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# 1 Introduction

## 1 Introduction

The dynamical Yang-Baxter equation plays an important role in current research on low dimensional integrable systems and in related areas of mathematics (see the reviews  and references therein). In the original form of this equation  the ‘dynamical variable’ belongs to the dual of a Cartan subalgebra of a simple Lie algebra, $`𝒢`$. Etingof and Varchenko  introduced a generalization of the classical dynamical Yang-Baxter equation (CDYBE) for which the variable lies in the dual of an arbitrary subalgebra $`𝒢`$. The CDYBE on $`𝒢`$ ensures the Jacobi identity of a Poisson bracket (PB) of a certain form on the phase space $`^{}\times G\times ^{}`$, where $`G`$ is a connected Lie group with Lie algebra $`𝒢`$, which thus becomes a Poisson-Lie (PL) groupoid . The distinguished special case $`=𝒢`$ has interesting applications . The corresponding PB on $`𝒢^{}\times G\times 𝒢^{}`$ can be viewed as a modification of the canonical PB of the cotangent bundle $`T^{}G`$ expressed in terms of redundant variables.

The idea developed in the present Letter is to replace $`T^{}G`$ in the construction of  by its PL analogue, the Heisenberg double , associated with a factorizable constant $`r`$-matrix. This will lead to a natural PL analogue of the CDYBE on $`𝒢`$. In fact, we shall obtain equation (24), which we call the ‘PL-CDYBE’, as the guarantee of the Jacobi identity of a PB on a PL groupoid of the form $`\stackrel{ˇ}{G}\times G\times \stackrel{ˇ}{G}`$, where $`\stackrel{ˇ}{G}`$ is a neighbourhood of $`eG`$ diffeomorphic to a corresponding domain in the dual $`G^{}`$ of the PL group $`G`$ equipped with the quadratic $`r`$-bracket.

The PL-CDYBE turns out to coincide with a special case of the generalized CDYBE that governs the chiral WZNW PBs for generic monodromy . This special case corresponds to PL symmetries in the chiral WZNW model, and in this context some remarkable solutions of (24) have been found in , too, although the fact that they are solutions was proved in quite an indirect manner only. We here give a self-contained presentation of these solutions, which has the advantage of showing also their uniqueness under a certain analyticity assumption. It will be clear that these solutions are the natural PL analogues of the canonical (Alekseev-Meinrenken) solution of the CDYBE on $`𝒢`$ found in .

The present Letter may serve as a starting point towards deriving generalizations of the CDYBE on $`𝒢`$ for which the dynamical variable belongs to the dual $`H^{}`$ of a PL subgroup $`H`$ of a PL group $`G`$. For this, one should extend the observation  that the CDYBE on $`𝒢`$ can be obtained by applying Dirac reduction to the PL groupoid that encodes the CDYBE on $`𝒢`$. We hope to return to this question in the future.

As for the organization of the rest of the Letter, the derivation of the PL-CDYBE is contained in Section 2, its analytic solutions are described in Section 3, and are further discussed in Section 4. Our results are summarized by Proposition 1 in Section 2 and by Proposition 2 in Section 3.

## 2 PL generalization of the CDYBE on $`𝒢`$

Consider a (real or complex) self-dual Lie algebra111A Lie algebra that admits an invariant scalar product, i.e. an invariant nondegenerate symmetric bilinear form, is called self-dual. A review of self-dual Lie algebras can be found in . $`𝒢`$ with a fixed invariant scalar product $`,`$ and a corresponding connected Lie group $`G`$. The scalar product is used to identify the dual space $`𝒢^{}`$ with $`𝒢`$. We below recall the derivation of the CDYBE on $`𝒢`$ and then generalize it to the PL case in correspondence with any antisymmetric constant solution $`r𝒢𝒢`$ of the modified CYBE:

$$[r_{12},r_{13}]+\text{cycl. perm.}=\frac{1}{4}f,$$
(1)
where $`f=f_{ab}^cT^aT^bT_c`$ with dual bases $`\{T_a\}`$ and $`\{T^b\}`$ of $`𝒢`$ satisfying $`[T_a,T_b]=f_{ab}^cT_c`$ and $`T_a,T^b=\delta _a^b`$. Summation over coinciding indices is understood and the notations $`C:=T_aT^a`$, $`r^\pm :=r\pm \frac{1}{2}C`$ are used throughout the Letter.

### 2.1 Recall of the CDYBE on $`𝒢`$

Let us introduce the phase space

$$𝒫:=𝒢\times G\times 𝒢=\{(\omega ^L,g,\omega ^R)|\omega ^{L,R}𝒢,gG\}$$
(2)
and equip it with the Poisson structure $`\{,\}_𝒫^0`$ defined as follows:

$`\{g_1,g_2\}_𝒫^0=0`$
$`\{\omega _1^L,\omega _2^L\}_𝒫^0={\displaystyle \frac{1}{2}}[C,\omega _2^L\omega _1^L]`$
$`\{\omega _1^L,g_2\}_𝒫^0=Cg_2`$
$`\{\omega _1^R,\omega _2^R\}_𝒫^0={\displaystyle \frac{1}{2}}[C,\omega _2^R\omega _1^R]`$
$`\{\omega _1^R,g_2\}_𝒫^0=g_2C`$
$`\{\omega _1^R,\omega _2^L\}_𝒫^0=0.`$ (3)
In this description of the PBs of the fundamental variables $`g`$, $`\omega ^{L,R}`$ we employ the standard tensorial notation  that implicitly refers to an arbitrary matrix representation of $`G`$. The formulae

$$\varphi :G\times 𝒫𝒫,\varphi :(q,(\omega ^L,g,\omega ^R))(q\omega ^Lq^1,qg,\omega ^R)$$
(4)
$$\psi :𝒫\times G𝒫,\psi :((\omega ^L,g,\omega ^R),q)(\omega ^L,gq,q^1\omega ^Rq)$$
(5)
define left- and right actions of the group $`G`$ on $`𝒫`$. These are Poisson actions in the usual sense, with respect to the zero PB on $`G=\{q\}`$, and the corresponding momenta that generate them are directly given by $`\omega ^L`$ and $`\omega ^R`$, respectively. The constraint

$$\omega ^R=g^1\omega ^Lg$$
(6)
defines a Poisson submanifold of $`(𝒫,\{,\}_𝒫^0)`$, which can be identified with the cotangent bundle $`T^{}G`$ with its canonical PB. Conversely, $`(𝒫,\{,\}_𝒫^0)`$ is obtained from the cotangent bundle by ‘forgetting’ this familiar relation between the left- and right momenta.

Now consider a (smooth or holomorphic) map $`:\stackrel{ˇ}{𝒢}𝒢𝒢`$, where $`\stackrel{ˇ}{𝒢}𝒢`$ is an open submanifold stable under the adjoint action of $`G`$. By using $``$, let us try to define a PB $`\{,\}_{\stackrel{ˇ}{𝒫}}`$ on the manifold $`\stackrel{ˇ}{𝒫}:=\stackrel{ˇ}{𝒢}\times G\times \stackrel{ˇ}{𝒢}𝒫`$ by the following formula:

$`\{g_1,g_2\}_{\stackrel{ˇ}{𝒫}}=(\omega ^L)g_1g_2g_1g_2(\omega ^R)`$
$`\{\omega _1^L,\omega _2^L\}_{\stackrel{ˇ}{𝒫}}={\displaystyle \frac{1}{2}}[C,\omega _2^L\omega _1^L]`$
$`\{\omega _1^L,g_2\}_{\stackrel{ˇ}{𝒫}}=Cg_2`$
$`\{\omega _1^R,\omega _2^R\}_{\stackrel{ˇ}{𝒫}}={\displaystyle \frac{1}{2}}[C,\omega _2^R\omega _1^R]`$
$`\{\omega _1^R,g_2\}_{\stackrel{ˇ}{𝒫}}=g_2C`$
$`\{\omega _1^R,\omega _2^L\}_{\stackrel{ˇ}{𝒫}}=0.`$ (7)
This formula differs from (3) only in the first line that contains $``$.

It is easy to check that the Jacobi identities of $`\{,\}_{\stackrel{ˇ}{𝒫}}`$ require $``$ to be equivariant,

$$(q\omega q^1)=(qq)(\omega )(q^1q^1)qG,\omega =\omega ^aT_a\stackrel{ˇ}{𝒢},$$
(8)
and to satisfy the equation

$$[_{12},_{13}]+T_3^a\frac{}{\omega ^a}_{12}+\text{cycl. perm.}=\text{on}\stackrel{ˇ}{𝒢},$$
(9)
where $``$ is some $`G`$-invariant constant element of $`𝒢𝒢𝒢`$. Equation (9) is the (modified) CDYBE on $`𝒢`$. (Strictly speaking, the term ‘modified’ should be used if $`0`$.)

The above interpretation of the CDYBE on $`𝒢`$ is taken from . Due to the equivariance property (8), the actions of $`G`$ given by $`\varphi `$ (4) and $`\psi `$ (5) yield Poisson actions on $`(\stackrel{ˇ}{𝒫},\{,\}_{\stackrel{ˇ}{𝒫}})`$ that are generated by the momenta $`\omega ^{L,R}`$ in the same way as in the $`=0`$ case. It is also explained in  that $`(\stackrel{ˇ}{𝒫},\{,\}_{\stackrel{ˇ}{𝒫}})`$ has the structure of a PL groupoid.

Let $``$ denote the holomorphic complex function given by

$$(z)=\mathrm{coth}zz^1,(0)=0.$$
(10)
By using the identification $`𝒢𝒢\mathrm{End}(𝒢)`$ defined by the scalar product on $`𝒢`$, one obtains  a solution of (9) by setting

$$(\omega ):=(\mathrm{ad}_\omega ),=f$$
(11)
with $`f`$ in (1). In  this $`r`$-matrix is called ‘canonical’ since it is actually the unique solution of (9) under assuming (11) as an ansatz with some holomorphic odd function regular at $`0`$. Generalizations of the canonical $`r`$-matrix are described in Section 3.

### 2.2 Derivation of the PL-CDYBE

A natural PL analogue, $`(P,\{,\}_P^0)`$, of the Poisson manifold $`(𝒫,\{,\}_𝒫^0)`$ is provided by

$$P:=G\times G\times G=\{(\mathrm{\Omega }^L,g,\mathrm{\Omega }^R)|\mathrm{\Omega }^{L,R}G,gG\}$$
(12)
with the PB $`\{,\}_P^0`$ defined by

$`\{g_1,g_2\}_P^0=rg_1g_2g_1g_2r`$
$`\{\mathrm{\Omega }_1^L,\mathrm{\Omega }_2^L\}_P^0=r\mathrm{\Omega }_1^L\mathrm{\Omega }_2^L+\mathrm{\Omega }_1^L\mathrm{\Omega }_2^Lr\mathrm{\Omega }_1^Lr^{}\mathrm{\Omega }_2^L\mathrm{\Omega }_2^Lr^+\mathrm{\Omega }_1^L`$
$`\{\mathrm{\Omega }_1^L,g_2\}_P^0=(r^+\mathrm{\Omega }_1^L\mathrm{\Omega }_1^Lr^{})g_2`$
$`\{\mathrm{\Omega }_1^R,\mathrm{\Omega }_2^R\}_P^0=\left(r\mathrm{\Omega }_1^R\mathrm{\Omega }_2^R+\mathrm{\Omega }_1^R\mathrm{\Omega }_2^Rr\mathrm{\Omega }_1^Rr^{}\mathrm{\Omega }_2^R\mathrm{\Omega }_2^Rr^+\mathrm{\Omega }_1^R\right)`$
$`\{\mathrm{\Omega }_1^R,g_2\}_P^0=g_2(r^+\mathrm{\Omega }_1^R\mathrm{\Omega }_1^Rr^{})`$
$`\{\mathrm{\Omega }_1^R,\mathrm{\Omega }_2^L\}_P^0=0.`$ (13)
The Poisson submanifold $`(T^{}G)_rP`$ specified by the constraint

$$\mathrm{\Omega }^R=g^1\mathrm{\Omega }^Lg$$
(14)
is the PL analogue of the cotangent bundle considered in . The formulae

$$\mathrm{\Phi }:G\times PP,\mathrm{\Phi }:(q,(\mathrm{\Omega }^L,g,\mathrm{\Omega }^R))(q\mathrm{\Omega }^Lq^1,qg,\mathrm{\Omega }^R)$$
(15)
$$\mathrm{\Psi }:P\times GP,\mathrm{\Psi }:((\mathrm{\Omega }^L,g,\mathrm{\Omega }^R),q)(\mathrm{\Omega }^L,gq,q^1\mathrm{\Omega }^Rq)$$
(16)
define left- and right actions of the group $`G`$ on $`P`$. These are PL actions if the group $`G=\{q\}`$ is endowed with the Sklyanin PB

$$\{q_1,q_2\}=rq_1q_2q_1q_2r,$$
(17)
and then $`\mathrm{\Omega }^{L,R}`$ yield group valued momenta generating these actions. It is well known  that the PB on $`G`$ appearing in the second line of (13) becomes the natural PB on the PL group $`G^{}`$ dual to $`G`$ if we locally identify $`G^{}`$ with $`G`$ in the standard manner. This PB on $`G`$ is sometimes referred to as the Semenov-Tian-Shansky PB. The Poisson space $`(𝒫,\{,\}_𝒫^0)`$ is a linearization of $`(P,\{,\}_P^0)`$ in the same sense in which $`T^{}G`$ is the linearization of its PL analogue (see e.g. ). This is further discussed in Section 4.

Now it should be clear how the above set of analogies can be extended to obtain a natural PL generalization of the CDYBE on $`𝒢`$. As input data, we consider a (smooth or holomorphic) map $`R:\stackrel{ˇ}{G}𝒢𝒢`$, where $`\stackrel{ˇ}{G}G`$ is an open submanifold stable under conjugation by any $`qG`$. We then require $`R`$ to define a PB, $`\{,\}_{\stackrel{ˇ}{P}}`$, on the manifold $`\stackrel{ˇ}{P}:=\stackrel{ˇ}{G}\times G\times \stackrel{ˇ}{G}`$ by means of following modification of (13):

$`\{g_1,g_2\}_{\stackrel{ˇ}{P}}=(r+R(\mathrm{\Omega }^L))g_1g_2g_1g_2(r+R(\mathrm{\Omega }^R))`$
$`\{\mathrm{\Omega }_1^L,\mathrm{\Omega }_2^L\}_{\stackrel{ˇ}{P}}=r\mathrm{\Omega }_1^L\mathrm{\Omega }_2^L+\mathrm{\Omega }_1^L\mathrm{\Omega }_2^Lr\mathrm{\Omega }_1^Lr^{}\mathrm{\Omega }_2^L\mathrm{\Omega }_2^Lr^+\mathrm{\Omega }_1^L`$
$`\{\mathrm{\Omega }_1^L,g_2\}_{\stackrel{ˇ}{P}}=(r^+\mathrm{\Omega }_1^L\mathrm{\Omega }_1^Lr^{})g_2`$
$`\{\mathrm{\Omega }_1^R,\mathrm{\Omega }_2^R\}_{\stackrel{ˇ}{P}}=\left(r\mathrm{\Omega }_1^R\mathrm{\Omega }_2^R+\mathrm{\Omega }_1^R\mathrm{\Omega }_2^Rr\mathrm{\Omega }_1^Rr^{}\mathrm{\Omega }_2^R\mathrm{\Omega }_2^Rr^+\mathrm{\Omega }_1^R\right)`$
$`\{\mathrm{\Omega }_1^R,g_2\}_{\stackrel{ˇ}{P}}=g_2(r^+\mathrm{\Omega }_1^R\mathrm{\Omega }_1^Rr^{})`$
$`\{\mathrm{\Omega }_1^R,\mathrm{\Omega }_2^L\}_{\stackrel{ˇ}{P}}=0.`$ (18)
We are interested in such Poisson structures for which the restrictions of $`\mathrm{\Phi }`$ (15) and $`\mathrm{\Psi }`$ (16) to $`\stackrel{ˇ}{P}`$ yield PL actions of the group $`G`$ equipped with the Sklyanin PB (17). As is easy to check, the ansatz (18) enjoys this PL symmetry if and only if $`R`$ is equivariant,

$$R(q\mathrm{\Omega }q^1)=(qq)R(\mathrm{\Omega })(q^1q^1)qG,\mathrm{\Omega }\stackrel{ˇ}{G}.$$
(19)
Therefore we assume (19) to hold. The equivariance of $`R`$ also guarantees the Jacobi identities

$$\{\{g_1,g_2\}_{\stackrel{ˇ}{P}},\mathrm{\Omega }_3^L\}_{\stackrel{ˇ}{P}}+\text{cycl. perm}=0,\{\{g_1,g_2\}_{\stackrel{ˇ}{P}},\mathrm{\Omega }_3^R\}_{\stackrel{ˇ}{P}}+\text{cycl. perm}=0.$$
(20)
To explain how this works, let $`\lambda ^a`$ and $`\rho ^a`$ denote the vector fields on $`G`$ that operate on the group element by left- and by right multiplication by $`T^a𝒢`$, respectively. In other words, $`\lambda ^a`$ and $`\rho ^a`$ are the right- and left-invariant vector fields associated with $`T^aT_eG`$, respectively. Introduce also

$$𝒟_\pm ^a:=(\rho ^a\pm \lambda ^a)\text{and}𝒟_a^\pm :=(\rho _a\pm \lambda _a).$$
(21)
In fact, (18) implies the relation

$`\{\{g_1,g_2\}_{\stackrel{ˇ}{P}},\mathrm{\Omega }_3^L\}_{\stackrel{ˇ}{P}}+\text{cycl. perm.}=\left([R_{12}(\mathrm{\Omega }^L),r_{13}^{}+r_{23}^{}]r_{ab}^{}𝒟_{}^aR_{12}(\mathrm{\Omega }^L)T_3^b\right)\mathrm{\Omega }_3^Lg_1g_2`$
$`\mathrm{\Omega }_3^L\left([R_{12}(\mathrm{\Omega }^L),r_{13}^++r_{23}^+]r_{ab}^+𝒟_{}^aR_{12}(\mathrm{\Omega }^L)T_3^b\right)g_1g_2.`$ (22)
The right hand side vanishes as a consequence of the infinitesimal version of (19),

$$𝒟_{}^aR_{12}(\mathrm{\Omega })=[R_{12}(\mathrm{\Omega }),T_1^a+T_2^a]\mathrm{\Omega }\stackrel{ˇ}{G},T^a𝒢.$$
(23)
The other Jacobi identity in (20) holds in a similar manner. The Jacobi identities involving $`\{\{g_1,\mathrm{\Omega }_2^L\}_{\stackrel{ˇ}{P}},\mathrm{\Omega }_3^L\}_{\stackrel{ˇ}{P}}`$ and $`\{\{g_1,\mathrm{\Omega }_2^R\}_{\stackrel{ˇ}{P}},\mathrm{\Omega }_3^R\}_{\stackrel{ˇ}{P}}`$ are automatically satisfied since they do not contain $`R`$. Note that $`\mathrm{\Omega }^{L,R}`$ serve as momentum maps for $`(\stackrel{ˇ}{P},\{,\}_{\stackrel{ˇ}{P}})`$ in the same way as they do for $`(P,\{,\}_P^0)`$. The only further requirement on $`R`$ imposed by the Jacobi identities of $`\{,\}_{\stackrel{ˇ}{P}}`$ is the PL-CDYBE described in following proposition.

Proposition 1. Let $`R:\stackrel{ˇ}{G}𝒢𝒢`$ be a (smooth or holomorphic) $`G`$-equivariant map (19). Formula (18) generates a PB on the (smooth or holomorphic) functions on $`\stackrel{ˇ}{P}`$ if and only if $`R`$ satisfies the PL-CDYBE given by

$$[R_{12},R_{13}]+\frac{1}{2}T_3^a𝒟_a^+R_{12}+\text{cycl. perm.}=\text{on}\stackrel{ˇ}{G},$$
(24)
where $``$ is an arbitrary $`G`$-invariant constant element of $`𝒢𝒢𝒢`$.

Proof. It is clear that (18) defines a PB if and only if the Jacobi identity involving $`\{\{g_1,g_2\}_{\stackrel{ˇ}{P}},g_3\}_{\stackrel{ˇ}{P}}`$ is satisfied. A straightforward calculation gives

$$\{\{g_1,g_2\}_{\stackrel{ˇ}{P}},g_3\}_{\stackrel{ˇ}{P}}+\text{cycl. perm.}=(\mathrm{\Omega }^L)(g_1g_2g_3)(g_1g_2g_3)(\mathrm{\Omega }^R),$$
(25)
where the expression $``$ reads as

$$(\mathrm{\Omega })=\left([r_{12}+R_{12},r_{13}+R_{13}]+T_3^a(r_{ab}𝒟_{}^b+\frac{1}{2}𝒟_a^+)R_{12}+\text{cycl. perm.}\right)(\mathrm{\Omega }).$$
(26)
By (25), the Jacobi identity requires $`(\mathrm{\Omega })`$ to be a $`G`$-invariant constant. We notice that the equivariance (23) of $`R`$ implies the relation

$$[r_{12}+R_{12},r_{13}+R_{13}]+\text{cycl. perm.}=[r_{12},r_{13}]+[R_{12},R_{13}]T_3^ar_{ab}𝒟_{}^bR_{12}+\text{cycl. perm.}$$
(27)
By inserting this and (1) into (26) we immediately obtain the PL-CDYBE (24). Q.E.D.

Remark 1. It is remarkable that the PL-CDYBE (24) does not contain any explicit reference to the background constant $`r`$-matrix used in (18). This equation first appeared in  as a condition on the ‘exchange $`r`$-matrices’ associated with PL symmetries in the chiral WZNW model. In this application the role of the group valued variable is played by the monodromy matrix of the chiral WZNW field, but the PBs of the monodromy matrix are different from the Semenov-Tian-Shansky PBs that appear in the second and fourth lines of (18).

Remark 2. The manifold $`\stackrel{ˇ}{P}=\stackrel{ˇ}{G}\times G\times \stackrel{ˇ}{G}`$ is a groupoid  with the partial multiplication

$$(\overline{\mathrm{\Omega }}^R,\overline{g},\overline{\mathrm{\Omega }}^L)(\mathrm{\Omega }^R,g,\mathrm{\Omega }^L)=(\widehat{\mathrm{\Omega }}^R,\widehat{g},\widehat{\mathrm{\Omega }}^L)$$
(28)
defined by the constraints

$$\overline{\mathrm{\Omega }}^L=\mathrm{\Omega }^R,\widehat{\mathrm{\Omega }}^R=\overline{\mathrm{\Omega }}^R,\widehat{\mathrm{\Omega }}^L=\mathrm{\Omega }^L,\widehat{g}=\overline{g}g.$$
(29)
These are first class constraints on $`\stackrel{ˇ}{P}\times \stackrel{ˇ}{P}\times \stackrel{ˇ}{P}^{}`$ if the first two factors are equipped with the PB $`\{,\}_{\stackrel{ˇ}{P}}`$ and $`\stackrel{ˇ}{P}^{}`$, the set of the hatted triples in (28), is equipped with the opposite PB. This means that the phase space $`(\stackrel{ˇ}{P},\{,\}_{\stackrel{ˇ}{P}})`$ is a PL groupoid . As far as the PBs are concerned, this PL groupoid appears to be different from the groupoids associated with the WZNW exchange $`r`$-matrices in  even in the special case when those exchange $`r`$-matrices satisfy the PL-CDYBE (24). It would be very interesting to clarify the relationship (which is perhaps an equivalence by some change of variables) between the PL groupoids $`(\stackrel{ˇ}{P},\{,\}_{\stackrel{ˇ}{P}})`$ and those constructed in .

## 3 A family of solutions of the PL-CDYBE

To simplify some arguments, in the main body of this section we assume that $`𝒢`$ is a complex simple Lie algebra and describe certain solutions of (24) in this case. These dynamical $`r`$-matrices were originally found in the context of the WZNW model . Their presentation below is considerably simpler than the one in  and our Proposition 2 includes a new uniqueness result as well. At the end of the section, it will be remarked that these solutions of (24) are available for any self-dual Lie algebra.

First note that for a simple Lie algebra the invariant $``$ in (24) must have the form

$$=\mu f,$$
(30)
where $`f`$ is given in (1) and $`\mu `$ is some constant. If (30) holds and we identify $`𝒢𝒢`$ with $`\mathrm{End}(𝒢)`$ by the scalar product on $`𝒢`$, then (24) can be equivalently rewritten as the requirement

$$[R(\mathrm{\Omega })X,R(\mathrm{\Omega })Y]\frac{1}{2}𝒟_X^+R(\mathrm{\Omega })Y,Z+\text{cycl. perm.}=\mu [X,Y],ZX,Y,Z𝒢,$$
(31)
where the cyclic permutations act on $`X,Y,Z`$ and we have

$$𝒟_X^+R(\mathrm{\Omega })=X^a𝒟_a^+R(\mathrm{\Omega })=\frac{d}{dt}|_{t=0}R(e^{tX}\mathrm{\Omega }e^{tX})\text{for}R:\stackrel{ˇ}{G}\mathrm{End}(𝒢).$$
(32)
We suppose the domain $`\stackrel{ˇ}{G}G`$ to be diffeomorphic to a neighbourhood of zero $`\stackrel{ˇ}{𝒢}𝒢`$ by means of the exponential map, and thus parametrize $`\mathrm{\Omega }\stackrel{ˇ}{G}`$ according to

$$\mathrm{\Omega }=e^\omega \text{with}\omega \stackrel{ˇ}{𝒢}.$$
(33)
We further write

$$R(e^\omega )=\stackrel{~}{R}(\omega )\text{for}\omega \stackrel{ˇ}{𝒢}.$$
(34)
Define the holomorphic complex function $`h`$ by

$$h(z)=\frac{1}{2}z\mathrm{coth}(\frac{1}{2}z),h(0)=1.$$
(35)
In fact, the required derivatives of $`R`$ can be expressed in terms of the variable $`\omega `$ as

$$\frac{1}{2}𝒟_X^+R(e^\omega )=\frac{d}{dt}|_{t=0}\stackrel{~}{R}(\omega +h(\mathrm{ad}_\omega )Xt).$$
(36)
This is a consequence of standard identities (e.g. ) expressing the left- and right-invariant vector fields on $`G`$ in the exponential parametrization.

Now let $`F`$ be a holomorphic complex function which is regular in a neighbourhood of $`z=0`$ and is odd, $`F(z)=F(z)`$. Then consider the ansatz

$$R(e^\omega )=F(\mathrm{ad}_\omega ),\omega \stackrel{ˇ}{𝒢}.$$
(37)
Note that $`F(\mathrm{ad}_\omega )`$ is given by means of the Taylor series of $`F(z)`$ around $`z=0`$ if $`\omega `$ is near enough to zero. This ansatz automatically guarantees the equivariance and the antisymmetry of the dynamical $`r`$-matrix $`R(e^\omega )`$.

Proposition 2. Let $`𝒢`$ be a complex simple Lie algebra. The ansatz (37) provides a solution of the PL-CDYBE (31), which is equivalent to (24), on a domain $`\stackrel{ˇ}{G}=\mathrm{exp}(\stackrel{ˇ}{𝒢})`$ if and only if the holomorphic odd function $`F(z)`$ is given by

$$F_\nu (z)=\nu \mathrm{coth}(\nu z)\frac{1}{2}\mathrm{coth}(\frac{1}{2}z),$$
(38)
where $`\nu `$ is an arbitrary constant related to the constant $`\mu `$ in (30) by $`\mu =\frac{1}{4}\nu ^2`$.

Proof. We start by noting that equation (31) is satisfied on $`\stackrel{ˇ}{𝒢}`$ if and only if it is satisfied on the dense, open submanifold of $`\stackrel{ˇ}{𝒢}`$ consisting of regular semisimple elements. Therefore we may subsequently fix $`\omega `$ to be an arbitrarily chosen regular semisimple element of $`\stackrel{ˇ}{𝒢}`$. For such an $`\omega `$ it is convenient to choose a basis of $`𝒢`$ spanned by root vectors $`E_\alpha `$ ($`\alpha \mathrm{\Delta }`$), where $`\mathrm{\Delta }`$ is the set of roots with respect to the Cartan subalgebra $``$ that contains $`\omega `$, and a basis $`H_i`$ of $``$. The ansatz (37) gives directly that

$$R(e^\omega )H_i=0,R(e^\omega )E_\alpha =F(\alpha (\omega ))E_\alpha .$$
(39)
The derivatives appearing in (31) can be computed with the aid of (36) and the equivariance of $`R`$, $`R(q\mathrm{\Omega }q^1)=\mathrm{Ad}_qR(\mathrm{\Omega })\mathrm{Ad}_{q^1}`$ for $`\mathrm{Ad}_q\mathrm{End}(𝒢)`$ $`qG`$. We find

$`𝒟_{E_\alpha }^+R(e^\omega )=2\theta (\alpha (\omega ))[R(e^\omega ),\mathrm{ad}_{E_\alpha }]\alpha \mathrm{\Delta },`$
$`𝒟_{H_i}^+R(e^\omega )=2F^{}(\mathrm{ad}_\omega )\mathrm{ad}_{H_i}H_i,`$ (40)
where we introduced the notation

$$\theta (z):=z^1h(z)=\frac{1}{2}\mathrm{coth}(\frac{1}{2}z).$$
(41)
This can be spelled out as

$`𝒟_{E_\alpha }^+R(e^\omega )E_\beta =2\theta (\alpha (\omega ))\left(F(\alpha (\omega )+\beta (\omega ))F(\beta (\omega ))\right)[E_\alpha ,E_\beta ]`$
$`𝒟_{E_\alpha }^+R(e^\omega )H_i=2\alpha (H_i)\theta (\alpha (\omega ))F(\alpha (\omega ))E_\alpha `$
$`𝒟_{H_i}^+R(e^\omega )E_\alpha =2\alpha (H_i)F^{}(\alpha (\omega ))E_\alpha `$
$`𝒟_{H_i}^+R(e^\omega )H_j=0,`$ (42)
for any $`\alpha ,\beta \mathrm{\Delta }`$. The first line of (42) simplifies if $`\beta =\alpha `$, since $`F(0)=0`$ by the oddness of $`F`$. The nontrivial conditions represented by (31) arise in the cases

$$X=E_\alpha ,Y=H_i,Z=E_\alpha \text{and}X=E_\alpha ,Y=E_\beta ,Z=E_{\alpha \beta },$$
(43)
where $`H_i`$ and $`\alpha ,\beta ,(\alpha +\beta )\mathrm{\Delta }`$. Indeed, by evaluating (31) for the independent choices in (43) we obtain that (31) under the ansatz (37) is equivalent to the following conditions on the holomorphic function $`F`$:

$$F^{}(z)+2\theta (z)F(z)+F^2(z)+\mu =0,F(0)=0,$$
(44)
and

$`F(z)F(w)F(z+w)(F(z)+F(w))\theta (z)(F(z+w)F(w))`$
$`\theta (w)(F(z+w)F(z))\theta (z+w)(F(z)+F(w))\mu =0.`$ (45)
The differential equation (44) arises from the first choice in (43), while the functional equation (45) arises from the second choice. Thus (45) must hold for nonzero $`z`$, $`w`$, $`(z+w)`$ in a neighbourhood of $`0`$.

Now the differential equation (44) is not difficult to solve. Let $`\chi (z)=F(z)+\theta (z)`$. Then the identity $`\theta ^2(z)+\theta ^{}(z)=\frac{1}{4}`$ and setting $`\mu =\frac{1}{4}\nu ^2`$ gives

$$\chi ^{}(z)+\chi ^2(z)=\nu ^2,\underset{z0}{lim}z\chi (z)=1.$$
(46)
The unique solution of this is

$$\chi (z)=\nu \mathrm{coth}(\nu z),$$
(47)
which yields

$$F(z)=\nu \mathrm{coth}(\nu z)\frac{1}{2}\mathrm{coth}(\frac{1}{2}z),\mu =\frac{1}{4}\nu ^2.$$
(48)
So far we have shown that for (37) to satisfy (31) it is necessary for $`F`$ to be given by (48) with some $`\nu `$. To see that it is also sufficient we must verify the functional equation (45). Using the identity $`\mathrm{coth}x\mathrm{coth}y\mathrm{coth}(x+y)(\mathrm{coth}x+\mathrm{coth}y)=1`$, it is easy to check that for $`F`$ given by (48), (45) does indeed hold. Q.E.D.

Remark 3. Let us comment on the domain of definition of the $`r`$-matrices provided by Proposition 2. The map $`R:\stackrel{ˇ}{G}:\mathrm{End}(𝒢)`$ is defined in (37) by a power series in $`\mathrm{ad}_{\mathrm{log}\mathrm{\Omega }}`$ if $`\mathrm{\Omega }`$ is near to $`eG`$. For generic $`\nu `$, the domain of this $`r`$-matrix can be extended naturally to contain all $`\mathrm{\Omega }`$ that has a unique logarithm and the eigenvalues of $`\mathrm{ad}_{\mathrm{log}\mathrm{\Omega }}`$ do not intersect the poles of the holomorphic function $`F_\nu `$. If $`\nu `$ is a half-integer, then our $`r`$-matrix can be expressed directly in terms of $`\mathrm{\Omega }`$. For example, we obtain

$$R(\mathrm{\Omega })=\frac{1}{2}\left(\mathrm{Ad}_\mathrm{\Omega }1\right)(\mathrm{Ad}_\mathrm{\Omega }+1)^1\text{for}\nu =1,$$
(49)
since $`F_1(z)=\frac{1}{2}(e^z1)(e^z+1)^1`$. The maximal domain of definition of $`R`$ in (49) contains all $`\mathrm{\Omega }G`$ for which $`1`$ is not an eigenvalue of $`\mathrm{Ad}_\mathrm{\Omega }`$. It is easy to verify directly that (49) solves the PL-CDYBE (31) with $`\mu =\frac{3}{4}`$ for any Lie group $`G`$ with a self-dual Lie algebra.

Remark 4. In fact, the statement of Proposition 2 remains valid if we replace the complex simple Lie algebra $`𝒢`$ with any (complex or real) self-dual Lie algebra. This can be proved by the method used in  to analyse the CDYBE (9) on an arbitrary self-dual Lie algebra. The arguments contained in  are also valid in this generality.

## 4 Discussion

In this Letter we have shown that equation (24) is a natural PL analogue of the CDYBE (9) on $`𝒢`$ and established a uniqueness result concerning the family of solutions of it given by (37) with (38). The PL-CDYBE together with these solutions appeared earlier in the concrete context of PL symmetries on the chiral WZNW phase space . The present work provides a new, purely group theoretic interpretation of this equation.

Since $`T^{}G`$ can be viewed as a ‘scaling limit’ of $`(T^{}G)_r`$ , it should be possible to view also the canonical solution (11) of the CDYBE on $`𝒢`$ as a limiting case of the $`r`$-matrices given in Proposition 2. We conclude by outlining how this comes about.

Let $`\{,\}_{\stackrel{ˇ}{P},\nu }`$ denote the PB (18) on $`\stackrel{ˇ}{P}`$ defined by $`R(\mathrm{\Omega }):=F_\nu (\mathrm{ad}_{\mathrm{log}\mathrm{\Omega }})`$ with (38). For an arbitrary constant $`\gamma `$, consider the map $`\pi _\gamma :\stackrel{ˇ}{𝒫}\stackrel{ˇ}{P}`$ given by the scaled exponential parametrization

$$\pi _\gamma :(\omega ^L,g,\omega ^R)(e^{\gamma \omega ^L},g,e^{\gamma \omega ^R}).$$
(50)
By choosing the domains $`\stackrel{ˇ}{𝒢}`$ and $`\stackrel{ˇ}{G}`$ so that this map is one-to-one222Of course, $`\omega ^L`$ and $`\omega ^R`$ are also restricted by the condition that $`F_\nu (\gamma \mathrm{ad}_\omega )`$ must be well-defined for $`\omega =\omega ^L,\omega ^R`$, but here we suppress this dependence of the domain $`\stackrel{ˇ}{𝒫}`$ on the parameters $`\gamma `$ and $`\nu `$ for brevity. A maximal domain arises naturally in the limit $`\gamma 0`$, which is used in (52)., the PB $`\gamma \{,\}_{\stackrel{ˇ}{P},\nu }`$ on $`\stackrel{ˇ}{P}`$ gives rise to a PB on $`\stackrel{ˇ}{𝒫}`$, which we denote by $`\{,\}_{\stackrel{ˇ}{𝒫}}^{\nu ,\gamma }`$. We then perform the limit $`\gamma 0`$, but in such a way that at the same time we let $`\nu `$ to be a function $`\nu _\gamma `$ for which

$$\underset{\gamma 0}{lim}(\gamma \nu _\gamma )=\tau $$
(51)
with some constant $`\tau `$. For functions $`\mathrm{\Psi }_1,\mathrm{\Psi }_2`$, the formula

$$\{\mathrm{\Psi }_1,\mathrm{\Psi }_2\}_{\stackrel{ˇ}{𝒫}}^\tau (\omega ^L,g,\omega ^R):=\underset{\gamma 0}{lim}\{\mathrm{\Psi }_1,\mathrm{\Psi }_2\}_{\stackrel{ˇ}{𝒫}}^{\nu _\gamma ,\gamma }(\omega ^L,g,\omega ^R)$$
(52)
is easily seen to define a PB on $`\stackrel{ˇ}{𝒫}`$. In fact, by inspecting the PBs of the basic variables $`g,\omega ^L,\omega ^R`$, we find that the PB $`\{,\}_{\stackrel{ˇ}{𝒫}}^\tau `$ has the form of the ansatz (7) with

$$(\omega )=_\tau (\mathrm{ad}_\omega )\text{where}_\tau (z):=\tau \mathrm{coth}(\tau z)z^1.$$
(53)
Since $`_\tau =0`$ for $`\tau =0`$, $`\{,\}_{\stackrel{ˇ}{𝒫}}^\tau `$ reproduces the original PB (3) on $`\stackrel{ˇ}{𝒫}`$ for $`\tau =0`$. For $`\tau =1`$ (53) becomes the canonical $`r`$-matrix in (11), and for an arbitrary $`\tau 0`$ it yields a solution of the CDYBE (9) with right hand side given by $`=\tau ^2f`$.

Thus the canonical $`r`$-matrix (11) is indeed a scaling limit of the $`r`$-matrices given by Proposition 2. This $`r`$-matrix serves as a source of many solutions of the CDYBE on subalgebras $`𝒢`$ by using Dirac reduction and by taking various limits . Its generalizations given by Proposition 2 may perhaps play an analogous role in the PL context, but this leads to questions outside the scope of the present Letter. Another open problem that could be interesting to study is to quantize these $`r`$-matrices. The related problem of quantizing solutions of the CDYBE on a non-Abelian base, such as on $`𝒢`$, has been investigated recently in .

Note added in proof upon publication in Lett. Math. Phys.: In the meantime we have found the change of variables alluded to at the end of Section 2. As will be described elsewhere, it operates by mapping the group-valued variable $`\mathrm{\Omega }`$ to the WZNW monodromy matrix $`M:=\mathrm{exp}(2\nu \mathrm{log}\mathrm{\Omega })`$.

## Acknowledgments

We are grateful to A. Gábor and J. Balog for discussions and for comments on the manuscript. L.F. was supported in part by the Hungarian Scientific Research Fund (OTKA) under T034170, T030099, T029802 and M036804.


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# Superconductivity in carbon nanotubes coupled to transition metal atoms.

## Abstract

The electronic structures of zig-zag and arm-chair single-walled carbon nanotubes interacting with a transitional-metal atomic nanowire of Ni have been determined. The Ni nanowire creates a large electron density of states (DOS) at the Fermi energy. The dependence of the enhanced DOS on the spin state and positioning of the transition-metal wire (inside or outside the nanotube) is studied. Preliminary estimates of the electron-phonon interaction suggest that such systems may have a superconducting transition temperature of $``$ 10-50 K. The signs of superconductivity seen in “ropes” of nanotubes may also be related to the effect of intrinsic transition-metal impurities.

The discovery of carbon nanotubes (CNT) has given rise to fascinating basic physics as well as tantalizing technological possibilitiesmit . The synthesis of CNTs naturally incorporates transition-metal (TM) atoms like Ni, Co, which are used as “seeds” for initiating growth. In addition, TM impurities are found in CNTs, as adsorbed species inside or outside the CNT walls. TM atoms occurring as substitutional impurities are energetically unfavourable, and annealing converts them into adsorbed speciesandriotisMD . Many studies of CNTs with alkali, Au, Ti, Co, Ni, etc., and rare earth atoms, have appeared in the literature and have clarified the binding energies and other aspects of these systemsmit ; meunier . Given the strong $`dd`$ interaction of TM atoms, and the directionality imposed by the CNTs, the TM atoms may form quasi one-dimensional transition-metal nano-wires (TMWs), on the inner or outer surface of the CNTsyang . From a theoretical point of view, the 1-D structure of the CNT, and the 1-D TMW, provide a realization of Luttinger liquids, Bethe ansatz problems, and novel spintronics.

The TMW transfers electrons to the CNTs and can transform semi-conducting CNTs into metals. If the electron density of states (DOS) at the Fermi surface could be strongly enhanced, the coupled system may respond by undergoing a Peierls or a Cooper-pairing transition. In fact, the possibility of superconductive interactions in pure CNTs themselves has been discussed, mainly within the Luttinger-liquid paradigmgonzales . Evidence for superconducting fluctuations, proximity effects etc., in CNTs have been reported tang . The quasi 1-D nature of the TM chain, and the CNT are modified by coupling them when electrons can hop from the CNT to the TMW and back. The Cooper pairing would involve electronic and phononic effects associated with the Ni-C as well as the Ni-Ni and C-C interactions. Even if these do not lead to superconductivity, we may expect some interesting and technologically exploitable properties from the TMW/CNT system.

The objective of this paper is to use tight-binding (TB) schemes, supported by density-functional first-principles calculations, for calculating the electronic energy bands, the density of states, and phonon properties of CNTs coupled to TMWs. The TB results are used for a preliminary discussion of the possibility of superconductivity in these systems. It is concluded that coupled CNT/TMW systems are promising superconductive materials whose special properties may be valuable in a variety of novel applications.

We use TB parameters obtained from fitting to first-principles calculations, or by adapting from Harrison’s universal parametersharrison  when justifiable. Our simulation cells (SC) contain one or two TM atoms and also one or two CNT unit cells, as the case may be. Single-walled CNTs are specified by the pair of numbers (n,m) which defines the chirality of the nanotube. These numbers specify the way a 2-dimensional graphite sheet is rolled to obtain the CNT. While the $`\pi `$\- electron system in the generic graphite sheet makes it conducting, the metallic or semiconducting nature of the CNT (i.e, its bandgap) is determined by the chosen (n,m) configuration. In this study we consider the two extreme sets, (n,0) and (n,n), which correspond to the zig-zag (ZZ) and arm-chair (AC) configurations.

The use of two Ni atoms per simulation cell allow us to consider ferro- or antiferromagnetic nearest-neighbour coupling. If one TM atom per SC were used, the Ni-Ni interaction is negligible and we have the case of doping with almost isolated TM atoms. A first-principles study of a 1-D chain of Ni atoms in isolation has been carried out by Freeman and colleaguesfreeman , and used to obtain the tight-binding parameters for the Slater-Koster method. While the diagonal parameters are strongly modified from the “universal” parameters of Harrison, the off-diagonal universal parameters are quite close to the results obtained from the fit to the first-principles calculations. The TB parameters are further evolved into a set of parameters which depends on the antiferromagnetic or ferromagnetic coupling between Ni neighbours by making the on-site energy of the Nickel $`d`$-orbital a function of the spin state of the Ni atom. Thus we have used $`ϵ_dϵ_d`$ = $`J`$ with a value of $`J`$ corresponding to the bulk Ni value. A better estimate, suitable for the 1-D chain may be obtained by fitting to a first-principles calculation, but the results are found to be rather insensitive to the spin configuration and may be considered illustrative. The bandstructure and DOS of the Ni wire (uncoupled from the CNT) are seen in panel (a) of Fig. 1. Here the, Ni wire which registers with the armchair CNT is a linear chain. The Ni wire which registers with the zigzag CNT is itself a zigzag chain. Its bandstructure and DOS before coupling to the CNT are shown in panels (a) of Fig. 2.

In panels (b) of Figs. 12 we show the bandstructure and DOS of the CNTs before coupling to the TMWs. The Slater-Koster approach for obtaining the electronic states of CNTs within a $`sp^3`$ basis is used. Many TB calculations for CNTs have been reported and the procedure is now well established. The AC(9,9) CNT, panel (b) of Fig. 1, has two bands crossing the Fermi energy near 2/3 of the $`\mathrm{\Gamma }X`$ line and hence it is metallic. The ZZ systems become metallic for specific values of n (for multiples of 3), and the bandgap for the semiconducting case is, to first order, a function of $`1/d`$. Here $`d`$ is the ideal CNT diameter given by $`d=(a_L/\pi )(m^2+m^2+mn)^{1/2}`$, where $`a_L=0.245`$ nm is the lattice constant in the 2-D graphene sheet. Panel (b) shows a very small flat DOS at $`E_F`$ for the isolated CNT. Figure 2 shows, in panels (b) the bandstructure and DOS of the zig-zag (12,0) nanotube without coupling to the TMW. Here also, although the nanotube is metallic, its small DOS at $`E_F`$ is hardly visible in panel (b).

We position the nanowire inside, or outside the CNT, and interacting with the carbon $`s`$ and $`p`$ bonded network forming the CNT wall. The TMW binds chemically to the CNT, unlike in the case of, e.g., Au or Al. The interaction of Ni atoms with CNTs have also been studied by Andriotis et al.andriotisMD , who determined the relaxation of substitutional and also adsorbed Ni atoms near (or inside)a single-walled CNT. Their simulations show that a Ni atom may migrate into a CNT, from the outside, using a vacancy in the CNT wall. These calculations, as well as other studies, already provide us with information regarding the optimal Ni-C distance ($``$ 0.2 nm). For the two-Ni SC we have taken the Ni-Ni bond to be nearly the same as that of the isolated nanowirefreeman , and registering with the $`a_L`$ distance on the CNT wall. This is consistent with the fact that the local structure of the CNT is only minimally affected by the presence of an adsorbed Ni atom inside or outside the CNT wall. However, as seen from our calculations, a large electron density of states is created at the Fermi point by the Ni nanowire, and the CNT becomes conducting, even if it were originally semiconducting (however, this is not always the case in Ti nanowires). The results for the coupled CNT/TMW are given in panels (c) of Figs.1-2.

The bandstructure of the Ni-wire/CNT system, panel (c), shows a nearly dispersionless (“flat”) band which crosses the Fermi energy, and also other Ni-like bands which show greater dispersion. The “flat” band relates to electron hopping via the Ni-C bond which is localized. It provides transport via hopping from the CNT to the TMW and back. The bands with linear dispersion found at the Fermi energy of isolated AC nanotubes (used in bosonization approaches) are no longer present in the coupled CNT/TMW systems. Note that the linear-k bands crossing $`E_F`$ in panel (b) have been repelled apart in the coupled AC system (c) and the bands derived from the Ni atoms are inserted near the Fermi energy. Also, the doubly degenerate bands in panel (b) are split in panel (c).

The density of states of the Ni chain, the (9,9)CNT and the coupled system are shown in Fig. 1. The main change in the DOS is the enhancement at and around the Fermi energy. The splitting of the bands has smoothened the DOS, as seen by comparing panels (b) and (c). Similar results are found in the density-functional calculations of Yang et al for metallic Ti nanowires coupled to CNTs.

Our calculations, and those of Yangyang  for Ti show that there is significant electron transfer between the CNT and the TM. The density of states $`N(ϵ_F)`$ for one-Ni atom in the simulation cell ( i.e, isolated Ni atoms) is three to four times stronger than the case with two-Ni atoms per cell. The TM wire retains some of its electrons on the wire, while the isolated Ni atoms inject more electrons into the CNT (this needs further confirmation from a more microscopic calculation). On the other hand, if one Ni atom were used in a simulation cell of 3 units, then the doping level would be lower and the effect is less. This implies that about 3-4% of Ni atoms in (9,9) or (12,0) nanotubes would be optimal for a highly enhanced $`N(ϵ_F)`$.

The presence of a significant density of states at the Fermi energy opens the possibility of structural relaxation via the electron-lattice interaction. This was in fact considered by Mintmire et al., and also Saito et al.mintmire , who concluded that the CNTs are stable with respect to Peierls-type distortions. The density-functional total-energy minimisations of Yang et al.yang  for CNTs coupled to Ti nanowires show only a slight local modification of the CNT lattice. Our calculations agree with this and the main effect arises from electron transfer and self-consistent readjustment of the Fermi energy. Hence we conclude that, even if isolated CNTs are unstable, the coupled CNT/TMW systems are stable with respect to Peierls distortions, and that the enhanced DOS, $`N(ϵ_F)`$ at the Fermi energy is available for modification by more subtle processes like Cooper pairing.

Graphite intercalation compounds (GIC) have very low transition temperatures $`T_c1`$ K, and $`N(ϵ_F)`$ values of $``$ 1-2 states/eV-spin for 60 Carbon atoms, and compares with the $`N(ϵ_F)10`$ states/eV-spin-C60 of alkali-doped fullerenes (ADF). Superconductivity in the ADFs have been discussed using purely electronic mechanismskievelson , but mostly using the McMillan-Eliashberg (ME) approach within the Migdal approximationschluter . Migdal’s approximation is more easily justified in the CNT/TMW systems for processes mediated by the heavy transition-metal atoms. Schluter et al.schluter , argued that the electron-phonon interaction in the ADFs is larger than in GICs because of the curvature effect absent in the GICsschluter . This argument applies equally to CNTs. The superconductivity in ADFs involves not only the “on-ball” processes, but also the much weaker hopping in a 3-D system of fullerene molecules. In studies on superconductivity of CNTs, the quasi 1-D character is claimed to be overcome by weak hopping between single CNTs in “ropes” of nanotubes. This hoping involves tunnelling through non-bonding interactions and is very poor. In fact, calculations by Delaney et al.delaney  show that the non-bonding interactions suppress the 1-D conductivity. On the other hand, in CNT/TMW coupled systems, electron transfer between two nanotubes occurs effectively via physical metallic contact between TMWs on adjacent CNT/TMW strands. Hence the systems aquire 3-D character and the main issue is to study the nature of the interactions on the individual CNT/TMW elements.

A force-constants model for the CNTssaitoP , extended to include Ni-Ni and Ni-C interactions can be used to study the phonons of the CNT/TMW system. Depending on the force constants we use, the high frequency Ni-Ni vibrations fall between 200-300 cm-1 and strongly interact with the “breathing” and “twisting” modes of the CNTs, while leaving the carbon high-energy optical modes relatively unaffected, except for lifting all degeneracies. The axial symmetry of the isolated CNT is broken in the coupled system, and a rich redistribution of the low-energy phonon modes is found.phonons  The radial modes are not too important in ADFs since they have little effect on the electronic structure at the Fermi level. In contrast, radial modes in the CNT/TMW systems couple strongly with the Fermi level bandstructure, and are many times more efficient in electron-phonon (e-p) coupling than the stiffer tangential modes. The e-p interaction associated with electron hopping between the CNT and the TMW, and along the TMW would bring new, strong coupling features absent in the pure CNTs. Electron transport in the Ni bands would also be subject to strong e-p interactions. The electron-phonon coupling constant is of the form

$$\lambda =N(ϵ_F)V=N(ϵ_F)\underset{i}{}\eta _i/<M_i\omega _i>$$
(1)
where the sum runs over all vibrational modes, with atomic masses $`M_i`$, and $`\omega _i`$ and $`\eta _i`$ being averaged contributions from phonon frequencies and Hopfield factors for the electronic states. The $`N(E_F)`$ depends somewhat on the Ni-spin configuration (ferro or antiferro), the location of the TMW (inside or outside the CNT), and the nature of the CNT (ZZ, AC), as seen in Table I, but a “grosso modo” value is 0.035 states/(eV-spinstate). To clarify the notation we have used here, (12,0)F$`Ni_2`$ indicates a calculation for a ZZ nanotube with two Ni atoms in a simulation cell containing 1 unit cell of the ZZ-CNT. Hence there are 48 carbon atoms, with 192 states, and each Ni atom has one $`s`$ and 5 $`d`$ states. The total number of spin-states is 408 per simulation cell, yielding a total $`N(ϵ_F)`$ of about 12 states per eV per simulation cell. The number reported in the Table is the $`N(ϵ_F)`$ per eV per spin-state. In the (9,9)AC system we use one unit cell in the simulation cell, giving 72 carbon atoms and two Ni atoms. The normalization enables us to compare the different structures given in Table I. When there is only one Ni atom per SC, there are no Ni-Ni interactions and the Ni electrons are (3-4% doping) most effective in augmenting the $`N(ϵ_F)`$ in ZZ nanotubes.

The 0.035 per eV per spin-state as defined previously is comparable to that in ADFs where $`N(E_F)`$ of 2-8 states/(eV-spin-$`C_{60}`$) have been quotedkumar ; schluter  The $`T_c`$ depends on the Coulomb parameter $`\mu `$. Koch et al.koch  have argued that $`\mu `$ is $``$ 0.1-0.2 even though the reduction due to retardation effects is absent in fullerene-like systems. Hence, using this range of parameters, the $`T_c`$ of CNT/Ni-wire coupled systems is found to be in the range 10-50 Kelvin.

A natural implication of our study is that the observed signs of CNT superconductivitytang , e.g., in “ropes” of CNTs may be due to intrinsic doping by TM impurities which cannot be removed completelydujardin . This can be examined via experiments in which the TM impurities are added or leached out in a controlled way. When isolated Ni atoms are attached, e.g, one Ni per 48 carbon atoms in a (12,0) CNT, the $`N(ϵ_F)`$ is enhanced. The random Ni-Ni contacts between such CNTs in ropes of CNTs could provide the higher dimensionality needed to stabilize the superconductivity. In conclusion, our calculations on CNT/TM systems suggest that couplings to suitable TM atoms stabilize any inherent superconductivity in the CNTs. These conclusions, based on tight-binding methods should stimulate more microscopic calculations as well as new experiments.


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# Enrichment of CH3F nuclear spin isomers by resonant microwave radiation

## I Introduction

Nuclear spin isomers of symmetrical molecules are fascinating objects Landau81 . Their properties are determined by nuclei’ spins deeply hidden in the molecule. Most known are the hydrogen isomers that demonstrate anomalous stability, 1 year at ambient temperature and pressure Farkas35 . Latest results on hydrogen isomers can be found in Ilisca92 ; Ilisca99PRL  and references therein. Many other molecules have spin isomers too. But so far their physical properties remain almost unknown. This makes investigations of spin isomers fundamentally important. Spin isomers have also practical applications, e.g., as spin labels, in isomer selective chemical reactions Quack77MP ; Uy97PRL , or in isomer enhanced NMR technique Bowers86PRL ; Natterer97PNMRS . These applications are developed solely with hydrogen isomers. Extension to other molecules needs efficient methods of isomer enrichment. For a long time enrichment of only hydrogen isomers was possible. Recently a few separation methods for polyatomic molecules have been developed (see the review Chap99ARPC ) that has advanced the field significantly. Further progress needs new enrichment methods.

New approach to the problem of isomer enrichment is based on the use of strong electromagnetic radiation. There are two modifications of the method. In the first one Ilichov98CPL ; Shalagin99JETPL  (earlier discussion of the radiation effects see in Ilisca88CPL ), radiation populates specific states of one spin isomer situated in the vicinity of states of other isomer that consequently results in the enrichment. In the second method Chap01PRA2 , enrichment appears due to combined action of population transfer, dynamical shift of molecular levels and light induced coherence. The latter method (coherent control of spin isomers) promises to be more efficient. To avoid any confusion, we note that the light-induced enrichment resulting from stimulating conversion of spin species differs radically from the previously known separation methods, e.g., light-induced drift method which separates physically the isomers Chap99ARPC .

There are no proofs yet that light-induced enrichment of spin isomers is feasible. We are aware of only one attempt to verify the proposals. It was done by microwave excitation of rotational transition in CH3F. The experiment did not give a positive result. At the time when this experiment was performed, only a qualitative theoretical model of the light-induced enrichment was available Ilichov98CPL . Presently, the understanding of the underlying physics has been improved substantially. In view of further experiments in this area it is desirable to examine the microwave induced enrichment of CH3F spin isomers in more detail. This is the goal of the present paper. Existing theoretical models of coherent control cannot be used for quantitative analysis directly because of their lacking to account the $`M`$-degeneracy of molecular states. Account of such degeneracy is another goal of this paper.

## II Qualitative picture and kinetic equation

Previous analysis has shown that significant enrichment can be obtained if radiation interacts with the states having large difference in populations. In this context, microwave excitation is not the best option but it has some advantages also. Theoretical description is simpler for pure rotational excitation. The levels positions are better known for ground vibrational states. From the experimental side, it is easier to find a radiation having proper frequency because of better frequency tunability of microwave sources.

We start with brief qualitative description of the phenomenon. CH3F has two types of states, ortho and para, shown in Fig. 1. The data in this figure correspond to the 13CH3F molecule and have been calculated using the molecular parameters from Papousek94JMS . Spin isomers of CH3F are distinguished by the total spin of the three hydrogen nuclei, $`I=3/2`$ for ortho and $`I=1/2`$ for para isomers. For ortho isomers only rotational quantum numbers $`K=0,3,6..`$ are allowed ($`K`$ is the projection of molecular angular momentum, J, on the molecular symmetry axis.) For para molecules only $`K=1,2,4,5\mathrm{}`$ are allowed Landau81 .

There are two close pairs of ortho and para states in the ground vibrational state of 13CH3F that are significantly mixed by the intramolecular perturbation, $`\widehat{V}`$, and that are important for the ortho-para conversion in the molecule. For a qualitative description, let us take into account only one of these pairs, $`mn`$, and assume that there is no external radiation yet. Suppose that the test molecule is placed into the ortho subspace. Due to the rotational relaxation caused by collisions, the molecule starts to shuttle up and down along the ladder of rotational states. Nonmagnetic collisions do not change the nuclear spin state directly, i.e., the relevant cross-section is zero, $`\sigma (ortho|para)=0`$. This shuttling along the rotational states inside the ortho subspace continues until the molecule jumps to the state $`m`$. During the free flight after that collision the intramolecular perturbation, $`\widehat{V}`$, admixes the para states $`n`$ to the ortho state $`m`$. Consequently, the next collision has a probability (usually very small) to transfer the molecule to other para states. This localizes the molecule inside the para subspace and the spin conversion occurs. This is the mechanism of radiation free nuclear spin conversion induced by the intramolecular state mixing Curl67JCP  (see also Chap91PRA ).

In case of a strong microwave radiation applied to the molecular transition $`qn`$ in the para subspace, mixing of the states is affected by the radiation which allows to control the ortho-para conversion. Influence of a radiation comes through the three major effects, level shift (dynamical Stark effect, well-known in nonlinear laser spectroscopy Rautian79 ; Cohen-Tannoudji92 ), level population change, and light-induced coherence. In general, these three components cannot be separated and work together.

In order to consider a real molecule, the above simplified picture has to be developed further. One has to account the molecular center-of-mass motion. Although the intramolecular mixing does not depend on molecular velocity, the radiation-molecular interaction does. Consequently, the ortho-para state mixing in coherent control depends on molecular velocity too.

Another complication comes from the degeneracy of molecular states. Even for the simplest case of pure radiation polarization (linear or circular) there are many excitation channels each having its own absorption coefficient and saturation parameter. These channels differ by $`M`$-quantum number, projection of J on the laboratory axis of quantization. It is important also to keep in mind that there are other degeneracies of states. Each state of 13CH3F in Fig. 1 is determined by the set of rotational quantum numbers ($`J,K,M`$), total spin of three hydrogen, $`I`$, its projections on the laboratory $`z`$-axis, $`\sigma `$, and $`z`$-projects of spins of carbon and fluorine nuclei, both having spin 1/2. The energy of rotational states of CH3F depends only on $`J`$ and $`K`$ quantum numbers, if tiny hyperfine contribution to the level energy is neglected. We end the qualitative picture by summarizing important parameters of 13CH3F in Table 1.

Quantitative analysis of the isomer coherent control will be performed using kinetic equation for the density matrix, $`\widehat{\rho }`$. The molecular Hamiltonian reads,

$$\widehat{H}=(\mathrm{}^2/2m_0)_𝐫^2+\widehat{H}_0+\mathrm{}\widehat{G}+\mathrm{}\widehat{V}.$$
(1)
Here the first term is the Hamiltonian of the molecular center-of-mass motion with $`m_0`$ being the molecular mass. The main part of the molecular internal Hamiltonian, $`\widehat{H}_0`$, has the eigen ortho and para states shown in Fig. 1. $`\mathrm{}\widehat{G}`$ describes the molecular interactions with the external radiation that will be taken in the form of monochromatic travelling wave,

$$\widehat{G}=(𝐄_0\widehat{𝐝}/\mathrm{})\mathrm{cos}(\omega _Lt\mathrm{𝐤𝐫}),$$
(2)
where $`𝐄_0`$, $`\omega _L`$ and $`𝐤`$ are the amplitude, frequency and wave vector of the electromagnetic radiation, respectively; $`\widehat{𝐝}`$ is the operator of the molecular electric dipole moment. $`\widehat{V}`$ is the intramolecular perturbation that mixes the ortho and para states in 13CH3F. The mixing of $`mn`$ pair ($`J`$=9,$`K`$=3–11,1) is performed by the spin-spin interaction between the molecular nuclei Chap91PRA ; Chap00EPJD , The pair $`m^{}n^{}`$ (20,3–21,1) is mixed by the spin-spin and spin-rotation interactions Chap91PRA ; Guskov99JPB ; Ilisca98PRA ; Cacciani02 . Account of the level degeneracy for the light-molecular interaction is a difficult problem, in general. It is most simple for the case of pure polarization, linear or circular. We will consider the electromagnetic radiation having linear polarization.

In the representation of the eigen states of $`\widehat{H}_0`$ ($`\alpha `$-states) and classical description of the molecular center-of-mass motion, kinetic equation reads Rautian79 ,

$$𝝆/t+𝐯𝝆=𝐒i[𝐆+𝐕,𝝆].$$
(3)
Here $`𝐒`$ is the collision integral; $`𝐯`$ is the molecular center-of-mass velocity. Spontaneous decay is not included in this equation because it is negligible for rotational transitions in comparison with the collisional relaxation.

Kinetic equation for the total concentration of para molecules can be obtained directly from Eq. (3),

$$\rho _p/t=2Rei(\rho _{m^{}n^{}}V_{n^{}m^{}}+\rho _{mn}V_{nm})𝑑𝐯.$$
(4)
Here the total concentration of para molecules, $`\rho _p=_\alpha \rho _p(\alpha ,𝐯)d𝐯,\alpha `$ para. Summation is made over all degenerate sublevels of the states $`m^{},n^{}`$ and $`m,n`$. In Eq. (4) a uniform spatial distribution of molecular density was assumed. Collision integral did not enter into Eq. (4) because by assumption collisions do not change the molecular spin state, i.e., $`_\alpha S_{\alpha \alpha }𝑑𝐯=0`$, if $`\alpha `$ ortho, or $`\alpha `$ para. G did not enter into Eq. (4) either because the matrix elements of G off-diagonal in nuclear spin states vanish.

The off-diagonal matrix elements $`\rho _{mn}`$ and $`\rho _{m^{}n^{}}`$ will be found in perturbation theory. Further we assume the perturbations $`\widehat{V}`$ being small and consider zero- and first-order terms of the density matrix,

$$𝝆=𝝆^{}+𝝆^{\prime \prime }.$$
(5)
Collisions in our system will be described by the model standard in the theory of light-molecule interaction. The off-diagonal elements of $`𝐒`$ have only decay terms,

$$S_{\alpha \alpha ^{}}=\mathrm{\Gamma }\rho _{\alpha \alpha ^{}};\alpha \alpha ^{}.$$
(6)
The decoherence rates, $`\mathrm{\Gamma }`$, are taken equal for all off-diagonal elements of collision integral. This assumption simplifies the theoretical model. Note, that the dependence of the relaxation rates on rotational quantum numbers is known Trappeniers79JCP .

The diagonal elements of $`𝐒`$ are expressed through the kernel of collision integral, $`A`$, in a usual way,

$$S(\alpha ,𝐯)=\underset{\alpha _1}{}A(\alpha ,𝐯|\alpha _1,𝐯_1)\rho (\alpha _1,𝐯_1)𝑑𝐯_1\rho (\alpha ,𝐯)\underset{\alpha _1}{}A(\alpha _1,𝐯_1|\alpha ,𝐯)𝑑𝐯_1.$$
(7)
We consider the model of strong collisions with the following collision kernel for para molecules

$$A(\alpha ,𝐯|\alpha _1,𝐯_\mathrm{𝟏})=\nu _rw_p(\alpha )\delta (𝐯𝐯_\mathrm{𝟏})+\nu _t\delta _{\alpha \alpha _1}f(𝐯);\alpha ,\alpha _1\text{p}ara,$$
(8)
and similar equation for ortho molecules. $`w_p(\alpha )`$ in Eq. (8) is the Boltzmann distribution of rotational state populations of para molecules,

$$w_p(\alpha )=Z_p^1\mathrm{exp}(E_\alpha /k_BT),$$
(9)
with $`Z_p`$ being the rotational partition function; $`E_\alpha `$ the rotational energy of $`\alpha `$-state; $`T`$ the gas temperature; $`k_B`$ the Boltzmann constant. The symmetry of CH3F is such that the partition functions for ortho and para molecules are practically equal at room temperature. Partition functions account all degeneracies of states (see Ref. Chap91PRA  for more details); $`f(𝐯)`$ in Eq. (8) is the Maxwell distribution,

$$f(𝐯)=\pi ^{3/2}v_0^3\mathrm{exp}(𝐯^2/v_0^2);v_0=\sqrt{2k_BT/m_0}.$$
(10)
In Eq. (8), two relaxation rates were introduced, rotational relaxation ($`\nu _r`$) that does not affect molecular velocity and translational relaxation ($`\nu _t`$) that equilibrates velocity but do not change rotational state. Note that the rotational relaxation is accompanied in our model by the relaxation in $`M`$ quantum numbers. Note also, that the collisions in the model do not change the molecular spin state. The introduction of different relaxation rates for different degrees of freedom makes the model of strong collisions more accurate and flexible. It allows to adjust the model to the particular experimental conditions. Because of its simplicity model of strong collisions is often used in laser physics and nonlinear spectroscopy, see, e.g., Rautian79 ; Dykhne80JETP ; Mironenko81IANS . Numerical values for the collisional parameters $`\mathrm{\Gamma },\nu _r`$, and $`\nu _t`$ will be determined later.

## III Microwave absorption

For the zero-order term of the density matrix one has the following kinetic equation,

$$𝝆^{}/t+𝐯𝝆^{}=𝐒^{}i[𝐆,𝝆^{}].$$
(11)
Electromagnetic field interacts with para molecules only. Consequently, ortho molecules remain at equilibrium in the zero-order perturbation theory. For the level populations of ortho molecules one has,

$$\rho _o^{}(\alpha ,𝐯)=(N\rho _p^{})w_o(\alpha )f(𝐯),$$
(12)
where $`N`$ is the total concentration of molecules.

Eqs. (6),(7),(8), and (11) allow to deduce an equation for the stationary populations of para molecules,

$$(\nu _r+\nu _t)\rho _p^{}(\alpha ,𝐯)=\nu _rw_p(\alpha )\rho _p^{}(𝐯)+\nu _tf(𝐯)\rho _p^{}(\alpha )+\rho _p^{}p[\delta _{\alpha q}\delta _{\alpha n}],$$
(13)
where the excitation probability, $`p`$, is defined as,

$$\rho _p^{}p=\frac{2\mathrm{\Gamma }|G_{qn}|^2}{\mathrm{\Gamma }^2+(\mathrm{\Omega }\mathrm{𝐤𝐯})^2}\left[\rho _p^{}(n,𝐯)\rho _p^{}(q,𝐯)\right].$$
(14)
In Eq. (13) the notations were introduced,

$$\rho _p^{}(𝐯)=\underset{\alpha para}{}\rho _p^{}(\alpha ,𝐯);\rho _p^{}(\alpha )=\rho _p^{}(\alpha ,𝐯)𝑑𝐯.$$
(15)
Eq. (14) is written in the rotating wave approximation. Nonzero matrix elements of $`𝐆`$ (electric field has linear polarization along $`z`$-axis) are given by,

$$G_{qn}=G(M)e^{i(\mathrm{𝐤𝐫}\mathrm{\Omega }t)};G(M)E_{10}(\overline{d_{10}})_{qn}/2\mathrm{},$$
(16)
where $`\mathrm{\Omega }=\omega _L\omega _{qn}`$ is the radiation frequency detuning from the absorption line center, $`\omega _{qn}`$; the bar over a symbol indicates a time-independent factor; $`E_{10}`$ and $`d_{10}`$ are spherical components of the electric field and electric dipole moment vectors, respectively Landau81 . The matrix elements of $`\widehat{d}_{10}`$ reads Landau81 ,

$$|(\overline{d_{10}})_{qn}|^2|d(M)|^2=(2J_q+1)(2J_n+1)\left(\begin{array}{ccc}J_q& 1& \hfill J_n\\ K& 0& \hfill K\end{array}\right)^2\left(\begin{array}{ccc}J_q& 1& \hfill J_n\\ M& 0& \hfill M\end{array}\right)^2d^2,$$
(17)
where (:::) stands for the 3j-symbol and $`d`$ is the permanent electric dipole moment of CH3F, $`d=1.86`$ D Freund74JMS .

Solution of Eq. (13) has no difficulty and can be presented in the form,

$$\rho _p^{}(\alpha ,𝐯)=\rho _p^{}w_p(\alpha )f(𝐯)+\rho _p^{}[(\tau _2\tau _1)p_1f(𝐯)+\tau _1p][\delta _{\alpha q}\delta _{\alpha n}],$$
(18)
where the relaxation times are $`\tau _1=(\nu _r+\nu _t)^1`$, $`\tau _2=\nu _r^1`$, and $`p_1=p𝑑𝐯`$. We have separated here the field-induced contributions nonequilibrium in $`\alpha `$ and v and nonequilibrium only in $`\alpha `$. Solution (18) shows that radiation affects the population of only two states, $`q`$ and $`n`$. This is the consequence of the accepted simple model of collisions.

The excitation probability can be found from Eqs. (14) and (18),

$`p_1`$ $`=`$ $`{\displaystyle \frac{0.5\mathrm{\Delta }w}{\tau _1(\kappa R)^1+\tau _2\tau _1}},`$
$`p`$ $`=`$ $`{\displaystyle \frac{\mathrm{\Gamma }^2f(𝐯)}{\mathrm{\Gamma }_B^2+(\mathrm{\Omega }\mathrm{𝐤𝐯})^2}}{\displaystyle \frac{p_1}{R}},`$ (19)
where the difference of the Boltzmann factors is $`\mathrm{\Delta }w=w_p(n)w_p(q)`$; the saturation parameter, $`\kappa `$, and saturation intensity, $`S_{sat}`$, are

$$\kappa =\frac{S}{S_{sat}},S_{sat}=\frac{c\mathrm{\Gamma }\mathrm{}^2}{8\pi \tau _1|d(M)|^2};$$
(20)
the homogeneous line width is $`\mathrm{\Gamma }_B=\mathrm{\Gamma }\sqrt{1+\kappa }`$, and

$$R=\frac{\mathrm{\Gamma }^2f(𝐯)d𝐯}{\mathrm{\Gamma }_B^2+(\mathrm{\Omega }\mathrm{𝐤𝐯})^2}.$$
(21)
This integral can be expressed through the probability integral, but for numerical calculations performed in this paper it is easier to calculate it straightforward.

In a similar way one can obtain from the kinetic equation (11) the off-diagonal density matrix element,

$$\overline{\rho }_{qn}^{}=i\frac{\rho _p^{}}{\overline{G}_{nq}}\frac{p}{2\mathrm{\Gamma }}[\mathrm{\Gamma }+i(\mathrm{\Omega }\mathrm{𝐤𝐯})].$$
(22)
We can adjust now parameters of the collision kernel (8). Kinetic equation (11) describes a diffusion process with the diffusion coefficient, $`D=v_0^2/2\nu _t`$. Diffusion coefficient for CH3F is equal to $`D10^2`$ cm2/s at the pressure 1 Torr. This determines the velocity equilibration rate, $`\nu _t=4.410^7`$ s-1/Torr.

Attenuation of the radiation is given by $`\mathrm{}\omega _L\rho _p_Mp_1`$. Consequently the absorption coefficient, $`\chi (\mathrm{\Omega })`$, is determined by the expression,

$$\chi (\mathrm{\Omega })=\mathrm{}\omega _L\rho _pS^1\underset{M}{}p_1.$$
(23)
In the low field limit ($`\kappa 0`$) it is reduced to,

$$\chi _{low}(\mathrm{\Omega })=\frac{\mathrm{}\omega _L}{2\tau _1}\rho _p\mathrm{\Delta }wR_{low}\underset{M}{}S_{sat}^1,$$
(24)
where $`R_{low}=lim_{S0}R`$ is the Foigt profile of the absorption line. If $`\mathrm{\Gamma }kv_0`$ the absorption line is Lorentzian having the width equal $`\mathrm{\Gamma }`$. Experimental data on $`\chi (\mathrm{\Omega })`$ for the rotational transition $`11,112,1`$ can be used to determine the value of $`\mathrm{\Gamma }`$. Equally, broadening of any other rotational transition can be used because in our collision model (6) one has the same $`\mathrm{\Gamma }`$ for all off-diagonal density matrix elements. There are experimental results on the broadening of the ortho-para transition (9,3)–(11,1) obtained from the level-crossing resonances in 13CH3F nuclear spin conversion. This experiment gave the value $`\mathrm{\Gamma }/P=1.910^8`$ s-1/Torr Nagels96PRL ; Chap00AMR  that will be used in the present calculations. The last unknown parameter, rotational relaxation, $`\nu _r`$, can be determined, e.g., from the power saturation of the absorption coefficient. This information is not available and we assume $`\nu _r=\mathrm{\Gamma }`$. This is reasonable, because the pressure broadening in molecules is determined mainly by the level population quenching, although this estimation for $`\nu _r`$ is probably too high.

We can now demonstrate the model at work by considering the microwave absorption by 13CH3F. Absorption spectrum is determined by the selection rules $`JJ+1`$, $`KK`$. The spectrum consists of groups of lines nearly equally separated by 50 GHz. Inside each group the lines, different in $`K`$, are rather dense. Spectrum near the line $`11,112,1`$ is shown in Fig. 2. The two spectra correspond to low radiation intensity and to $`S=100`$ mW/cm2 and the gas pressure equal 30 mTorr in both cases.

Saturation intensity for the line $`11,112,1`$ is equal to 43 W/cm2 ($`M=11`$) and 6.8 W/cm2 ($`M=0`$) at the gas pressure 1 Torr. $`S_{sat}`$ is proportional to the pressure squared, thus at 30 mTorr, $`S_{sat}`$6 mW/cm2. An example of the absorption coefficient saturation is given in Fig. 3. Because the Doppler width of the transition is small, $`kv_0=0.74`$ MHz, low field absorption in the line center depends weakly on CH3F pressure if $`P100`$ mTorr. Another example of the saturation effect is shown in Fig. 4. Here the relative level population difference $`[\rho _p(n)\rho _p(q)]/\rho _p\mathrm{\Delta }w`$ is given as a function of radiation intensity. One can see that radiation having $`S=100`$ mW/cm2 decreases the level population difference significantly.

## IV First order theory

The kinetic equation for the first order term of the density matrix $`𝝆^{\prime \prime }`$ is obtained from Eq. (3),

$$𝝆^{\prime \prime }/t+𝐯𝝆^{\prime \prime }=𝐒^{\prime \prime }i[𝐆,𝝆^{\prime \prime }]i[𝐕,𝝆^{}].$$
(25)
Ortho-para conversion is determined by the terms $`\rho _{m^{}n^{}}^{\prime \prime }`$ and $`\rho _{mn}^{\prime \prime }`$ because zero order matrix elements off-diagonal in nuclear spins vanish (see Eq. (4)). Radiation does not affect the levels $`m^{}`$ and $`n^{}`$. Consequently, the matrix element $`\rho _{m^{}n^{}}^{\prime \prime }`$ is not different from the case of the field free conversion Chap91PRA ,

$$\rho _{m^{}n^{}}^{\prime \prime }=\frac{iV_{m^{}n^{}}}{\mathrm{\Gamma }+i\omega ^{}}[\rho _p^{}(n^{},𝐯)\rho _o^{}(m^{},𝐯)],$$
(26)
where $`\omega ^{}\omega _{m^{}n^{}}`$. The density matrix element $`\rho _{mn}^{\prime \prime }`$ can be obtained from the equations which are deduced from Eq. (25),

$`(/t+𝐯+\mathrm{\Gamma })\rho _{mn}^{\prime \prime }i\rho _{mq}^{\prime \prime }G_{qn}`$ $`=`$ $`iV_{mn}[\rho _p^{}(n,𝐯)\rho _o^{}(m,𝐯)];`$
$`(/t+𝐯+\mathrm{\Gamma })\rho _{mq}^{\prime \prime }i\rho _{mn}^{\prime \prime }G_{nq}`$ $`=`$ $`iV_{mn}\rho _{nq}^{}.`$ (27)
Substitutions, $`V_{mn}=\overline{V}_{mn}e^{i\omega t},(\omega \omega _{mn});\rho _{mn}^{\prime \prime }=\overline{\rho }_{mn}^{\prime \prime }e^{i\omega t};\rho _{mq}^{\prime \prime }=\overline{\rho }_{mq}^{\prime \prime }e^{i[(\mathrm{\Omega }+\omega )t\mathrm{𝐤𝐫}]}`$, transform Eqs. (27) to algebraic equations which can be easily solved. The density matrix element that one needs for the kinetic equation (4) reads,

$$\overline{\rho }_{mn}^{\prime \prime }=i\overline{V}_{mn}\frac{[\mathrm{\Gamma }+i(\mathrm{\Omega }+\omega \mathrm{𝐤𝐯})][\rho _p^{}(n,𝐯)\rho _o^{}(m,𝐯)]+i\overline{G}_{qn}\overline{\rho }_{nq}^{}}{(\mathrm{\Gamma }+i\omega )[\mathrm{\Gamma }+i(\mathrm{\Omega }+\omega \mathrm{𝐤𝐯})]+|G(M)|^2}.$$
(28)
Note that indices $`m,n,q`$ in Eqs. (28) represent the set of quantum numbers that comprise all degenerate sublevels. Consequently, one has nonzero terms $`\overline{\rho }_{mn}^{\prime \prime }`$ for the combination of quantum numbers which are allowed by the selection rules for $`\widehat{V}`$.

## V Conversion rates

Solutions for $`\overline{\rho }_{m^{}n^{}}^{\prime \prime }`$ and $`\overline{\rho }_{mn}^{\prime \prime }`$ together with the level populations from Eq. (18) and the off-diagonal matrix element from Eq. (22) allow to present Eq. (4) as,

$$\rho _p/t=N(\gamma _{po}^{}+\gamma _{po})\rho _p\gamma ;\gamma \gamma _{po}^{}+\gamma _{op}^{}+\gamma _{po}+\gamma _{op}\gamma _n\gamma _c.$$
(29)
In this equation we have neglected the small difference between the total concentration of para molecules, $`\rho _p`$, and its zero order approximation, $`\rho _p^{}`$. The partial conversion rates in Eq. (29) have the following definition. The field free conversion rate through the upper level pair, $`m^{}n^{}`$,

$$\gamma _{po}^{}=\frac{2\mathrm{\Gamma }|V_{m^{}n^{}}|^2}{\mathrm{\Gamma }^2+\omega ^2}w_o(m^{}).$$
(30)
Equation for $`\gamma _{op}^{}`$ is obtained from $`\gamma _{po}^{}`$ by substitution the Boltzmann factor $`w_p(n^{})`$ instead of $`w_o(m^{})`$. Summation is made here over all degenerate substates of $`m^{}`$ and $`n^{}`$ states. The rate $`\gamma _{po}`$ is given by,

$$\gamma _{po}=|V_{mn}|^2\left[\frac{2\mathrm{\Gamma }}{\mathrm{\Gamma }^2+\omega ^2}+ReF_1f(𝐯)𝑑𝐯\right]w_o(m)$$
(31)
Equation for $`\gamma _{op}`$ is obtained from $`\gamma _{po}`$ by substitution the Boltzmann factor $`w_p(n)`$ instead of $`w_o(m)`$. The rates $`\gamma _{po}`$ and $`\gamma _{op}`$ are field dependent. Their zero field limits coincide with the field free conversion rates through the pair of states $`mn`$. The “non-coherent” contribution to the conversion, the rate $`\gamma _n`$, originated from the radiation-induced level population change in Eq. (28), is given by,

$$\gamma _n=|V_{mn}|^2\left[\frac{2\mathrm{\Gamma }\tau _2p_1}{\mathrm{\Gamma }^2+\omega ^2}+2Re[(\tau _2\tau _1)p_1f(𝐯)+\tau _1p]F_1𝑑𝐯\right].$$
(32)
And finally, the “coherent” contribution to the conversion rate, $`\gamma _c`$, originated from the $`\overline{\rho }_{nq}^{}`$ in Eq. (28) is,

$$\gamma _c=|V_{mn}|^2\left[\frac{p_1}{\mathrm{\Gamma }^2+\omega ^2}+\frac{1}{\mathrm{\Gamma }}RepF_2𝑑𝐯\right]$$
(33)
In Eqs. (31),(32), and (33) the following functions were introduced,

$`F_1`$ $`=`$ $`\left(1{\displaystyle \frac{\mathrm{\Gamma }_1+i\omega _1}{\mathrm{\Gamma }+i\omega }}\right){\displaystyle \frac{1}{\mathrm{\Gamma }_1+i(\mathrm{\Omega }+\omega _1\mathrm{𝐤𝐯})}};\mathrm{\Gamma }_1=\mathrm{\Gamma }\left(1+{\displaystyle \frac{|G(M)|^2}{\mathrm{\Gamma }^2+\omega ^2}}\right);`$
$`F_2`$ $`=`$ $`{\displaystyle \frac{\mathrm{\Gamma }+\mathrm{\Gamma }_1+i\omega _1}{\mathrm{\Gamma }+i\omega }}{\displaystyle \frac{1}{\mathrm{\Gamma }_1+i(\mathrm{\Omega }+\omega _1\mathrm{𝐤𝐯})}};\omega _1=\omega \left(1{\displaystyle \frac{|G(M)|^2}{\mathrm{\Gamma }^2+\omega ^2}}\right).`$ (34)
Interpretation of the introduced conversion rates can be considered as follows. Strong resonant radiation splits the molecular states, change the levels populations and introduce coherences in the molecule. The field dependent part of $`\gamma _{po}`$ can be considered as due to the radiation induced level crossing. This term has resonance at $`\mathrm{\Omega }=\omega _1`$. The first term of $`\gamma _n`$ is due to the population effect. It has the resonance at $`\mathrm{\Omega }=0`$ where the excitation probability has maximum. The second part of $`\gamma _n`$ is due to the population change and level-crossing. It has two resonances, at $`\mathrm{\Omega }=0`$ and at $`\mathrm{\Omega }=\omega _1`$. The coherent contribution, $`\gamma _c`$, has also resonances at these two frequencies.

The two peaks in the conversion rate spectra have rather distinctive features. The first one, at $`\mathrm{\Omega }=0`$, is quite similar to the radiation free conversion rate, e.g., $`\gamma _{po}^{}`$ (Eq. (30)). In our case $`\omega \mathrm{\Gamma }`$ and the amplitudes of the peaks at $`\mathrm{\Omega }=0`$ are proportional to $`\mathrm{\Gamma }`$, thus to the gas pressure. In the limit $`\omega \mathrm{\Gamma }`$, contributions to the conversion rate provided by these terms are similar to the ordinary gas kinetic processes which are proportional to the gas pressure also.

The resonances at $`\mathrm{\Omega }=\omega _1`$ have completely different signature that would result from a field free conversion pattern of a degenerate ortho-para level pair. In this case the conversion rate has $`1/\mathrm{\Gamma }`$ dependence, see, e.g., Eq. (30). It allows us to refer to the resonances at $`\mathrm{\Omega }=\omega _1`$ as produced by the crossing the ortho and para levels and resulting from the applied electromagnetic field. To reveal this property of the resonances at $`\mathrm{\Omega }=\omega _1`$, let us estimate the integral,

$$I=\frac{f(𝐯)d𝐯}{\mathrm{\Gamma }_1+i(\mathrm{\Omega }+\omega _1\mathrm{𝐤𝐯})},$$
(35)
at the radiation frequency $`\mathrm{\Omega }=\omega _1`$. If the limit of large Doppler broadening is valid, $`\mathrm{\Gamma }_1kv_0`$, the integrand in Eq. (35) has sharp resonance at $`𝐯=0`$. One can substitute $`f(𝐯)`$ by $`f(0)`$ in Eq. (35) and obtain, $`I1/kv_0`$. Thus, the conversion is produced through the degenerate ortho-para level pair (level crossing) having the width equal the Doppler width, $`kv_0`$. In the opposite limit of large homogeneous broadening, $`\mathrm{\Gamma }_1kv_0`$, one can neglect $`\mathrm{𝐤𝐯}`$ in the denominator of the integrand (35) and obtain $`I1/\mathrm{\Gamma }_1`$. Again, this is the conversion through the crossed ortho and para states but having the width $`\mathrm{\Gamma }_1`$ now.

It would be useful to compare the results of the present model with the qualitative model Ilichov98CPL . This comparison cannot be made directly because in Ilichov98CPL  rovibrational excitation of CH3F was considered. But one can apply the idea of light-induced enrichment solely through the level population change and make the comparison. In the present notations, the field effect from the level population change is given by the first term in Eq. (32),

$$\gamma _{n1}=\frac{2\mathrm{\Gamma }|V_{mn}|^2}{\mathrm{\Gamma }^2+\omega ^2}\tau _2p_1.$$
(36)
It gives larger amplitude for the peak at $`\mathrm{\Omega }=0`$ than the present model. In the present model one has partial cancellation of peaks at $`\mathrm{\Omega }=0`$, see the first terms in the expressions for $`\gamma _n`$ and $`\gamma _c`$. Because of the assumption, $`\mathrm{\Gamma }=\nu _r`$, made in the collision model we have two times smaller peak at $`\mathrm{\Omega }=0`$ in the present model. The cancellation is less significant if $`\mathrm{\Gamma }`$ is larger in comparison with $`\nu _r`$.

We turn now to numerical calculations of the conversion rates in 13CH3F. Contribution from $`m^{}n^{}`$ pair is difficult to calculate using Eq. (30) directly because of some uncertainty in the parameters involved. Instead, one can use the experimental value, $`\gamma _{po}^{}=2.310^3`$ s-1/Torr Nagels96PRL ; Chap00AMR  and scale it linear in pressure. Such pressure dependence for $`\gamma _{po}^{}`$ is valid if $`\mathrm{\Gamma }\omega ^{}`$ (see Eq. (30)) which is fulfilled for the pressures $`P<10`$ Torr.

Calculation of the rates $`\gamma _{po}`$, $`\gamma _n`$, and $`\gamma _c`$ needs the matrix elements $`V_{mn}`$. Mixing of the states $`m`$ and $`n`$ is performed by the intramolecular spin-spin interaction between the nuclei of 13CH3F. Dependence of $`V_{mn}`$ on nuclear spin variables is accounted easily by summation because other factors in Eqs. (31)-(33) do not depend on nuclear spins. Then, the only remaining degeneracy is in $`M`$-quantum numbers. This quantity reads,

$$|V_{mn}|^2=(2J_m+1)(2J_n+1)\left(\begin{array}{ccc}\hfill J_m& 2& \hfill J_n\\ \hfill K_m& q& \hfill K_n\end{array}\right)^2\left(\begin{array}{ccc}\hfill J_m& 2& \hfill J_n\\ \hfill M^{}& M^{}M& \hfill M\end{array}\right)^2𝒯_{2,q}^2.$$
(37)
Here $`𝒯_{2,q}`$ ($`q=K_mK_n=2`$) is the magnitude of the spin-spin interaction and summation is made in all nuclear spin projections. The value of $`𝒯_{2,2}`$ calculated from the molecular structure is equal to 69.2 kHz. This value is confirmed by the experiment Cosleou00EPJD . But in this paper we have to take somewhat smaller value, $`𝒯_{2,2}=64.1`$ kHz, as it was obtained self-consistently for the three parameters, $`𝒯_{2,2}`$, $`\mathrm{\Gamma }`$, and $`\gamma _{po}^{}`$ Chap00AMR .

Examples of the conversion rates are shown in Fig. 5. The upper panel gives the rate $`\gamma `$ for two pressures, 30 mTorr and 100 mTorr. The radiation intensity in both cases is equal to 100 mW/cm2. One can see that the peak at $`\mathrm{\Omega }=\omega _1`$ is $``$3 times larger at 30 mTorr than at 100 mTorr. There is also peak at $`\mathrm{\Omega }=0`$ having “negative amplitude” but it is too small to be visible in the upper panel. The lower panel shows the field dependent rates, $`(\gamma _n+\gamma _c)`$. They are taken with the same sign as they contribute to $`\gamma `$ in Eq. (29). One can see from this panel that the pressure dependences of the amplitudes of these two peaks are opposite. This is the consequence of the crossing of ortho and para states at $`\mathrm{\Omega }=\omega _1`$ and off-resonant nature of the peak at $`\mathrm{\Omega }=0`$.

Broadening of the two peaks in the conversion rate are very different too. The peak at $`\mathrm{\Omega }=0`$ has the broadening as ordinary absorption line does. At large saturation parameter, $`\kappa `$, its width is $`2|G|`$ and grows rather fast with intensity. The width of the peak at $`\mathrm{\Omega }=\omega _1`$ is given by $`\mathrm{\Gamma }(1+|G|^2/\omega ^2)`$. Consequently, the power broadening of this peak is very small at our conditions. Fig. 5 illustrates the difference in the peaks widths.

## VI Enrichment

Solution of the kinetic equation (29) can be presented as,

$$\rho _p(t)=\overline{\rho }_p+(\rho _p(0)\overline{\rho }_p)\mathrm{exp}(\gamma t);\overline{\rho }_p=N(\gamma _{po}^{}+\gamma _{po})/\gamma ,$$
(38)
where $`\overline{\rho }_p`$ and $`\rho _p(0)`$ are the steady-state and initial (equilibrium) concentrations of para molecules, respectively. Enrichment of para molecules will be defined as,

$$\beta (\mathrm{\Omega })=\frac{\overline{\rho }_p}{\rho _p(0)}1.$$
(39)
Partition functions for ortho and para isomers of CH3F are equal. Consequently, $`\gamma _{po}^{}=\gamma _{op}^{}`$, $`\gamma _{po}=\gamma _{op}`$ and enrichment, $`\beta (\mathrm{\Omega })`$, can be expressed as,

$$\beta (\mathrm{\Omega })=(\gamma _n+\gamma _c)/\gamma ,$$
(40)
which will be used for the numerical calculations of $`\beta (\mathrm{\Omega })`$. One can note from Eq. (40) that despite the rates $`\gamma _{po}`$ and $`\gamma _{op}`$ have rather large field dependent parts (see Fig. (5)), they alone would not produce an enrichment. It can be understood because these field dependent parts are due to the mixing of states shifted by radiation but having equilibrium populations (see Eq. (31)). Conversion through the mixing of equilibrium populated states does not affect the ortho-to-para ratio. Examples of the enrichment $`\beta (\mathrm{\Omega })`$ are given in Fig. 6. At the pressure 30 mTorr and radiation intensity $`S=100`$ mW/cm2, enrichment peak at $`\mathrm{\Omega }=\omega _1`$ is $``$3% and it is $``$4 times higher than the enrichment at $`\mathrm{\Omega }=0`$. At larger radiation intensity, amplitude of the enrichment peak, $`\beta (\omega _1)`$, saturates at $``$5%. The peak at $`\mathrm{\Omega }=0`$ grows to $``$1%.

The simplified model that accounts only the radiation-induced level population change predicts a factor two higher peak at $`\mathrm{\Omega }=0`$ than the present model. As was discussed above, in the present model one has partial cancellation of contributions originated from the rates $`\gamma _n`$ and $`\gamma _c`$ which results in a smaller enrichment. Another significant difference between these models is that the simplified model does not predict an enrichment at $`\mathrm{\Omega }=\omega _1`$.

Broadening of the two peaks in enrichment is very distinctive and is similar to the peaks of conversion rate, although there is some difference. The enrichment peak at $`\mathrm{\Omega }=\omega _1`$ is broader than the peak of $`\gamma `$ because of large $`\gamma _{po}`$ and $`\gamma _{op}`$ at resonant frequency in the denominator of Eq. (40).

## VII Discussion and Conclusions

We have developed a model of spin isomer coherent control that accounts for the molecular level degeneracy in magnetic quantum numbers. This degeneracy together with the account of molecular center-of-mass motion allow now to apply the model to real molecules, having actual level structure and ortho-para mixing Hamiltonian. The developed model was used to analyse the microwave induced enrichment of spin isomers in 13CH3F. Spectrum of the conversion rate consists of two peaks with the peak at $`\mathrm{\Omega }=\omega _1`$ being two orders of magnitude higher than the peak at $`\mathrm{\Omega }=0`$.

The enrichment spectrum has also two peaks at the same frequencies. One can obtain 3% enrichment using forbidden (for ordinary absorption) resonance at $`\mathrm{\Omega }=\omega _1`$, gas pressure 30 mTorr at room temperature and radiation intensity $`S=100`$ mW/cm2. Amplitude of the peak at $`\mathrm{\Omega }=0`$ is 4 times smaller. Cooling the gas to 200 K would increase enrichment to $``$5% because of the increase of the level population difference. At higher radiation intensity enrichment saturates at $``$5% if the gas temperature $`T=295`$ K and at $``$7% if $`T=200`$ K.

For the practical implementation of the microwave enrichment, the use of the peak at $`\mathrm{\Omega }=\omega _1`$ has a few advantages. Enrichment here is significantly larger than at $`\mathrm{\Omega }=0`$. Moreover, spurious effects can decrease the enrichment at $`\mathrm{\Omega }=0`$ even further. It can be due to the gas heating by radiation. Note, that for the peak at $`\mathrm{\Omega }=\omega _1`$ absorption is negligible and there is no gas heating. Another spurious affect may be due to the resonant exchange of rotational quanta between ortho and para isomers. This effect prevents depopulation of one rotational state by radiation (state $`n`$ in our case) in comparison with the population of the state $`m`$ having nearly equal energy. Again, the peak at $`\mathrm{\Omega }=\omega _1`$ has the advantage of very low absorption coefficient and thus low radiation induced population change. Finally, the disadvantage of the peak at $`\mathrm{\Omega }=0`$ is the spurious absorption by the line $`11,012,0`$ (Fig. 2). Although at low pressures this line is well separated from the line $`11,112,1`$ (the gap is 10 MHz), power broadening partially overlap these lines. On other hand, the peak $`\mathrm{\Omega }=\omega _1`$ is situated at the blue side of the line $`11,012,0`$ being 120 MHz away from the nearest absorption line (Fig. 2).

Enrichment obtained by microwave excitation of 13CH3F at reasonable experimental conditions is not large, $``$3%. On the other hand, there are some applications where such enrichment could be significant, e.g., in spin isomer enhanced NMR technique Bowers86PRL ; Natterer97PNMRS . Note that for the standard 200 MHz NMR the difference in Boltzmann factors between Zeeman states, which determines the amplitude of NMR signal, is only $`310^5`$. If even a fraction of the 3% isomer enrichment would be transported to the Zeeman level populations it would enhance the NMR signal significantly.

Apart from any possible applications of microwave enrichment, which is by far too early to discuss now, observation of the microwave enrichment would have prove-of-principle importance for the coherent control of spin isomers. It is interesting to note also that the isomer enrichment at $`\mathrm{\Omega }=\omega _1`$ would demonstrate an example of enhanced access to weak processes in molecules through the isomer enrichment Chap01JPB . Suppose, one would like to measure the absorption at $`\mathrm{\Omega }=\omega _1`$ directly. At the conditions considered in the paper, $`\chi (\omega _1)610^6`$ cm-1 which is rather difficult to measure. This value has to be compared with the 3% enrichment in the coherent control which should not be difficult to measure.

## Acknowledgments

The authors are indebted to K.A.Nasyrov for the useful discussions of light-molecule interaction theory. This work was supported in part by the Russian Foundation for Basic Research (RFBR), grant No. 01-03-32905

Table 1. Positions of levels in 13CH3F. Molecular parameters are from Ref. Papousek94JMS .

| Notation | $`J,K`$ | $`I`$ | E(cm-1) | Frequency (MHz) |
| --- | --- | --- | --- | --- |
| $`m^{}`$ | 20,3 | 3/2 | 387.1 | 351.01$`\pm 0.16`$ ($`m^{}n^{}`$) |
| $`n^{}`$ | 21,1 | 1/2 | 387.1 |  |
| $`q`$ | 12,1 | 1/2 | 133.7 | 596294.285$`\pm `$0.013 ($`qn`$) |
| $`n`$ | 11,1 | 1/2 | 113.8 | 130.99$`\pm `$0.15 ($`nm`$) |
| $`m`$ | 9,3 | 3/2 | 113.8 | 596425.28$`\pm `$0.15 ($`qm`$) |

* Notation in Fig. 1.