alpha (𝐩)g_\lambda (𝐩,\omega _n)\eta _\lambda ^\beta (𝐩)^{},`$ (30)
$`F_{\alpha \beta }(𝐩,\omega _n)`$ $`=`$ $`{\displaystyle \underset{\lambda }{}}\eta _\lambda ^\alpha (𝐩)f_\lambda (𝐩,\omega _n)\eta _\lambda ^\beta (𝐩),`$ (31)
and split $`g_\lambda (𝐩,\omega _n)`$ and $`f_\lambda (𝐩,\omega _n)`$ into their symmetric and antisymmetric in $`\lambda `$ parts

$$g_\lambda =g_\mathrm{s}+\frac{1}{/}2\lambda g_{\mathrm{as}},f_\lambda =f_\mathrm{s}+\frac{1}{/}2\lambda f_{\mathrm{as}}.$$
(32)
Eq. (32) implies that $`\widehat{G}=\widehat{G}_\mathrm{s}+\widehat{G}_{\mathrm{as}}`$ and $`\widehat{F}=\widehat{F}_\mathrm{s}+\widehat{F}_{\mathrm{as}}`$. Antisymmetric parts of $`g_\lambda `$ and $`f_\lambda `$ (and also of $`\widehat{G}`$ and $`\widehat{F}`$) originate because of the splitting of the energy spectrum by the SO interaction. It is convenient to write $`\widehat{G}_\mathrm{s}`$ and $`\widehat{G}_{\mathrm{as}}`$ (and also $`\widehat{F}_\mathrm{s}`$ and $`\widehat{F}_{\mathrm{as}}`$) in terms of the Pauli matrices $`𝝈`$ and the unit matrix $`\sigma _0`$. After some algebra we get

$$\widehat{G}_\mathrm{s}(𝐩,\omega _n)=g_\mathrm{s}(𝐩,\omega _n)\sigma _0,$$
(33)
$$\widehat{G}_{\mathrm{as}}(𝐩,\omega _n)=\frac{1}{/}2g_{\mathrm{as}}(𝐩,\omega _n)(𝐩^0\times 𝝈)𝐧,$$
(34)
$$\widehat{F}_\mathrm{s}(𝐩,\omega _n)=[f_\mathrm{s}(𝐩,\omega _n)\mathrm{e}^{i\phi _𝐩}]\sigma _y,$$
(35)
$$\widehat{F}_{\mathrm{as}}(𝐩,\omega _n)=[f_{\mathrm{as}}(𝐩,\omega _n)\mathrm{e}^{i\phi _𝐩}]\sigma _y(𝝈𝐩^0),$$
(36)
where $`𝐩^0=𝐩/p`$. One sees that phase factors $`\mathrm{e}^{i\phi (𝐩)}`$ drop out from both $`\widehat{F}_\mathrm{s}`$ and $`\widehat{F}_{\mathrm{as}}`$ according to Eqs. (24,27). $`\widehat{G}_{\mathrm{as}}`$ and $`\widehat{F}_{\mathrm{as}}`$ components of the Green functions are of the order of unity but only inside a narrow ring of the momentum space, $`\mathrm{\Delta }pp_+p_{}`$, between two Fermi surfaces.

Both contributions to $`\widehat{G}`$ are invariants of the group C∞v, however, they are of opposite parity if the transformation $`𝐩𝐩`$, rotation by $`\pi `$ around the $`z`$ axis, is performed only in coordinate space with spin remaining unchanged. Both $`\widehat{G}_{\mathrm{as}}`$ and $`\widehat{F}_{\mathrm{as}}`$ depend on the azimuth of $`𝐩^0`$. The factor $`(𝝈𝐩^0)`$ is a pseudo-scalar of the 3D inversion group. We attribute to $`\widehat{G}_{\mathrm{as}}`$ a number of transport effects in normal conductors with lifted spin degeneracy which have been observed or predicted.

Existence of non-zero $`\widehat{F}`$-function, Eqs. (35) and (36), means the broken gauge symmetry in the SC state, $`U(1)`$. Eq. (16), when expressed in terms of the functions $`F_{\alpha \beta }(𝐩,\omega _n)`$, reflects permutational symmetry of the wave function of the two electrons of the pair, $`(𝐩,\alpha )`$ and $`(𝐩,\beta )`$. If there is the 3D inversion center, one can make the total wave function odd either by choosing an antisymmetric spin wave function while the space part is symmetric (singlet pairing, $`S=0`$), or, vice versa, by choosing a symmetric spin wave function while the space part is antisymmetric (triplet pairing) ($`S=1`$), see Ref. . Therefore, $`F_{\alpha \beta }(\sigma _y)_{\alpha \beta }`$ for $`S=0`$ and $`F_{\alpha \beta }(\sigma _y(𝝈𝐩))_{\alpha \beta }`$ for $`S=1`$. For the broken 3D inversion near the surface, the Cooper pair wave function $`\widehat{F}`$ becomes a mixture of singlet and triplet pairings. $`\widehat{F}_\mathrm{s}(𝐩,\omega _n)`$ is the singlet part component, while $`\widehat{F}_{\mathrm{as}}(𝐩,\omega _n)`$ provides for the triplet admixture. Note that this term comes about even for the short range interaction $`U(|𝐫𝐫^{}|)\delta (𝐫𝐫^{})`$.

As an example of the phenomenon in which breaking the parity of the order parameter manifests itself, we calculate the spin susceptibility $`\chi ^{\mathrm{sp}}(T)`$ of the surface SC state. It can be directly tested by Knight shift experiments. For systems with strong SO coupling, the total magnetic susceptibility $`\chi `$ cannot be split into the orbital and spin parts. However, when $`\alpha v_F`$ such a division is justified, and we find $`\chi ^{\mathrm{sp}}`$ neglecting the quantization of the orbital motion. Following Ref. , we calculate the tensor $`\chi _{ij}^{\mathrm{sp}}`$ ($`i,j=x,y,z`$) as a linear spin response to the magnetic field $`𝐁`$

$$\chi _{ij}^{\mathrm{sp}}=\mu _\mathrm{B}^2T\nu (\epsilon _F)\underset{\omega _n}{}𝑑\xi \mathrm{tr}\{\sigma _i\widehat{G}(𝐩,\omega _n)\sigma _j\widehat{G}(𝐩,\omega _n)\sigma _i\widehat{F}(𝐩,\omega _n)\sigma _j\widehat{F}^+(𝐩,\omega _n)\}.$$
(37)
Here the trace is taken over the spin indices, $`\nu (\epsilon _F)=p_F/2\pi v_F`$ is the density of states at the Fermi level (per one spin orientation), and $`\mu _\mathrm{B}`$ is the Bohr magneton. In the normal state the right hand side of Eq. (37) diverges because of Landau singularity, and to resolve it the summation over $`\omega _n`$ should be performed first. Finally

$$\chi _N^{\mathrm{sp}}=2\mu _\mathrm{B}^2\nu (\epsilon _F).$$
(38)
Remarkably, $`\chi _N^{\mathrm{sp}}`$ found in the weak field limit, $`\mu _\mathrm{B}B\alpha p_F`$, when Zeeman splitting is small compared to the SO splitting, is isotropic and coincides exactly with the Pauli susceptibility. Since the difference in $`\chi ^{\mathrm{sp}}`$ in the normal and SC states comes from the integration over the region of only about $`\mathrm{\Delta }(T)`$ near $`\epsilon _F`$, the appropriate integral converges. Therefore, in these terms the integration over $`\xi `$ can be performed first. Non-diagonal components of $`\chi ^{\mathrm{sp}}`$ are equal zero because of the C∞v symmetry, while for the diagonal components of $`\chi ^{\mathrm{sp}}`$ somewhat cumbersome calculations result in

$$\chi _{}^{\mathrm{sp}}(T)=\chi _N^{\mathrm{sp}}\left\{1\pi T\underset{\omega _n}{}\frac{\mathrm{\Delta }^2(T)}{\sqrt{\omega _n^2+\mathrm{\Delta }^2(T)}}\frac{1}{\omega _n^2+\mathrm{\Delta }^2(T)+(\alpha p_F)^2}\right\}$$
(39)
$$\chi _{}^{\mathrm{sp}}(T)=\frac{1}{/}2\chi _{}^{\mathrm{sp}}(T)+\frac{1}{/}2\chi _N^{\mathrm{sp}}\left\{1\underset{\omega _n}{}\frac{\pi T\mathrm{\Delta }^2(T)}{\left(\omega _n^2+\mathrm{\Delta }^2(T)\right)^{3/2}}\right\}.$$
(40)
It follows from Eqs. (39) and (40) that $`\chi _{}^{\mathrm{sp}}(T)\chi _{}^{\mathrm{sp}}(T)`$ and $`\chi _{}^{\mathrm{sp}}(0)`$, $`\chi _{}^{\mathrm{sp}}(0)0`$, i.e., spin succeptibility is anisotropic and does not turn into zero at $`T=0`$. We attribute this fact to the admixture of the triplet state to the $`s`$-type SC ground state because of the broken parity. For $`\alpha p_F\mathrm{\Delta }(T)`$, it follows from Eqs. (39,40) that $`\chi _{}^{\mathrm{sp}}(0)\frac{2}{/}3[\alpha p_F/\mathrm{\Delta }(T)]^2\chi _N^{\mathrm{sp}}`$ and $`\chi _{}^{\mathrm{sp}}(0)\frac{1}{/}3[\alpha p_F/\mathrm{\Delta }(T)]^2\chi _N^{\mathrm{sp}}`$. Hence, for $`\alpha =0`$ the BCS result $`\chi _{}^{\mathrm{sp}}(0)=\chi _{}^{\mathrm{sp}}(0)=0`$ is recovered. In the opposite limit $`\mathrm{\Delta }(T)\alpha p_F`$, we get $`\chi _{}^{\mathrm{sp}}(0)\chi _N^{\mathrm{sp}}`$ and $`\chi _{}^{\mathrm{sp}}(0)\chi _N^{\mathrm{sp}}/2`$, hence, $`\chi _{}^{\mathrm{sp}}(T)`$ is nearly $`T`$ independent while $`\chi _{}^{\mathrm{sp}}(T)`$ drops twice when $`T`$ changes from $`T_c`$ to $`T=0`$.

In conclusion, we have shown that spin-orbit interaction lifts the spin degeneracy for 2D (surface) superconductor resulting in the two gapped branches in the energy spectrum. Thermodynamics of such a state would be almost identical to a BCS like superconductor. It turns out that due to broken 3D inversion symmetry at the surface, the pair wave function is the mixture of singlet and triplet components. To the best of our knowledge, such a mixture has never been studied before. As the result, strong anisotropy appears in the spin-susceptibility tensor and the Knight shift. Splitting of two gapped branches in the momentum space depends on the strength of SO coupling. The latter can considerably exceed the SC scale $`T_c`$ to be observed by other means.

L. P. G. thanks Z. Fisk for discussions of a possibility to observe surface SC in tungsten bronzes in the field-effect-transistor geometry. His work was supported by the National High Magnetic Field Laboratory through the NSF Cooperative agreement No. DMR-9521035 and the state of Florida.