text:
# On the Sutherland Spin Model of 𝐵_𝑁 Type and its Associated Spin Chain

## I Introduction

Since the publication of the pioneering papers of Calogero Ca71  and Sutherland Su71 ; Su72 , the study of solvable and integrable quantum many-body problems has become a fruitful field of research with multiple connections in many branches of contemporary mathematics and physics. From a mathematical standpoint, one of the key developments in the field was the discovery by Olshanetsky and Perelomov of an underlying $`A_N`$ root system structure for both the Calogero and Sutherland models OP83 . The integrability of these models follows by expressing the Hamiltonian as one of the radial parts of the Laplace–Beltrami operator in a symmetric space associated with the given root system. It was also shown in this paper that the original inverse square (Calogero) and trigonometric/hyperbolic (Sutherland) potentials arise as appropriate limits of the most general potential in this class, given by the Weierstrass $`\mathrm{}`$-function, and that integrable models associated to other root systems also exist. The rational and trigonometric Calogero–Sutherland (CS) models are also *exactly solvable*, in the sense that their eigenfunctions and eigenvalues can be computed algebraically. In fact, the study of the eigenfunctions of these models has led to significant advances in the theory of multivariate orthogonal polynomials LV96 ; BF97 ; Du98 . Apart from their mathematical interest, CS models have found numerous applications in diverse areas of physics such as soliton theory Ka95 ; Po95 , fractional statistics and anyons BM96 ; CL99 , random matrix theory TSA95 , and Yang–Mills theories GN94 ; DF98 , to name only a few.

During the last decade, CS models with internal degrees of freedom have been actively explored by a variety of methods, including the exchange operator formalism MP93 , the Dunkl operators approach BGHP93 ; Ch94 ; Du98 , reduction by discrete symmetries Po99 , and construction of Lax pairs HW93 ; HW93b ; IS01 . Historically, the first CS models with spin discussed in the literature were related to the original models of $`A_N`$ type introduced by Calogero and Sutherland HH92 ; BGHP93 ; HW93 ; HW93b ; MP93 ; SS93 . The integrability of these CS spin models was established in some cases by relating the Hamiltonian to a quadratic combination of Dunkl operators of $`A_N`$ type Du89 ; Ch91 ; Po92 . The $`B_N`$ counterpart of the $`A_N`$ CS spin models mentioned above were first considered by Yamomoto Ya95 . In this paper, the spectrum of the rational $`B_N`$ spin model was explicitly determined, and its integrability was shown by means of the Lax pair approach. In Ref. YT96 , Yamamoto and Tsuchiya presented an alternative proof of the integrability of this model using Dunkl operators of $`B_N`$ type. The same operators were later employed by Dunkl to construct a complete basis of eigenfunctions Du98 . In contrast, the trigonometric/hyperbolic $`B_N`$ spin model has received remarkably little attention. In our recent paper FGGRZ01b  we proved that this model is exactly solvable in the sense of Turbiner Tu88 ; Tu92 , meaning that its Hamiltonian leaves invariant a known infinite increasing sequence (or *flag*) of finite-dimensional linear spaces of smooth spin functions. In fact, in FGGRZ01b  we developed a systematic method for constructing exactly (or in some cases partially) solvable $`B_N`$-type CS models with spin by combining several families of Dunkl operators. The key elements of this method —first introduced in the $`A_N`$ case in FGGRZ01 — are: i) the definition of a new family of Dunkl operators, and ii) the construction of a very wide class of quadratic combinations of these operators and those in the other two families considered by Dunkl in Du98 .

The interest on CS spin models has been further enhanced by their close connections with integrable spin chains of Haldane–Shastry type Ha88 ; Sh88 . Spin chains describe a fixed arrangement of particles that interact through their spins. A well-known example is the Heisenberg spin chain, whose spins are equally spaced and interact only with their nearest neighbors. The Haldane–Shastry model was actually the first one-dimensional spin chain with long range interactions whose spectrum could be computed exactly. In this model, the spin sites are equally spaced in a circle and interact with each other with strength decreasing as the inverse square of the chord distance between the sites. The integrability of the Haldane–Shastry spin chain was proved by Fowler and Minahan in FM93 . Polychronakos later realized that the commuting conserved quantities of the Haldane–Shastry spin chain can be elegantly deduced from those of the (dynamical) Sutherland spin model of $`A_N`$ type by applying what he called the “freezing trick” Po93  (see also SS93 ). This corresponds to taking the strong coupling limit in the Sutherland spin model and restricting to states with no momentum excitations, so that the internal degrees of freedom remain the only relevant variables in the problem and the particles are “frozen” at their classical equilibrium positions. This observation is, in principle, valid for any integrable spin Calogero–Sutherland model. For instance, in Ref. Po93  the freezing trick is applied to the spin Calogero model with rational interaction to construct a new integrable spin chain of rational type in which the sites are no longer equally spaced. The spectrum of this chain was later calculated by Frahm Fr93  and Polychronakos Po94 . Bernard, Pasquier and Serban BPS95  studied the spin chain associated with the trigonometric Sutherland model, establishing its integrability for certain values of the parameters in the Hamiltonian.

The aim of this paper is twofold. In the first place, we prove the integrability of the hyperbolic Sutherland spin model of $`B_N`$ type, from which we are also able to deduce the integrability of the spin chain associated with this model. Secondly, we give an explicit formula for the eigenvalues of the dynamical model whose corresponding (square-integrable) eigenfunctions lie in the invariant flag mentioned above. The paper is organized as follows. In Section II we introduce a family of commuting Dunkl operators of $`B_N`$ type. We show that the sums of even powers of these Dunkl operators generate a complete set of commuting integrals of motion of the Hamiltonian of the model. The commutation relations satisfied by the Dunkl operators and the usual permutation and sign reversing operators, which possess a richer structure than in the rational case, play a key role in the proof of this result. In Section III we analyze the spectrum of the Hamiltonian for any value of the spin. Our analysis is based on the fact that the Dunkl operators leave invariant a flag of finite-dimensional linear spaces of smooth scalar functions. This flag yields a corresponding invariant flag of smooth spin functions for the hyperbolic $`B_N`$ Sutherland Hamiltonian. We construct a partially ordered basis of this “spin” flag in which the Hamiltonian is represented by a triangular matrix. In this way we can explicitly compute the eigenvalues of the restriction of the Hamiltonian to the (finite-dimensional) intersection of the spin flag with the Hilbert space of the system. We shall use the term *algebraic* in what follows to refer to the these eigenvalues and its corresponding eigenfunctions. It remains an open problem to determine whether the algebraic sector of the spectrum actually coincides with the discrete spectrum. We also study in detail the (algebraic) ground state, determining its degeneracy for all values of the spin. In Section IV we define the spin chain associated with the hyperbolic Sutherland spin model of $`B_N`$ type, and apply the freezing trick to derive a complete family of commuting integrals of motion of this chain.

## II Integrability of the Sutherland Spin Model of $`B_N`$ Type

The Hamiltonian of the hyperbolic $`B_N`$ Sutherland spin model is defined by

$`H^{}={\displaystyle \underset{i}{}}_{x_i}^2`$ $`+2a{\displaystyle \underset{i<j}{}}\left[\mathrm{sinh}^2x_{ij}^{}(a+S_{ij})+\mathrm{sinh}^2x_{ij}^+(a+\stackrel{~}{S}_{ij})\right]`$ (1)
$`+b{\displaystyle \underset{i}{}}\mathrm{sinh}^2x_i(b+S_i)b^{}{\displaystyle \underset{i}{}}\mathrm{cosh}^2x_i\left(b^{}+S_i\right),`$
where $`x_{ij}^\pm =x_i\pm x_j`$ and $`a,b,b^{}`$ are real parameters. Here and in what follows, any summation or product index without an explicit range will be understood to run from $`1`$ to $`N`$, unless otherwise constrained. The operators $`S_{ij}`$ and $`S_i`$ in Eq. (1) act on the finite-dimensional Hilbert space

$$𝒮=|s_1,\mathrm{},s_N|s_i=M,M+1,\mathrm{},M;M\frac{1}{2},$$
(2)
associated to the particles’ internal degrees of freedom, as follows:

$`S_{ij}|s_1,\mathrm{},s_i,\mathrm{},s_j,\mathrm{},s_N=|s_1,\mathrm{},s_j,\mathrm{},s_i,\mathrm{},s_N,`$ (3)
$`S_i|s_1,\mathrm{},s_i,\mathrm{},s_N=|s_1,\mathrm{},s_i,\mathrm{},s_N.`$
We have also used the customary notation $`\stackrel{~}{S}_{ij}=S_iS_jS_{ij}`$.

The operators $`S_{ij}`$ and $`S_i`$ are represented in $`𝒮`$ by $`(2M+1)^N`$-dimensional Hermitian matrices, and obey the following algebraic relations:

$$\begin{array}{c}S_{ij}^2=1,S_{ij}S_{jk}=S_{ik}S_{ij}=S_{jk}S_{ik},S_{ij}S_{kl}=S_{kl}S_{ij},\\ S_i^2=1,S_iS_j=S_jS_i,S_{ij}S_k=S_kS_{ij},S_{ij}S_j=S_iS_{ij},\end{array}$$
(4)
where the indices $`i,j,k,l`$ take distinct values in the range $`1,\mathrm{},N`$. The algebra $`𝔖`$ generated by the operators $`S_{ij},S_i`$ is thus isomorphic to the group algebra of the Weyl group $`𝒲_N`$ of type $`B_N`$, also known as the hyperoctahedral group.

We shall also make use of the permutation operators $`K_{ij}=K_{ji}`$ and the sign reversing operators $`K_i`$ ($`1ijN`$), whose action on a function $`f(𝐱)`$, with $`𝐱=(x_1,\mathrm{},x_N)^N`$, is defined as follows:

$`(K_{ij}f)(x_1,\mathrm{},x_i,\mathrm{},x_j,\mathrm{},x_N)=f(x_1,\mathrm{},x_j,\mathrm{},x_i,\mathrm{},x_N),`$ (5)
$`(K_if)(x_1,\mathrm{},x_i,\mathrm{},x_N)=f(x_1,\mathrm{},x_i,\mathrm{},x_N).`$
The operators $`K_{ij}`$ and $`K_i`$ obey algebraic identities analogous to (4). We shall denote by $`𝔎𝔖`$ the algebra generated by the coordinate permutation and sign changing operators $`K_{ij}`$ and $`K_i`$. Note also that the operators $`\mathrm{\Pi }_{ij}=K_{ij}S_{ij}`$ and $`\mathrm{\Pi }_i=K_iS_i`$ generate an algebra $`𝔚`$ isomorphic to $`𝔎`$ and $`𝔖`$. From now on we shall identify the abstract group $`𝒲_N`$ with its realizations generated by the operators $`K_{ij},K_i`$ on $`C^{\mathrm{}}(^N)`$, $`S_{ij},S_i`$ on $`𝒮`$, or $`\mathrm{\Pi }_{ij},\mathrm{\Pi }_i`$ on $`C^{\mathrm{}}(^N)𝒮`$, depending on the context.

The Hamiltonian (1) describes a system of $`N`$ identical particles, whose physical states are therefore either totally symmetric or totally antisymmetric under particle exchange. Moreover, since $`H^{}`$ clearly commutes with the family of commuting operators $`\mathrm{\Pi }_i`$ ($`i=1,\mathrm{},N`$), we can choose a basis of common eigenfunctions of $`H^{}`$ and all the operators $`\mathrm{\Pi }_i`$. Given an element $`\psi _k`$ of this basis, it follows from the commutation relations of the sign reversing operators $`\mathrm{\Pi }_i`$ with the permutation operators $`\mathrm{\Pi }_{ij}`$ that $`\mathrm{\Pi }_i\psi _k=ϵ_k\psi _k`$, independently of $`i`$. In principle, the parity $`ϵ_k`$ could depend on $`k`$. However, we shall see in the following section that all the algebraic eigenfunctions have the same parity, and that this parity is determined by the sign of the parameter $`b`$. From now on we shall assume, for definiteness, that we are dealing with a system of fermions whose algebraic states are also antisymmetric under sign reversal of each particle’s spatial and internal coordinates. This covers what is perhaps the physically most interesting case, namely that of a system of spin $`1/2`$ particles, for which the internal degrees of freedom are naturally interpreted as the particles’ spin. The results of this paper can be easily modified to treat any other choice of the particles’ statistics and parity.

In the rest of this section we shall prove the integrability of the model (1) by expressing the Hamiltonian in terms of the following family of $`B_N`$-type Dunkl operators:

$$\begin{array}{c}J_i=_{x_i}a\underset{ji}{}\left[(1+\mathrm{coth}x_{ij}^{})K_{ij}+(1+\mathrm{coth}x_{ij}^+)\stackrel{~}{K}_{ij}\right]\hfill \\ \hfill \left[b(1+\mathrm{coth}x_i)+b^{}(1+\mathrm{tanh}x_i)\right]K_i+2a\underset{j<i}{}K_{ij},\end{array}$$
(6)
where $`\stackrel{~}{K}_{ij}=K_iK_jK_{ij}`$. The operators $`J_i`$ are related to the operators introduced by Yamamoto Ya95  in connection with the trigonometric $`BC_N`$ spin Sutherland model.

A key property of the Dunkl operators (6) is their commutativity:

$$[J_i,J_j]=0,i,j=1,\mathrm{},N.$$
(7)
We shall also make use of the following commutation relations between the operators $`K_{ij},K_i`$ and the operators $`J_i`$:

$`[K_{ij},J_k]=\{\begin{array}{cc}2a(K_{jk}K_{ik})K_{ij},\hfill & i<k<j\hfill \\ 0,\hfill & \text{otherwise}\hfill \end{array}`$ (8)
$`K_{ij}J_iJ_jK_{ij}=2a\left(1+{\displaystyle \underset{i<l<j}{}}K_{ij}K_{il}\right),`$ (9)
$`K_{ij}J_jJ_iK_{ij}=2a\left(1+{\displaystyle \underset{i<l<j}{}}K_{ij}K_{jl}\right),`$ (10)
$`[K_i,J_j]=2aK_{ij}(K_jK_i),[K_j,J_i]=0,`$ (11)
$`\{K_i,J_i\}=2(b+b^{})2a{\displaystyle \underset{l>i}{}}K_{il}(K_i+K_l),`$ (12)
where $`i<j`$ and $`k`$ are three distinct indices ranging from $`1`$ to $`N`$. Note that the Dunkl operators of rational type considered in Ref. YT96  satisfy the latter equations with the right-hand side replaced by zero. The nonvanishing of the right-hand side of Eqs. (8)–(12) gives rise to some nontrivial technical points in the proof of the integrability of the Hamiltonian (1), as we shall see below.

Another important property of the Dunkl operators $`J_i`$ is that they preserve the linear space

$$_m=\mu (𝐱)\mathrm{exp}\left(2\underset{i}{}n_ix_i\right)|n_i=m,m+1,\mathrm{},m,i=1,\mathrm{},N,$$
(13)
where

$$\mu (𝐱)=\underset{i<j}{}\left|\mathrm{sinh}x_{ij}^{}\mathrm{sinh}x_{ij}^+\right|^a\underset{i}{}\left|\mathrm{sinh}x_i\right|^b\left|\mathrm{cosh}x_i\right|^b^{},$$
(14)
for any nonnegative integer $`m`$. This fact will prove crucial for the calculation of the spectrum of the hyperbolic $`B_N`$ Sutherland spin model.

We define a mapping $`{}_{}{}^{}:𝔇𝔎𝔇𝔖`$, where $`𝔇`$ denotes the algebra of linear differential operators on $`C^{\mathrm{}}(^N)`$, as follows. If $`D𝔇`$, we set

$$\left(DK_{\alpha _1}\mathrm{}K_{\alpha _r}\right)^{}=(1)^rDS_{\alpha _r}\mathrm{}S_{\alpha _1},$$
(15)
where $`\alpha _k`$ stands for $`ij`$ or $`i`$. The mapping  is then linearly extended to $`𝔇𝔎`$. For instance, the Hamiltonian of the hyperbolic $`B_N`$ Sutherland spin model (1) is obtained by applying the “star” mapping to the operator

$`H={\displaystyle \underset{i}{}}_{x_i}^2`$ $`+2a{\displaystyle \underset{i<j}{}}\left[\mathrm{sinh}^2x_{ij}^{}(aK_{ij})+\mathrm{sinh}^2x_{ij}^+(a\stackrel{~}{K}_{ij})\right]`$ (16)
$`+b{\displaystyle \underset{i}{}}\mathrm{sinh}^2x_i(bK_i)b^{}{\displaystyle \underset{i}{}}\mathrm{cosh}^2x_i\left(b^{}K_i\right).`$
Let $`\mathrm{\Lambda }_0`$ be the antisymmetrisation operator, defined by the relations $`\mathrm{\Lambda }_0^2=\mathrm{\Lambda }_0`$ and $`\mathrm{\Pi }_{ij}\mathrm{\Lambda }_0=\mathrm{\Lambda }_0`$, $`j>i=1,\mathrm{},N`$. More explicitly,

$$\mathrm{\Lambda }_0=\frac{1}{N!}\underset{l=1}{\overset{N!}{}}ϵ_lP_l,$$

where $`P_l`$ denotes an element of the realization of the symmetric group generated by the operators $`\mathrm{\Pi }_{ij}`$, and $`ϵ_l`$ is the signature of $`P_l`$. For instance, if $`N=2,3`$ the antisymmetriser $`\mathrm{\Lambda }_0`$ is given by

$`N=2:\mathrm{\Lambda }_0={\displaystyle \frac{1}{2}}(1\mathrm{\Pi }_{12}),`$
$`N=3:\mathrm{\Lambda }_0={\displaystyle \frac{1}{6}}(1\mathrm{\Pi }_{12}\mathrm{\Pi }_{13}\mathrm{\Pi }_{23}+\mathrm{\Pi }_{12}\mathrm{\Pi }_{13}+\mathrm{\Pi }_{12}\mathrm{\Pi }_{23}).`$
The total antisymmetriser $`\mathrm{\Lambda }`$ with respect to the action of the operators $`\mathrm{\Pi }_{ij}`$ and $`\mathrm{\Pi }_i`$ is determined by the relations $`\mathrm{\Lambda }^2=\mathrm{\Lambda }`$ and

$$\mathrm{\Pi }_{ij}\mathrm{\Lambda }=\mathrm{\Lambda },\mathrm{\Pi }_i\mathrm{\Lambda }=\mathrm{\Lambda },j>i=1,\mathrm{},N.$$
(17)
It may be easily shown that

$$\mathrm{\Lambda }=\frac{1}{2^N}\left(\underset{i}{}(1\mathrm{\Pi }_i)\right)\mathrm{\Lambda }_0.$$

Since $`K_{ij}^2=K_i^2=1`$, the relations (17) are equivalent to

$$K_{ij}\mathrm{\Lambda }=S_{ij}\mathrm{\Lambda },K_i\mathrm{\Lambda }=S_i\mathrm{\Lambda },j>i=1,\mathrm{},N.$$
(18)
¿From these relations and the definition of the star mapping it follows immediately that

$$A\mathrm{\Lambda }=A^{}\mathrm{\Lambda }$$
(19)
for every operator $`A𝔇𝔎`$. The proof of the integrability of the hyperbolic $`B_N`$ Sutherland spin model is based on the following lemmas.

###### Lemma 1.

If $`B𝔇𝔖`$ satisfies $`B\mathrm{\Lambda }=0`$, then $`B=0`$.

###### Proof.

The operator $`B𝔇𝔖`$ is of the form

$$B=\underset{iI}{}f_i(𝐱)B_i^i,$$
(20)
where $`B_i𝔖`$, $`f_iC^{\mathrm{}}(^N)`$, $`i=(i_1,\mathrm{},i_N)`$ is a multiindex belonging to a finite subset $`I_0^N`$ (with $`_0=\{0,1,2,\mathrm{}\}`$), and $`^i=_1^{i_1}\mathrm{}_N^{i_N}`$. Let us denote by $`W_l`$, with $`lL=\{1,\mathrm{},2^NN!\}`$, the elements of the realization of the Weyl group $`𝒲_N`$ generated by the operators $`\mathrm{\Pi }_{ij}`$ and $`\mathrm{\Pi }_i`$. The action of the total antisymmetrisation operator $`\mathrm{\Lambda }`$ over a factored state $`\psi =\phi (𝐱)|s`$, with $`\phi C^{\mathrm{}}(^N)`$ and $`|s𝒮`$, is given by

$$\mathrm{\Lambda }\psi =\underset{lL}{}ϵ_l(W_l\phi )W_l|s,$$
(21)
where $`ϵ_l=\pm 1`$ is the parity of the total number of generators $`\mathrm{\Pi }_{ij}`$, $`\mathrm{\Pi }_i`$ in any decomposition of $`W_l`$. By hypothesis,

$$B(\mathrm{\Lambda }\psi )=\underset{iI,lL}{}ϵ_lf_i(𝐱)^i\left(W_l\phi \right)B_i(W_l|s)=0.$$
(22)
Applying the latter equation to a family of functions $`\left\{\phi _j(𝐱)\right\}_{jI\times L}`$ satisfying the condition

$$det\left[^i\left(W_l\phi _j\right)\right]_{jI\times L}^{iI,lL}0,$$
(23)
we obtain

$$B_i(W_l|s)=0,\text{for all }iI,lL.$$

In particular (taking $`lL`$ so that $`W_l`$ is the identity) $`B_i|s=0`$ for all $`iI`$. Since $`|s𝒮`$ is arbitrary, it follows that $`B_i=0`$ for all $`iI`$, and hence $`B`$ vanishes identically. ∎

###### Lemma 2.

If $`B𝔇𝔎`$ commutes with $`\mathrm{\Lambda }`$ then $`(AB)^{}=A^{}B^{}`$ for all $`A𝔇𝔎`$.

###### Proof.

Using Eq. (19) and the hypothesis repeatedly we obtain:

$$(AB)^{}\mathrm{\Lambda }=AB\mathrm{\Lambda }=A\mathrm{\Lambda }B=A^{}\mathrm{\Lambda }B=A^{}B\mathrm{\Lambda }=A^{}B^{}\mathrm{\Lambda }.$$

The statement follows from the previous lemma. ∎

We shall often make use of the following immediate consequence of Lemma 2:

###### Lemma 3.

If $`A,B𝔇𝔎`$ commute with $`\mathrm{\Lambda }`$ then $`[A,B]^{}=[A^{},B^{}]`$.

We shall now construct a complete family of commuting integrals of motion for the hyperbolic $`B_N`$ Sutherland spin Hamiltonian (1). The construction is based on the observation that the operator $`H`$ in Eq. (16) can be expressed as

$$H=\underset{i}{}J_i^2.$$
(24)
By (7), the operators

$$I_p=\underset{i}{}J_i^{2p},p,$$
(25)
commute with one another. In view of the previous lemma, it suffices to prove that $`I_p`$ commutes with the total antisymmetriser $`\mathrm{\Lambda }`$ for all $`p`$ to conclude that the star operators $`I_p^{}`$ ($`p`$) form a commuting family of integrals of motion of $`H^{}=I_1^{}`$. We shall in fact prove the following stronger result:

###### Lemma 4.

The operators $`I_p`$ $`(p)`$ commute with the permutation and sign changing operators $`K_{ij}`$ and $`K_i`$.

###### Proof.

First of all, the elementary permutation $`K_{i,i+1}`$ commutes with $`I_p`$ for $`i=1,\mathrm{},N1`$. Indeed, $`K_{i,i+1}`$ commutes with $`J_j`$ for $`ji,i+1`$ by (8), while for $`j=i,i+1`$ we have

$`K_{i,i+1}J_i^{2p}`$ $`=J_{i+1}^{2p}K_{i,i+1}2a{\displaystyle \underset{r=0}{\overset{2p1}{}}}J_i^{2pr1}J_{i+1}^r,`$
$`K_{i,i+1}J_{i+1}^{2p}`$ $`=J_i^{2p}K_{i,i+1}+2a{\displaystyle \underset{r=0}{\overset{2p1}{}}}J_i^{2pr1}J_{i+1}^r.`$
Since an arbitrary permutation can be expressed as the product of elementary permutations, this shows that $`K_{ij}`$ commutes with $`I_p`$ for all $`ij`$. Secondly, the sign reversing operator $`K_N`$ commutes with $`I_p`$ for all $`p`$, since

$`K_NJ_i=J_iK_N,\text{if}i<N,`$
while
$`K_NJ_N^2=J_NK_NJ_N2(b+b^{})J_N=J_N^2K_N.`$
This implies that $`K_i`$ commutes with $`I_p`$ for an arbitrary $`i=1,\mathrm{},N`$, since

$$0=K_{iN}[K_NK_{iN},I_p]=K_{iN}[K_{iN}K_i,I_p]=[K_i,I_p].$$

The operators $`I_p^{}`$ ($`p`$) thus form an infinite commuting family. Moreover, by examining the terms of highest order in the partial derivatives one can easily conclude that the set $`\{I_p^{}\}_{p=1}^N`$ is algebraically independent. We have thus proved the main result of this section:

###### Theorem 1.

The operators $`\{I_p^{}\}_{p=1}^N`$ form a complete family of commuting integrals of motion for the hyperbolic $`B_N`$ Sutherland spin Hamiltonian $`H^{}=I_1^{}`$.

We also note that the constants of motion $`I_p^{}`$ ($`p`$) commute with the total permutation and sign changing operators $`\mathrm{\Pi }_{ij}`$ and $`\mathrm{\Pi }_i`$. This is a consequence of Lemma 4 and the following general fact:

###### Lemma 5.

If $`A𝔇𝔎`$ commutes with $`K_{ij}`$ (resp. $`K_i`$) then $`A^{}`$ commutes with $`\mathrm{\Pi }_{ij}`$ (resp. $`\mathrm{\Pi }_i`$).

###### Proof.

We can write

$$A=\underset{\gamma \mathrm{\Gamma }}{}D_\gamma K_\gamma ,$$
(26)
where $`K_\gamma `$ is a monomial in $`K_{kl}`$ and $`K_l`$, $`D_\gamma 𝔇`$, and $`\mathrm{\Gamma }`$ is a finite set such that $`\{K_\gamma \gamma \mathrm{\Gamma }\}`$ is linearly independent. By hypothesis

$$A=K_{ij}AK_{ij}=\underset{\gamma \mathrm{\Gamma }}{}K_{ij}(D_\gamma )K_{ij}K_\gamma K_{ij}$$
(27)
where $`K_{ij}(D_\gamma )`$ is the image of $`D_\gamma `$ under the natural action of $`K_{ij}`$ in $`𝔇`$. Comparing (27) with (26) we conclude that for each $`\gamma \mathrm{\Gamma }`$ there exists $`\gamma ^{}\mathrm{\Gamma }`$ such that $`K_{ij}K_\gamma K_{ij}=K_\gamma ^{}`$, and

$$K_{ij}(D_\gamma )=D_\gamma ^{}.$$

On the other hand we have

$$\mathrm{\Pi }_{ij}A^{}\mathrm{\Pi }_{ij}=\underset{\gamma \mathrm{\Gamma }}{}K_{ij}(D_\gamma )S_{ij}K_\gamma ^{}S_{ij}=\underset{\gamma \mathrm{\Gamma }}{}K_{ij}(D_\gamma )K_\gamma ^{}^{}=\underset{\gamma \mathrm{\Gamma }}{}D_\gamma ^{}K_\gamma ^{}^{}.$$

Since $`(\gamma ^{})^{}=\gamma `$, we have $`\mathrm{\Gamma }^{}=\mathrm{\Gamma }`$, and therefore the right-hand side of the previous formula equals $`A^{}`$. The equality $`\mathrm{\Pi }_iA^{}\mathrm{\Pi }_i=A^{}`$ is established in a similar way. ∎

## III Spectrum of the Sutherland Spin Model of $`B_N`$ Type

We shall now study the algebraic sector of the spectrum of the $`B_N`$-type Sutherland spin model (1). The starting point in our discussion is the invariance under $`H`$ of the space $`_m`$ for all $`m=0,1,\mathrm{}`$, which is an immediate consequence of Eq. (24) and the definition of the operators $`J_i`$. We shall construct a basis of the $`H`$-invariant space $`_m`$ with respect to which the matrix of $`H|__m`$ is upper triangular, thereby obtaining an exact formula for the spectrum of this operator.

To derive the spectrum of $`H^{}`$ from that of $`H`$, we shall make use of the identity

$$H^{}\left[\mathrm{\Lambda }\left(\phi |s\right)\right]=\mathrm{\Lambda }\left[(H\phi )|s\right],$$
(28)
where $`\phi C^{\mathrm{}}(^N)`$ and $`|s𝒮`$. The latter identity, which is an immediate consequence of Eq. (19) and Lemma 4, implies that the spaces

$$_m=\mathrm{\Lambda }(_m𝒮),m=0,1,\mathrm{},$$
(29)
are invariant under $`H^{}`$. From the basis of $`_m`$ triangularizing $`H|__m`$ we shall construct a basis of $`_m`$ with respect to which $`H^{}|__m`$ is also represented by an upper triangular matrix. In this way we shall determine the spectrum of the Sutherland spin model of $`B_N`$ type (1).

Let us start by computing the spectrum of the operator $`H`$. Following closely the approach of Ref. BGHP93  for spin models of $`A_N`$ type, we shall define a suitable partial ordering in the set of (scaled) exponential monomials

$$f_n(𝐱)=\mu (𝐱)\mathrm{exp}\left(2\underset{i}{}n_ix_i\right),n=(n_1,\mathrm{},n_N),mn_im,$$
(30)
spanning the subspaces $`_m`$. We shall then show that the operator $`H`$ is represented by a triangular matrix in any partially ordered basis of $`_m`$.

The partial ordering in the basis (30) is defined as follows. Given a multiindex $`n=(n_1,\mathrm{},n_N)^N`$, we define the nonnegative and nonincreasing multiindex $`[n]`$ by

$$[n]=(\left|n_{i_1}\right|,\mathrm{},\left|n_{i_N}\right|),\text{where}\left|n_{i_1}\right|\mathrm{}\left|n_{i_N}\right|.$$
(31)
If $`n,n^{}\left[^N\right]`$ are nonnegative and nonincreasing multiindices, we shall say that $`nn^{}`$ if $`n_1n_1^{}=\mathrm{}=n_{i1}n_{i1}^{}=0`$ and $`n_i<n_i^{}`$. For two arbitrary multiindices $`n,n^{}^N`$, by definition $`nn^{}`$ if and only if $`[n][n^{}]`$. The partial ordering $``$ in $`^N`$ induces a partial ordering in the exponential monomial basis (30), namely $`f_nf_n^{}`$ if and only if $`nn^{}`$. The action of the Weyl group on the basis (30) preserves this partial ordering, i.e., if $`f_nf_n^{}`$ then $`Wf_nWf_n^{}`$ for all $`W𝒲_N`$.

If $`n=(n_1,\mathrm{},n_N)\left[^N\right]`$ and $`s`$, we shall use the following notation:

$`\mathrm{\#}(s)`$ $`=\mathrm{card}\{i:n_i=s\},`$
$`\mathrm{}(s)`$ $`=\mathrm{min}\{i:n_i=s\},`$
with $`\mathrm{}(s)=+\mathrm{}`$ if $`n_is`$ for all $`i=1,\mathrm{},N`$. For instance, if $`n=(5,2,2,1,1,1,0)`$ then $`\mathrm{\#}(1)=3`$ and $`\mathrm{}(1)=4`$. The computation of the spectrum of $`H`$ is based on the following result:

###### Proposition 1.

If $`n\left[^N\right]`$ is a nonnegative and nonincreasing multiindex, the following identity holds:

$$J_if_n=\lambda _{n,i}f_n+\underset{\begin{array}{c}n^{}^N\\ n^{}n\end{array}}{}c_{n,i}^n^{}f_n^{},$$
(32)
where $`c_{n,i}^n^{}`$ and

$$\lambda _{n,i}=\{\begin{array}{cc}2n_i+b+b^{}+2a\left(N+i+1\mathrm{\#}(n_i)2\mathrm{}(n_i)\right),\hfill & n_i>0\hfill \\ bb^{}+2a(iN),\hfill & n_i=0.\hfill \end{array}$$
(33)
###### Proof.

After some algebra one readily obtains the following expression:

$`J_if_n=f_n[`$ $`2n_i+b+b^{}+2a(N1)2a{\displaystyle \underset{j<i}{}}\left({\displaystyle \frac{\alpha _{ij}^{n_jn_i}1}{\alpha _{ij}1}}+{\displaystyle \frac{\beta _{ij}^{1n_in_j}1}{\beta _{ij}1}}\right)`$
$`2a{\displaystyle \underset{j>i}{}}\left({\displaystyle \frac{\alpha _{ij}^{1+n_jn_i}1}{\alpha _{ij}1}}+{\displaystyle \frac{\beta _{ij}^{1n_in_j}1}{\beta _{ij}1}}\right)`$ (34)
$`2b{\displaystyle \frac{z_i^{12n_i}1}{z_i1}}2b^{}{\displaystyle \frac{z_i^{12n_i}+1}{z_i+1}}],`$
where

$$z_i=\mathrm{e}^{2x_i},\alpha _{ij}=z_iz_j^1,\beta _{ij}=z_iz_j.$$

Consider, for instance, the first term in $`\alpha _{ij}`$ in Eq. (34). Since $`j<i`$, $`n_jn_i`$. If $`n_j=n_i`$ this term vanishes. If $`n_j>n_i`$ we have

$$f_n\frac{\alpha _{ij}^{n_jn_i}1}{\alpha _{ij}1}=f_n\left(1+\underset{r=1}{\overset{n_jn_i1}{}}z_j^rz_i^r\right),$$
(35)
where the last sum only appears if $`n_jn_i>1`$. In this case we have $`0<\mathrm{max}\{n_jr,n_i+r\}<n_j`$ for all $`r=1,\mathrm{},n_jn_i1`$, so the multiindices of the monomials in the summation symbol in Eq. (35) satisfy

$$(n_1,\mathrm{},n_jr,\mathrm{},n_i+r,\mathrm{},n_N)n.$$

It may be likewise verified that the multiindices $`n^{}`$ of the monomials arising from the remaining terms in Eq. (34) either coincide with $`n`$ or satisfy $`n^{}n`$. The value of $`\lambda _{n,i}`$ given in Eq. (33) can be computed by evaluating the constant part of the expression in square brackets in the right-hand side of Eq. (34). For instance, the first term in $`\alpha _{ij}`$ in Eq. (34) contributes the quantity $`2a\left(\mathrm{}(n_i)1\right)`$ to $`\lambda _{n,i}`$. ∎

Note that Eq. (32) does not hold if $`n`$ does not belong to $`\left[^N\right]`$, so that Proposition 1 in general does not determine the spectrum of the restriction of $`J_i`$ to $`_m`$. On the other hand, for an arbitrary multiindex $`n^N`$ we shall only need the following weaker result:

###### Corollary 1.

If $`n^N`$ then

$$J_if_n=\underset{\begin{array}{c}n^{}^N\\ [n^{}][n]\end{array}}{}\gamma _{n,i}^n^{}f_n^{},$$
(36)
for some real constants $`\gamma _{n,i}^n^{}`$.

###### Proof.

We have

$$J_if_n=J_iWf_{[n]},$$

where $`W`$ is any element of $`𝒲_N`$ such that $`f_n=Wf_{[n]}`$. Eq. (36) then follows from the previous proposition, the commutation relations (8)–(12) and the invariance of the partial ordering $``$ under the action of the Weyl group. ∎

The algebraic spectrum of $`H`$ can be computed in closed form using the previous results, which imply the following proposition:

###### Proposition 2.

For all $`n^N`$ the following identity holds:

$$Hf_n=\underset{i}{}\lambda _{[n],i}^2f_n+\underset{\begin{array}{c}n^{}^N\\ n^{}n\end{array}}{}c_n^n^{}f_n^{},\text{with }c_n^n^{}.$$
(37)
###### Proof.

Let $`W`$ be any element of $`𝒲_N`$ such that $`f_n=Wf_{[n]}`$. Since $`H=I_1`$ commutes with $`W`$ by Lemma 4, from (32) we obtain

$$Hf_n=WHf_{[n]}=\underset{i}{}\lambda _{[n],i}^2f_n\underset{\begin{array}{c}n^{}^N,i\\ n^{}[n]\end{array}}{}\lambda _{[n],i}c_{[n],i}^n^{}Wf_n^{}\underset{\begin{array}{c}n^{}^N,i\\ n^{}[n]\end{array}}{}c_{[n],i}^n^{}WJ_if_n^{}.$$

Eq. (37) follows immediately from the latter equation, Corollary 1 and the invariance of the partial ordering $``$ under the action of the Weyl group. ∎

Let $`_m=\left\{f_{n(j)}\right|j=1,\mathrm{},(2m+1)^N\}`$ be any exponential monomial basis of the linear space $`_m`$ partially ordered according to $``$, i.e., such that if $`n(j)n(k)`$ then $`j<k`$. The previous proposition implies that the matrix of the restriction of $`H`$ to $`_m`$ with respect to $`_m`$ is upper triangular. The eigenvalues of this matrix are its diagonal elements

$$E_n=\underset{i}{}\lambda _{[n],i}^2;mn_jm,j=1,\mathrm{},N.$$
(38)
It should be noted, however, that the algebraic eigenfunctions of $`H`$ must satisfy appropriate boundary conditions that we shall now discuss. In the first place, since the potential of the $`B_N`$-type spin Sutherland Hamiltonian (1) diverges on the hyperplanes $`x_i\pm x_j=0`$, $`1ijN`$, as $`(x_i\pm x_j)^2`$, we must require that the eigenfunctions of $`H`$ vanish faster than $`(x_i\pm x_j)^{1/2}`$ near these hyperplanes. This yields the conditions (cf. Eq. (14))

$$a,b>\frac{1}{2}.$$
(39)
Secondly, the eigenfunctions must be square-integrable on their domain, which (without loss of generality) shall be taken as the open set $`X^N`$ given by

$$0<x_N<\mathrm{}<x_1.$$
(40)
The algebraic eigenfunctions lying in $`_m`$ will satisfy this condition if and only if

$$\frac{1}{2}(b+b^{})+a(N1)+m<0.$$
(41)
The latter inequality implies that the number of algebraic levels of $`H`$ is finite, since $`m`$ cannot exceed the integer $`m_1`$ defined by

$$m_1=\mathrm{max}\left\{m_0|\frac{1}{2}(b+b^{})+a(N1)+m<0\right\}.$$
(42)
Note, in particular, that there are no algebraic eigenfunctions unless the parameters in the potential verify the inequality

$$\frac{1}{2}(b+b^{})+a(N1)<0.$$
(43)
¿From now on, we shall work on the maximal $`H`$-invariant subspace $`_{m_1}`$. Remark 1. We could also have considered algebraic eigenfunctions of the Hamiltonian (1) antisymmetric under permutations but even under sign reversals. On these eigenfunctions, the action of the operators $`S_{ij}`$ and $`S_i`$ coincides with that of the operators $`K_{ij}`$ and $`K_i`$, respectively. Therefore Eq. (15) in the definition of the star mapping should be replaced by

$$\left(DK_{\alpha _1}\mathrm{}K_{\alpha _r}\right)^{}=(1)^r^{}DS_{\alpha _r}\mathrm{}S_{\alpha _1},$$

where $`r^{}`$ is the number of permutation operators in the monomial $`K_{\alpha _1}\mathrm{}K_{\alpha _r}`$. As a consequence, the Hamiltonian (1) is the image under the new star mapping of the operator $`H(b,b^{})`$, with $`H(b,b^{})`$ given by Eq. (16). It follows from Eqs. (39) and (43) that $`H^{}`$ possesses algebraic eigenfunctions of even parity if and only if

$$a>\frac{1}{2},b<\frac{1}{2},\frac{1}{2}(b+b^{})+a(N1)<0.$$
(44)
In particular, these inequalities and Eqs. (39) and (43) imply that $`H^{}`$ cannot have both odd and even parity algebraic eigenfunctions for any values of the parameters.
Let us turn now to the algebraic spectrum of the $`B_N`$-type Sutherland spin model (1). First of all, if Eqs. (39) and (43) are satisfied the wavefunctions in $`_{m_1}`$ are normalizable and well behaved near the singular hyperplanes. Secondly, if $`\phi _{m_1}`$ is an eigenfunction of $`H`$ with eigenvalue $`E`$ and $`|s𝒮`$ is an arbitrary spin state, it follows from Eq. (28) that $`\mathrm{\Lambda }\left(\phi |s\right)_{m_1}`$ is either zero or an eigenfunction of $`H^{}`$ with the same energy $`E`$. The algebraic spectrum of $`H^{}`$ is thus a subset of the algebraic spectrum of $`H`$. Instead of studying the conditions under which $`\mathrm{\Lambda }\left(\phi |s\right)`$ does not vanish, in the next proposition we shall directly construct from $`_{m_1}`$ a basis of $`_{m_1}`$ with respect to which the matrix of $`H^{}|_{_{m_1}}`$ is upper triangular. We shall use the following notation:

$$m_0=\overline{\frac{N\overline{M}}{2M+1}},$$
(45)
where $`\overline{x}`$ denotes the smallest integer greater than or equal to $`x`$.

###### Proposition 3.

The $`H^{}`$-invariant space $`_{m_1}`$ is nonzero if and only if $`m_0m_1`$. If this condition holds, a basis of $`_{m_1}`$ consists of states of the form

$$\mathrm{\Lambda }\left(f_n|s_1,\mathrm{},s_N\right),$$
(46)
where $`n\left[^N\right]`$ and $`|s_1,\mathrm{},s_N`$ satisfy:

$`i`$ $`)\mathrm{\#}(n_i)\{\begin{array}{cc}2M+1,\hfill & \text{if}0<n_im_1\hfill \\ \overline{M},\hfill & \text{if}n_i=0;\hfill \end{array}`$ (47)
$`ii`$ $`)s_i>s_j,\text{if}n_i=n_j\text{and}i<j;`$ (48)
$`iii`$ $`)s_i>0,\text{if}n_i=0.`$ (49)
###### Proof.

In the first place, since $`\mathrm{\Lambda }W=ϵ(W)\mathrm{\Lambda }`$ for any element $`W`$ of the realization of $`𝒲_N`$ generated by $`\mathrm{\Pi }_{ij}`$, $`\mathrm{\Pi }_i`$, the space $`_{m_1}`$ is spanned by states of the form $`\mathrm{\Lambda }\left(f_n|s\right)`$, where $`n\left[^N\right]`$ and $`|s𝒮`$. Moreover, from the definition of the total antisymmetriser $`\mathrm{\Lambda }`$ it follows that a state of the form (46) with $`n[^N]`$ vanishes if and only if either $`s_i=s_j`$ when $`n_i=n_j>0`$ and $`ij`$, or $`s_i=\pm s_j`$ when $`n_i=n_j=0`$ and $`ij`$, or $`s_i=0`$ when $`n_i=0`$. In particular, the condition (47) is necessary to ensure that the state (46) does not vanish. Since this condition cannot hold if $`n_1<m_0`$, and $`n_1m_1`$ for all states in $`_{m_1}`$, it follows that $`_{m_1}`$ is trivial if $`m_1<m_0`$.

On the other hand, if $`m_0m_1`$ all the states (46)–(49) are nonzero, and it is immediate to show that they are also linearly independent. Moreover, any nonzero state of the form (46) with $`n[^N]`$ can be written as

$$\mathrm{\Lambda }\left[W\left(f_n|s_1,\mathrm{},s_N\right)\right]=ϵ(W)\mathrm{\Lambda }\left(f_n|s_1,\mathrm{},s_N\right),$$

where $`n`$ and $`|s_1,\mathrm{},s_N`$ satisfy (47)–(49), and $`W𝒲_N`$ is an element of the stabilizer of $`f_n`$. ∎

###### Corollary 2.

If $`m_0m_1`$, the dimension of the $`H^{}`$-invariant space $`_{m_1}`$ is given by

$$dim\left(_{m_1}\right)=\left(\genfrac{}{}{0pt}{}{m_1(2M+1)+\overline{M}}{N}\right).$$
(50)
###### Proof.

Indeed, from Eqs. (48)–(49) it easily follows that

$$dim\left(_{m_1}\right)=\underset{N_0+\mathrm{}+N_{m_1}=N}{}\left(\genfrac{}{}{0pt}{}{\overline{M}}{N_0}\right)\left(\genfrac{}{}{0pt}{}{2M+1}{N_1}\right)\mathrm{}\left(\genfrac{}{}{0pt}{}{2M+1}{N_{m_1}}\right)=\left(\genfrac{}{}{0pt}{}{m_1(2M+1)+\overline{M}}{N}\right).$$

The algebraic spectrum of the hyperbolic $`B_N`$ Sutherland spin model (1) follows directly from Proposition 3:

###### Theorem 2.

If $`m_0m_1`$, the algebraic energies of $`H^{}`$ are given by

$$E_n^{}=\underset{i}{}\lambda _{n,i}^2,$$
(51)
where $`n\left[^N\right]`$ satisfies the condition (47) and $`\lambda _{n,i}`$ is given by Eq. (33).

###### Proof.

Let $`\psi _{n,s}=\mathrm{\Lambda }\left(f_n|s_1,\mathrm{},s_N\right)`$ be an element of the basis (46)–(49) of $`_{m_1}`$. Using Eqs. (37) and (28) we easily obtain

$$H^{}\psi _{n,s}=\underset{i}{}\lambda _{n,i}^2\psi _{n,s}+\underset{\begin{array}{c}n^{}^N\\ n^{}n\end{array}}{}c_n^n^{}\mathrm{\Lambda }\left(f_n^{}|s_1,\mathrm{},s_N\right).$$
(52)
The state $`\mathrm{\Lambda }\left(f_n^{}|s_1,\mathrm{},s_N\right)`$ is proportional to a basis element of the form $`\psi _{n^{\prime \prime },s^{}}`$, with $`f_{n^{\prime \prime }}=Wf_n^{}`$ for some element $`W`$ of $`𝒲_N`$ and $`n^{\prime \prime }n`$. Therefore the matrix of $`H^{}|_{_{m_1}}`$ in the basis (46)–(49) is also upper triangular, with diagonal elements given by (51). ∎

The algebraic ground state of the Hamiltonian $`H^{}`$ and its degeneracy $`d`$ can be determined using Proposition 3 and the previous theorem:

###### Proposition 4.

The multiindex $`n`$ yielding the algebraic ground state and the degeneracy of this state are given by
i) $`N\overline{M}`$: $`n=0,d=\left({\displaystyle \genfrac{}{}{0pt}{}{\overline{M}}{N}}\right);`$
ii) $`N>\overline{M}`$:

$`n=(\stackrel{r}{\stackrel{}{m_0,\mathrm{},m_0}},\stackrel{2M+1}{\stackrel{}{m_01,\mathrm{},m_01}},\mathrm{},\stackrel{2M+1}{\stackrel{}{1,\mathrm{},1}},\stackrel{\overline{M}}{\stackrel{}{0,\mathrm{},0}}),`$ (53)
$`d=\left({\displaystyle \genfrac{}{}{0pt}{}{2M+1}{r}}\right),`$
ii)  where $`r=N(m_01)(2M+1)\overline{M}`$.

###### Proof.

Note, first of all, that from the definition (45) of $`m_0`$ it follows that $`1r2M+1`$. Let $`n\left[^N\right]`$ be a nonnegative and nonincreasing multiindex satisfying $`n_1m_1`$ and Eq. (47). The contribution to the algebraic energy (51) of all the terms $`\lambda _{n,i}^2`$ such that $`n_i`$ is equal to a fixed value $`k\{n_j\}_{j=1}^N`$ can be easily evaluated in closed form. Indeed, denoting for brevity

$$i_0=\mathrm{}(k),i_1=\mathrm{}(k)+\mathrm{\#}(k)1,$$

$$\alpha =\frac{1}{2a}\left(b+b^{}+2a(N1)\right),\alpha _k=\alpha \frac{k}{a},$$

from (33) we have, for $`k>0`$,

$`{\displaystyle \underset{i=i_0}{\overset{i_1}{}}}\lambda _{n,i}^2`$ $`=4a^2{\displaystyle \underset{i=i_0}{\overset{i_1}{}}}(ii_0i_1\alpha _k+1)^2`$
$`=4a^2\mathrm{\#}(k)\left[\alpha _k^2+\left(i_0+i_12\right)\alpha _k+{\displaystyle \frac{1}{3}}\left(i_0^2+i_0i_1+i_1^2\right){\displaystyle \frac{1}{6}}\left(7i_0+5i_1\right)+1\right].`$ (54)
Similarly, the contribution to the algebraic energy of all the terms in Eq. (51) with $`k=0`$

$$\underset{i=i_0}{\overset{i_1}{}}\lambda _{n,i}^2=4a^2\underset{i=i_0}{\overset{i_1}{}}(i+\alpha 1)^2$$
(55)
is easily seen to equal the right-hand side of Eq. (54), since $`\alpha _0=\alpha `$. The derivative of the right-hand side of Eq. (54) with respect to $`k`$, with $`i_0`$ and $`i_1`$ fixed, is given by

$$4a\mathrm{\#}(k)(2\alpha _k+i_0+i_12).$$
(56)
This is clearly positive, since $`i_0+i_120`$ and $`\alpha _k\alpha \frac{m_1}{a}>0`$ on account of (42). Hence the energy decreases if $`k`$ decreases, $`i_0`$ and $`i_1`$ being fixed. It follows that any multiindex $`n`$ corresponding to the minimum value of the algebraic energy must be of the form

$$n=(m,\mathrm{},m,m1,\mathrm{},m1,\mathrm{},ϵ,\mathrm{},ϵ),$$
(57)
where $`ϵ=0`$ or $`ϵ=1`$ and $`m_0mm_1`$.

Let $`k`$ be an integer in the range $`1`$ to $`m`$. We shall consider next the change in the algebraic energy associated to the multiindex (57) when $`\mathrm{\#}(k)`$ decreases by $`1`$, while $`\mathrm{\#}(k1)`$ increases by $`1`$ (including the case in which $`k=ϵ=1`$ and therefore $`\mathrm{\#}(k1)=\mathrm{\#}(0)=0`$). Suppose, for instance, that $`k2`$. Denoting $`i_2=\mathrm{}(k1)+\mathrm{\#}(k1)1`$, the change in the algebraic energy is given by

$`4a^2({\displaystyle \underset{i=i_0}{\overset{i_11}{}}}(ii_0i_1\alpha _k+2)^2{\displaystyle \underset{i=i_1}{\overset{i_2}{}}}(ii_1i_2\alpha _{k1}+1)^2`$ (58)
$`+{\displaystyle \underset{i=i_0}{\overset{i_1}{}}}(ii_0i_1\alpha _k+1)^2+{\displaystyle \underset{i=i_1+1}{\overset{i_2}{}}}(ii_1i_2\alpha _{k1})^2)`$
$`=4\left(1+2a(\alpha _k+i_11)\right)4(1+2a\alpha _k)<0.`$
It may be similarly verified that when $`k=1`$ and either $`ϵ=0`$ or $`ϵ=1`$ the change in the algebraic energy is negative. This implies that the multiindex $`n`$ yielding the algebraic ground state is of the form (53) if $`N>\overline{M}`$, and zero otherwise. The degeneracy of the algebraic ground state then follows immediately from Proposition 3. ∎

The algebraic ground energy can be easily obtained from the previous proposition and Eqs. (33) and (38). Indeed, denoting

$$\nu =2M+1,c=b+b^{}+2m_0a,$$

the algebraic ground energy for even $`\nu `$ (that is, half-integer $`M`$) is given by

$$E_{0,e}^{}=\frac{1}{3}\nu m_0\left(4m_0^2(a\nu 1)6cm_0a\nu 2\right)+\frac{1}{3}(a^23c^2)N+2acN^2\frac{4}{3}a^2N^3,$$

while for odd $`\nu `$ (integer $`M`$), the algebraic ground energy reads

$$E_{0,o}^{}=E_{0,e}^{}+m_0\left(a+2c+2m_0(1a\nu )\right).$$

## IV The $`B_N`$-Type Sutherland Spin Chain

In this section we shall introduce a quantum spin chain closely related to the hyperbolic $`B_N`$ Sutherland spin model (1). We shall establish the integrability of this chain by explicitly constructing a complete family of commuting integrals of motion associated with the integrals $`I_p^{}`$ of the Hamiltonian (1).

The starting point in this construction is the following expansion of the hyperbolic $`B_N`$ Sutherland spin Hamiltonian (1) in terms of the parameter $`a`$:

$$H^{}=\underset{i}{}_{x_i}^2+a^{}+a^2U(𝐱),$$
(59)
where

$`^{}={\displaystyle \underset{ij}{}}\left[\mathrm{sinh}^2x_{ij}^{}S_{ij}+\mathrm{sinh}^2x_{ij}^+\stackrel{~}{S}_{ij}\right]+{\displaystyle \underset{i}{}}\left(\beta \mathrm{sinh}^2x_i\beta ^{}\mathrm{cosh}^2x_i\right)S_i`$ (60)
$`U(𝐱)={\displaystyle \underset{ij}{}}\left(\mathrm{sinh}^2x_{ij}^{}+\mathrm{sinh}^2x_{ij}^+\right)+{\displaystyle \underset{i}{}}\left(\beta ^2\mathrm{sinh}^2x_i\beta ^2\mathrm{cosh}^2x_i\right)`$ (61)
and

$$\beta =\frac{b}{a},\beta ^{}=\frac{b^{}}{a}.$$

The Hamiltonian of the hyperbolic Sutherland spin chain of $`B_N`$ type is by definition the operator $`^0`$, where the superscript $`0`$ means that the coordinates $`x_i`$ are replaced by the equilibrium points $`x_i^0`$ of the potential $`U`$, which satisfy the system

$$\frac{U}{x_i}(x_1^0,\mathrm{},x_N^0)=0,i=1,\mathrm{},N.$$
(62)
A necessary condition for the system (62) to have a solution in the region $`x_i>0`$, $`i=1,\mathrm{},N`$, is that $`\beta ^2>\beta ^2+2(N1)`$. In fact, there is strong numerical evidence that a solution exists if and only if $`|\beta ^{}|>|\beta |+2(N1)`$. Note that this inequality corresponds to the condition (43) (when $`b>0`$) or (44) (when $`b<0`$) necessary for the existence of square-integrable algebraic eigenfunctions of the dynamical model, a fact certainly deserving further study.

Let us define the operator $`𝒥_iC^{\mathrm{}}(^N)𝔎`$ by

$$J_i=_{x_i}a𝒥_i,i=1,\mathrm{},N.$$
(63)
We shall also denote

$$_p=\underset{i}{}𝒥_i^{2p},p.$$
(64)
Note that $`_1`$ is the coefficient of $`a^2`$ in $`I_1=H`$, and thus equals $`U(𝐱)`$ by Eq. (59). We shall prove below that the operators $`\{_p^0\}_{p=1}^N`$ form a complete family of commuting integrals of motion for the Sutherland $`B_N`$ spin chain Hamiltonian $`^0`$. Let us begin by establishing the commutativity of the operators $`_p^0`$ for all $`p`$. In fact, the following stronger result holds:

###### Proposition 5.

The operators $`_p^{}`$ $`(p)`$ form a commuting family.

###### Proof.

The proposition follows directly from the commutativity of the operators $`I_p^{}`$, taking into account that $`_p^{}`$ is the coefficient of $`a^{2p}`$ in the expansion of $`I_p^{}`$ in powers of $`a`$. ∎

We show next that $`_p^0`$ commutes with $`^0`$ for all $`p`$. Note that this is not a consequence of the previous proposition, since $`^0`$ is not proportional to $`_1^0=U(𝐱^0)`$.

###### Proposition 6.

The operators $`_p^0`$ $`(p)`$ commute with the $`B_N`$ Sutherland spin chain Hamiltonian $`^0`$.

###### Proof.

From (24) it follows that

$$[H,J_i]=0,i=1,\mathrm{},N.$$

Using Eqs. (6) and (59) in the previous identity and equating to zero the coefficient of $`a^2`$ in the resulting expression we obtain

$$[,𝒥_i]=\frac{U}{x_i},i=1,\mathrm{},N.$$

It follows that

$$[,_p]=\underset{i=1}{\overset{N}{}}\underset{r=0}{\overset{2p1}{}}\left(\genfrac{}{}{0pt}{}{2p1}{r}\right)𝒥_i^r\frac{U}{x_i}𝒥_i^{2pr1}𝒞_p.$$

The operator $`𝒞_1=[,U(𝐱)]`$ vanishes identically, since $``$ does not contain partial derivatives and $`U(𝐱)`$ is a symmetric even function of $`𝐱`$. Note, however, that $`𝒞_p`$ need not vanish for $`p>1`$. Expanding in powers of $`a`$ the identities $`[H,\mathrm{\Lambda }]=[I_p,\mathrm{\Lambda }]=0`$ we obtain

$$[,\mathrm{\Lambda }]=[_p,\mathrm{\Lambda }]=0,p.$$

By Lemma 3 we have

$$[^{},_p^{}]=𝒞_p^{},p.$$
(65)
¿From the symmetry of the function $`U(𝐱)`$ with respect to permutations and sign changes it follows that $`U/x_i`$ commutes with $`K_{jk}`$ and $`K_j`$ for $`j,ki`$, while

$`K_{ij}{\displaystyle \frac{U}{x_i}}={\displaystyle \frac{U}{x_j}}K_{ij},K_i{\displaystyle \frac{U}{x_i}}={\displaystyle \frac{U}{x_i}}K_i.`$
¿From these identities one can easily show that $`𝒞_p^{}`$ is of the form

$$𝒞_p^{}=\underset{i}{}\frac{U}{x_i}𝒞_{p,i}^{},p.$$

The commutativity of $`^0`$ with $`_p^0`$ follows from the latter equation, Eq. (65) and the definition of the equilibrium points (62). ∎

Finally, we prove the algebraic independence of the set $`\{_p^0\}_{p=1}^N`$, thus establishing the integrability of the hyperbolic Sutherland spin chain of $`B_N`$ type:

###### Theorem 3.

The operators $`\{_p^0\}_{p=1}^N`$ form a complete family of commuting integrals of motion for the $`B_N`$ Sutherland spin chain Hamiltonian $`^0`$.

###### Proof.

The set $`\{_p^0\}_{p=1}^N`$ is algebraically independent, since the operators $`𝒥_i^0`$ ($`i=1,\mathrm{},N`$) are linearly independent and commute with each other. The counterpart of Lemma 2 for the inverse of the star operator implies that the family $`\{_p^0\}_{p=1}^N`$ is also algebraically independent. The lemma now follows from the identity $`_p^0=_p^0`$. ∎

Note also that the constants of motion $`_p^0`$ ($`p`$) commute with the total permutation and sign reversing operators $`\mathrm{\Pi }_{ij}`$ and $`\mathrm{\Pi }_i`$. This follows from the identities $`[I_p^{},\mathrm{\Pi }_{ij}]=[I_p^{},\mathrm{\Pi }_i]=0`$ by taking the coefficient of $`a^{2p}`$.

###### Acknowledgements.

This work was partially supported by the DGES under grant PB98-0821. R. Zhdanov would like to acknowledge the financial support of the Spanish Ministry of Education and Culture during his stay at the Universidad Complutense de Madrid. The authors would also like to thank the referee for several helpful remarks.


format: text

text:
# Persistent currents due to point obstacles

## 1 Introduction

Persistent currents in rings threaded by a magnetic flux are one of the characteristic features of mesoscopic systems – see, e.g., \[CGR, CWB\] and numerous other theoretical and experimental papers where they were discussed. Recall that for a charged particle (an electron) confined to a loop $`C`$ the effect is contained in the dependence of the corresponding eigenvalues $`E_j`$ on the flux $`\varphi `$ threading the loop measured in the units of flux quanta, $`2\pi \mathrm{}c|e|^1`$. Specifically the derivative $`E_j/\varphi `$ equals $`\frac{1}{c}I_j`$, where $`I_j`$ is the persistent current in the $`j`$–th state. In particular, if the particle motion on the loop is free, we have

$$E_j(\varphi )=\frac{\mathrm{}^2}{2m^{}}\left(\frac{2\pi }{L}\right)^2(j+\varphi )^2,$$
(1.1)
where $`L`$ is the loop circumference, so the currents depend linearly on the applied field.

The above example represents an ideal case when the particle is strictly confined to the loop. On the other hand, there are many situations when a particle in a magnetic field can be transported being localized essentially in the vicinity of a barrier or an interface. A prominent example are the edge currents \[Ha, MS\]. They attracted a new wave of interest recently when in several papers \[BP, FGW, FM, MMP\] conditions were derived under which such a transport remained preserved in the presence of a disorder.

Even weaker interaction giving rise to a magnetic transport, this time without a classical analogue, was found in \[EJK\], where the Landau Hamiltonian was perturbed by a straight equidistant array of $`\delta `$ potentials. It was shown that such an operator has bands of absolutely continuous spectrum in the gaps between the Landau levels. An independent evidence for the transport in this situation was found in \[Ue\].

The question we are going to ask in this paper is the following. If we take a finite array of identical $`\delta `$ potentials in the plane making a loop, does the mentioned transport give rise to persistent currents? As we will see the answer is in general positive if the effective radii of the $`\delta `$ potentials (specified below – see (2.4)) and the cyclotronic radius corresponding to the field intensity are much smaller than the loop size. We also discuss the effect of disorder manifested by randomization of the coupling constants and show that the effect is sensitive to such perturbations: in an example with a ring of 12 obstacles a variation larger than 1% leads to a localization.

## 2 The model

### 2.1 2D magnetic systems with point obstacles

As we said above, we are going to study a charged particle in the plane subject to a homogeneous magnetic field perpendicular to the plane interacting with an equidistant array of point obstacles placed at points $`\stackrel{}{a}_j,j=1,\mathrm{},N`$, belonging to a closed loop. The simplest example is the situation when the latter is a circle,

$$\stackrel{}{a}_j=(R\mathrm{cos}\frac{2\pi j}{N},R\mathrm{sin}\frac{2\pi j}{N}),j=1,\mathrm{},N.$$
(2.1)
For the sake of brevity we shall write $`\stackrel{}{a}:=(\stackrel{}{a}_1,\mathrm{},\stackrel{}{a}_N)`$. The obstacles will be modeled by $`\delta `$ potentials so formally the Hamiltonian of the system can be written as

$$H=\left(i\stackrel{}{}\stackrel{}{A}(\stackrel{}{x})\right)^2+\underset{j=1}{\overset{N}{}}\stackrel{~}{\alpha }_j\delta (\stackrel{}{x}\stackrel{}{a}_j),$$
(2.2)
where $`\stackrel{}{A}`$ is the appropriate vector potential which we choose here in the circular gauge,

$$\stackrel{}{A}(\stackrel{}{x})=(\frac{1}{2}By,\frac{1}{2}Bx).$$

To make things simple we have used rationalized units in (2.2) putting $`\mathrm{}=c=e=2m^{}=1`$. On the other hand, the two-dimensional $`\delta `$ interaction is an involved object. To give it meaning and to specify the true coupling parameter which would replace the formal $`\stackrel{~}{\alpha }_j`$’s, we use the definition based on self-adjoint extensions which is discussed thoroughly in \[AGHH\], see also \[DO, GHŠ\] for the situation with a magnetic field. A $`\delta `$ interaction is determined by means of the boundary conditions

$$L_1(\psi ,\stackrel{}{a}_j)+2\pi \alpha _jL_0(\psi ,\stackrel{}{a}_j)=0,j=1,\mathrm{},N,$$
(2.3)
which couple the generalized boundary values

$$L_0(\psi ,\stackrel{}{a}):=\underset{|\stackrel{}{x}\stackrel{}{a}|0}{lim}\frac{\psi (\stackrel{}{x})}{\mathrm{ln}|\stackrel{}{x}\stackrel{}{a}|},L_1(\psi ,\stackrel{}{a}):=\underset{|\stackrel{}{x}\stackrel{}{a}|0}{lim}\left[\psi (\stackrel{}{x})L_0(\psi ,\stackrel{}{a})\mathrm{ln}|\stackrel{}{x}\stackrel{}{a}|\right].$$

We now put $`\alpha :=(\alpha _1,\mathrm{},\alpha _N)`$ and denote by $`H_{\alpha ,\stackrel{}{a}}^B`$ the Hamiltonian of our model, which acts as free outside the interaction support,

$$H_{\alpha ,\stackrel{}{a}}^B\psi (\stackrel{}{x})=\left(i\stackrel{}{}\stackrel{}{A}(\stackrel{}{x})\right)^2\psi (\stackrel{}{x})$$

for $`\stackrel{}{x}\stackrel{}{a}`$, and its domain consists of all functions which belong to the Sobolev class $`W^{2,2}(^2\stackrel{}{a})`$ and satisfy the boundary conditions (2.3).

The parameters $`\alpha _j`$ characterizing the “strength” of the interaction are not trivial \[EŠ, CS\]; this is clear from the fact that the free (Landau) Hamiltonian, which we denote as $`H^B`$, corresponds to $`\alpha _j=\mathrm{},j=1,\mathrm{},N`$. The difference between $`\alpha _j`$ and the formal coupling constants used in (2.2) reflects the nontrivial way in which the two-dimensional point interaction arises in the limit of scaled potentials. To understand the $`\alpha _j`$’s it is more natural to associate them with the scattering length: by \[EŠ\] the point interaction with the parameter $`\alpha `$ reproduces the low-energy behaviour of the scattering upon an obstacle of the radius $`\rho `$ provided

$$\alpha =\frac{1}{2\pi }\mathrm{ln}\rho .$$
(2.4)
### 2.2 Spectral properties of $`H_{\alpha ,\stackrel{}{a}}^B`$

The spectrum of the free operator $`H^B`$ is the series of infinitely degenerate eigenvalues $`B(2n+1),n=0,1,\mathrm{}`$. A finite number of point interactions leaves the essential spectrum intact so $`\sigma _{\mathrm{ess}}(H_{\alpha ,\stackrel{}{a}}^B)`$ consists again of the Landau levels. Moreover, it follows from general principles \[We, Sec .8.3\] that $`N`$ point interactions can give rise to at most $`N`$ eigenvalues in each gap of $`\sigma (H^B)`$. It is this discrete spectrum which is the object of our interest.

To find it we can make use of Krein’s formula \[AGHH, App. A\] which expresses the resolvent kernel of $`H_{\alpha ,\stackrel{}{a}}^B`$ by means of that of the free operator, specifically

$$(H_{\alpha ,\stackrel{}{a}}^Bz)^1(\stackrel{}{x},\stackrel{}{x}^{})=G_B(\stackrel{}{x},\stackrel{}{x}^{};z)+\underset{j,m=1}{\overset{N}{}}[\mathrm{\Lambda }_{\alpha ,\stackrel{}{a}}^B(z)]_{jm}^1G_B(\stackrel{}{x},\stackrel{}{a}_j;z)G_B(\stackrel{}{a}_m,\stackrel{}{x}^{};z),$$
(2.5)
where $`\mathrm{\Lambda }^B\mathrm{\Lambda }_{\alpha ,\stackrel{}{a}}^B(z)`$ is the $`N\times N`$ matrix with the elements

$$\mathrm{\Lambda }_{jm}^B:=\left(\alpha _j\xi (B;z)\right)\delta _{jm}G_B(\stackrel{}{a}_j,\stackrel{}{a}_m;z)(1\delta _{jm}),$$

where $`G_B(\stackrel{}{x},\stackrel{}{x}^{};z)`$ is the resolvent kernel of $`H^B`$ and $`\xi (B;z)`$ its regularized value at the singularity,

$$\xi (B;z):=\underset{\stackrel{}{x}^{}\stackrel{}{x}}{lim}\left[G_B(\stackrel{}{x},\stackrel{}{x}^{};z)+\frac{1}{2\pi }\mathrm{ln}|\stackrel{}{x}\stackrel{}{x}^{}|\right]$$
(2.6)
which is independent of $`\stackrel{}{x}`$. The sought discrete spectrum is given by the singularities of the second term at the r.h.s. of (2.5), or in other words, by solutions of the spectral condition

$$det\mathrm{\Lambda }_{\alpha ,\stackrel{}{a}}^B(z)=0.$$
(2.7)
If $`z=z_0`$ satisfies this, it is an eigenvalue of the operator $`H_{\alpha ,\stackrel{}{a}}^B`$ and the equation $`\mathrm{\Lambda }_{\alpha ,\stackrel{}{a}}^B(z_0)d=0`$ has a nontrivial solution in $`^N`$; the corresponding non-normalized eigenfunction is then

$$\psi _{\alpha ,\stackrel{}{a}}^{B,z_0}=\underset{j=1}{\overset{N}{}}d_jG_B(\stackrel{}{a}_j,;z_0)$$
(2.8)
as can be checked by a standard argument \[AGHH\].

To make use of the above formulae we need the explicit form of the free Green’s function. It is known \[DMM\] to be

$$G_B(\stackrel{}{x},\stackrel{}{x}^{};z)=\frac{1}{4\pi }\mathrm{\Phi }_B(\stackrel{}{x},\stackrel{}{x}^{})\mathrm{\Gamma }\left(\frac{|B|z}{2|B|}\right)U(\frac{|B|z}{2|B|},\mathrm{\hspace{0.17em}1};\frac{|B|}{2}|\stackrel{}{x}\stackrel{}{x}^{}|^2),$$
(2.9)
where

$$\mathrm{\Phi }_B(\stackrel{}{x},\stackrel{}{x}^{}):=\mathrm{exp}\left[\frac{iB}{2}(x_1x_1^{})(x_2+x_2^{})\frac{|B|}{4}|\stackrel{}{x}\stackrel{}{x}^{}|^2\right]$$

and $`U(u,v;\zeta )`$ is the singular confluent hypergeometric (or Kummer) function \[AS, Chap. 13\]. Using the asymptotic formula

$$U(u,1;\zeta )=\frac{1}{\mathrm{\Gamma }(u)}\left[\mathrm{ln}\zeta +\psi (u)2\psi (1)+(O)(\zeta ^2\mathrm{ln}^2\zeta )\right]$$

with $`\psi (u)`$ being the digamma function and $`\psi (1)=\gamma =0.577\mathrm{}`$ the Euler number we find

$$\xi (B;z)=\frac{1}{4\pi }\left[\psi \left(\frac{|B|z}{2|B|}\right)+2\gamma +\mathrm{ln}\frac{|B|}{2}\right].$$
(2.10)
In this way we have derived the explicit form of the matrix $`\mathrm{\Lambda }_{\alpha ,\stackrel{}{a}}^B(z)`$ appearing in the condition (2.7).

## 3 The results

In Fig. 1, we show the energy spectra of the system as a function of the common coupling strength $`\alpha _i=\alpha `$. In this example, the $`Np=12`$ of $`\delta `$-interactions are placed equidistantly on the ring of circumference $`L=2\pi `$. We can make this assumption without loss of generality. It is true that scaling systems with 2D point interactions reveals peculiar properties \[CS2\], but in effect changing the size of the system is equivalent to the shift of $`\alpha `$ on a constant proportional to logarithm of the scaling factor. One can see from this figure that, for our choice of the system size, the coupling becomes strong as the parameter approaches the value $`\alpha =1`$, in which case the eigenvalues split from the Landau levels of unperturbed system form a bunch of negative-energy states; recall that by(2.4) it corresponds to the scattering length $`\rho =e^{2\pi }`$.

The properties of these states are made clear by plotting their energies as the function of the magnetic field $`B`$. We set the strength parameter to be $`\alpha =1`$. In the top lines of Fig. 2, several lowest states are shown for for three cases $`Np=6`$, $`Np=12`$ and $`Np=24`$. As the number of the $`\delta `$-scatterers increases, one clearly sees the emergence of parabolic $`B`$ dependence, which is the hallmark of the persistent current we have been looking for. The situation becomes clearer when we plot derivatives $`dE/dB`$ and $`d^2E/dB^2`$ as the function of $`B`$. A direct evidence of the existence of persistent current in our system is shown in Fig. 3, in which the probability flux current is depicted for $`Np=12`$ case for the magnetic field strengths $`B=0.5`$, $`B=1.0`$, $`B=1.5`$ and $`B=2.0`$.

As with the “usual” persistent currents, one has to take into account the imperfection when thinking about the use of the effect in designing various devices. Thus the question of the robustness of the persistent current in our system is of interest. We test it by allowing random fluctuation of the coupling strengths of the $`\delta `$-scatterers. In Fig. 4, we plot the $`E`$, $`dE/dB`$ and $`d^2E/dB^2`$ as the function of $`B`$ as before, but letting the coupling strength of each scatterer to vary randomly by the amount $`\mathrm{\Delta }\alpha `$ uniformly around the central value $`\alpha =1`$. The fluctuations are taken to be $`\mathrm{\Delta }\alpha =0.01`$, $`\mathrm{\Delta }\alpha =0.02`$ and $`\mathrm{\Delta }\alpha =0.03`$ from the left to right. The number of $`\delta `$-scatterers is again set to be $`Np=12`$. Some examples of probability current flow patterns at $`B=0.5`$ for each case are shown in Fig. 5. While a more detailed analysis of such random perturbations is required, Figs. 4-5 suggest that the persistent current generated by the array of $`\delta `$-scatterers is sensitive to small fluctuations of the strength; one typically needs the accuracy of less the 1% to have the persistent current intact down to the ground state.

In conclusion, we have demonstrated a purely quantum mechanism able to create persistent currents in systems with arrays of tiny obstacles in magnetic field; it is the the wave nature of electrons which is responsible for this counterintuitive phenomenon. The result might eventually have a practical impact on the design of the quantum ring devices, however, the effect of localization by random perturbations deserves a deeper study.

### Acknowledments

P.E. appreciates the hospitality extended to him at the Kochi University of Technology where a part of this work was done. The research has been partially supported by GAAS and the Czech Ministry of Education within the projects A1048101 and ME170, and also by Grant-in-Aid for Scientific Research (C) (No. 13640413) by the Japanese Ministry of Science and Education.


text:
# Lattice model of gas condensation within nanopores

## I INTRODUCTION

A focus of current attention in statistical physics is the behavior of matter in confining geometries bar ; guyer ; tal ; page ; sar ; liu ; chan ; thom ; gubb ; schoen ; art ; evans . An extreme version of this problem arises for adsorption within nanotubes, a case for which the transverse dimensions may be of order molecular sizes. One expects an important parameter in this class of problem to be the ratio $`R^{}`$ of the diameter of the molecule to that of the tube. When this ratio is of the order one, the adsorbate may be well described by a one-dimensional (1D) model. As $`R^{}`$ decreases, one expects there to arise successively a sequence of onion-like concentric shells of matter; the number of possible shells is critically dependent on the value of $`R^{}`$. Accompanying the variation in $`R^{}`$ is a variation of energy scales, which are the crucial variables in the thermodynamics of the system.

There have been performed many studies of specific geometries and specific adsorbate-substrate combinations, as recently reviewed by Gelb et al gelb . However, there have been relatively few studies undertaken of the general problem of adsorption in pores in the case of variable $`R^{}`$. The present work represents an effort in that direction. Here, we employ a highly oversimplified lattice model of adsorption ebner ; olive  designed for cases when one or two concentric phases of matter (but no more) may be present. Since the present analysis is limited by the assumption of just two distinct species of lattice sites, it describes just the $`R^{}1`$ regime. Hence, there are assumed to be four possible phases for this geometry: an empty phase $`(E)`$, an axial phase $`(A)`$, in which atoms are adsorbed only on the cylinder’s axis, a cylindrical shell phase $`(S)`$, in which atoms condense close to the cylinder’s wall, and a full phase $`(F)`$, in which both axial and shell sites are populated with atoms. These are depicted schematically in Fig.1. We assume a model which includes both pore-site interactions and nearest neighbor interactions. Since the pore attraction is usually different for shell and axial sites, we may think of the axial and shell atoms as two different species interacting each other with a common value of the chemical potential $`\mu `$. The same idea was explored in adsorption problems involving two types of binding sites machta . Besides the pore attraction, the atoms experience an intra-species interaction (axial-axial or shell-shell) and an inter-species interaction (axial-shell). The phase behavior depends on the values of these various energies, especially on the attractive or repulsive character of the inter-species interaction.

Section $`2`$ of this paper presents results at zero temperature $`(T)`$ for the exact phase behavior as a function of the interactions. Section $`3`$ reports a mean field evaluation of the phase behavior at finite $`T`$. The adsorption behavior given by finite $`T`$ isotherms is compared to the phase diagrams at $`T=0`$. Section $`4`$ describes the relation between the lattice models and some examples of possible realistic situations, i.e., gases adsorbed in carbon nanotubes of various radii. Ultimately, we would like to relate the systems’ properties to energy scales present in the real problem. Since these may not be known, it becomes possible in principle to deduce these by comparing experimentally observed phase behavior with that predicted by the model. In view of the approximations inherent in the lattice model, we believe that our results provide a qualitative picture of the expected phase behavior and its evolution with the size ratio $`R^{}`$ mentioned above.

## II ZERO TEMPERATURE ANALYSIS

As a starting point, we consider adsorption in infinite cylindrical pores at $`T=0`$. The possible phases are described in the introduction. The cases when the shell-axial interaction is attractive or repulsive are investigated separately. We will illustrate in detail our analysis for the case of an attractive inter-species interaction. Initially, to simplify the discussion, assume that the analysis can be divided into two alternative approaches. In one, we consider the only possible phases to be $`E,A`$ and $`F`$. In the other, we consider just the phases $`E,S`$ and $`F`$. We show below that this separation into two distinct treatments encompasses all possibilities for the case of attractive interactions between $`A`$ and $`S`$ sites. However, in the case of a repulsive interaction, this division of the problem into two parts does not work, necessitating a somewhat more complicated numerical analysis.

The phase transition diagrams are constructed on the basis of free energy considerations. The shell species is adsorbed on a 2D lattice of sites, with the interaction energy $`ϵ_s`$ between particles at adjacent sites. For simplicity, this 2D lattice on a cylindrical surface is taken as a square lattice; hence, the number of nearest shell neighbors of a shell atom $`z_s`$ is $`4`$. The axial species is adsorbed on a 1D lattice of sites, of interaction strength $`ϵ_a`$ and coordination number $`z_a=2`$. We include also the interaction between axial and shell sites, denoted by $`ϵ_{sa}`$. Throughout the paper, we express all energies, chemical potentials and temperatures in units of $`ϵ=ϵ_s=ϵ_a`$ , the absolute value of the interatomic interaction. For simplicity, we assume that shell atoms sit on rings whose centers are occupied by axial atoms. The number of axial neighbors for a shell site $`(z_{sa})`$ is $`1`$ and the number of shell neighbors for an axial site $`(z_{as})`$ is larger than $`1`$.

We first determine the equilibrium phase as a function of $`\mu `$. The axial, shell and full grand free energies ($`\mathrm{\Omega }=F\mu N`$, where $`F`$ is the Helmholtz free energy) at $`T=0`$ , can be written as:

$$\mathrm{\Omega }_a=N_a(V_a\frac{z_a}{2})\mu N_a$$
(1)
$$\mathrm{\Omega }_s=N_s(V_s\frac{z_s}{2})\mu N_s$$
(2)
$$\mathrm{\Omega }_f=N_a(V_a\frac{z_a}{2})+N_s(V_s\frac{z_s}{2})+N_sz_{sa}ϵ_{sa}\mu (N_a+N_s)$$
(3)
where $`N_{a(s)}`$ is the number of sites in the axial (shell) phase and $`V_{a(s)}`$ is the interaction potential energy experienced by the axial (shell) site due to the nanotube environment. Adsorption in nanopores at $`T=0`$ can occur only if the adsorbate is attracted to the interior of the nanopore, i.e. $`V_{a(s)}<0`$. We denote the ratio of axial to shell densities (number of atoms per pore length) as $`\gamma =N_a/N_s`$. The axial and shell cohesive energies per particle are respectively:

$$E_a=(V_az_a/2)$$
(4)
$$E_s=(V_sz_s/2)$$
(5)
These energies consist of the pore attraction energy and the nearest neighbor interaction (the factor of $`1/2`$ avoids double counting). With this notation, and replacing $`z_{sa}`$ by $`1`$, the grand free energies can be rewritten as:

$$\frac{\mathrm{\Omega }_a}{N_s}=\gamma E_a\gamma \mu $$
(6)
$$\frac{\mathrm{\Omega }_s}{N_s}=E_s\mu $$
(7)
$$\frac{\mathrm{\Omega }_f}{N_s}=\gamma E_aE_s+ϵ_{sa}\mu (\gamma +1)$$
(8)
One observes that the adsorption behavior (as a function of $`\mu `$) depends on four parameters: $`\gamma `$, $`ϵ_{sa}`$, $`E_a`$ and $`E_s`$. The $`T=0`$ isotherms are determined by finding the minimum of these $`\mathrm{\Omega }`$ values and comparing the result with the empty lattice result $`\mathrm{\Omega }_E=0`$. The axial phase is favored relative to the empty phase if $`\mathrm{\Omega }_a<0`$, i.e.

$$\mu >E_a$$
(9)
The full phase is lower in grand free energy than the empty phase if $`\mathrm{\Omega }_f<0`$, i.e.

$$\mu >(E_sE_a\gamma +ϵ_{sa})/(1+\gamma )$$
(10)
The axial phase is favored relative to the full phase if $`\mathrm{\Omega }_a<\mathrm{\Omega }_f`$, implying

$$\mu <E_s+ϵ_{sa}$$
(11)
An analogous argument is true for the shell phase. $`\mathrm{\Omega }_s<0`$ implies

$$\mu >E_s$$
(12)
Note that $`\mathrm{\Omega }_s<\mathrm{\Omega }_f`$ if

$$\mu <E_a+\frac{ϵ_{sa}}{\gamma }$$
(13)
First, we construct two independent phase diagrams with $`E_{a(s)}`$ and $`\mu `$ as coordinates, corresponding to $`(E,S,F)`$ and $`(E,A,F)`$ cases. Then, by inspecting the diagrams, we learn how to combine them into a single diagram applicable to both cases at once. We first analyze the $`E,S,F`$ possible phase transitions alone. The $`\mu `$ regime of each phase is determined by comparison using the equations $`(10),(12),(13)`$. The transitions between these phases occur at values of $`\mu `$ such that the inequalities $`(10),(12),13)`$ become equalities. In addition, we have to take into consideration that the chemical potential of the pore condensation should be smaller than the chemical potential of bulk condensation in the simple cubic lattice Ising model, which is $`\mu _0=3`$. (Of course, transitions can occur within the pore for $`\mu >\mu _0`$, but one does not ordinarily study them.) Due to this restriction, we can distinguish two cases. The first occurs when the $`SF`$ transition is below saturation ($`E_a+ϵ_{sa}/\gamma <3`$). Then, all three phases $`E,S,F`$ are possible, as shown in $`Fig.2a`$. The alternative scenario occurs when the $`SF`$ transition is above saturation ($`E_a+ϵ_{sa}/\gamma >3`$). In this case, there are only two possible phases, $`E`$ and $`S`$, as shown in $`Fig.2b`$.

The $`E,A,F`$ phase analysis is very similar to that above for $`E,S,F`$. The two cases which can be distinguished here are : $`a)E_s+ϵ_{sa}>3`$, when all three phases ($`E,A,F`$) are possible and $`b)E_s+ϵ_{sa}<3`$ , when there are only two possible phases, $`E`$ and $`A`$.

So far, the phase transition behavior has been derived from two separate analyses: $`E,S,F`$ and $`E,A,F`$. We now show how the parameter values may be assessed in order to establish which of the two analyses is appropriate to a given system, i.e. a specified set of parameters. To do so, we need to compare values of $`\mathrm{\Omega }_a`$ and $`\mathrm{\Omega }_s`$. The difference between the relevant free energies satisfies:

$$\frac{\mathrm{\Omega }_s\mathrm{\Omega }_a}{N_s}=E_s+E_a\gamma \mu (1\gamma )$$
(14)
As can be seen from $`eqn.9`$ , the $`EA`$ transition occurs at $`\mu _{ea}=E_a`$. In the limit $`\mu =\mu _{ea}`$, then

$$\frac{\mathrm{\Omega }_s\mathrm{\Omega }_a}{N_s}=(E_sE_a)$$
(15)
If $`E_a<E_s`$, then $`\mathrm{\Omega }_s<\mathrm{\Omega }_a`$ at this value of $`\mu `$. At higher value of $`\mu `$ ($`>\mu _{ea}`$), $`\mathrm{\Omega }_s`$ remains less than $`\mathrm{\Omega }_a`$. Hence a transition to the axial phase does not occur for any $`\mu `$. If, instead, $`E_s<E_a`$, then $`\mathrm{\Omega }_a<\mathrm{\Omega }_s`$ and the axial phase is stable at $`\mu =\mu _{ea}`$. Is it possible that $`\mathrm{\Omega }_s\mathrm{\Omega }_a`$ changes sign for higher $`\mu `$ (corresponding to an $`A`$ to $`S`$ transition)? This would require $`\mathrm{\Omega }_a=\mathrm{\Omega }_s`$ at a transition value $`\mu =\mu _{as}`$ such that

$$\mu _{as}=\frac{E_a(\gamma \rho )}{1\gamma }$$
(16)
where $`\rho =E_a/E_s<1`$. Hence $`\rho \gamma >3(1\gamma )/E_a>1\gamma `$. This implies $`\rho >1`$, which violates the assumption $`E_s<E_a`$. This rules out such a possibility.

The same examination can be done at the $`ES`$ transition line, $`\mu _{es}=E_s`$; we then find that for $`E_s<E_a`$, the shell phase does not occur. Hence the possibilities are either $`E_s>E_a`$ (never the $`A`$ phase) or $`E_a>E_s`$ (never the $`S`$ phase). This justifies the separate analyses used above for the two distinct cases which can arise.

Because the two cases correspond to different regimes of parameter space, $`E_s>E_a`$ and $`E_s<E_a`$, they can be merged in a phase diagram which has as coordinates the interactions present in our problem: $`E_a`$ and $`E_s`$. One has only to analyze $`Fig.2a,b`$ and find the adsorption sequences as a function of both interactions when $`\mu `$ is increased. $`Fig.3`$ exhibits the regimes of distinct adsorption sequences. All possible sequences occur except those ruled out by the thermodynamic stability condition $`\mu /N>0`$. The region denoted $`E`$ corresponds to repulsive, or weakly attractive, pore-gas interactions, so that no atoms adsorb inside the pore. In the $`EA`$ region, the shell phase’s chemical potential of condensation is greater than $`3`$, so the F phase does not occur. Physically, the $`EA`$ region corresponds to a repulsive, or weakly attractive, pore-shell interaction and an attractive pore-axis interaction; hence, atoms adsorb only at the axial sites . In the $`EAF`$ region, the attraction in the axial phase is larger than that in the shell phase, so that the axial region is occupied first and then the shell follows at higher $`\mu `$. Similar reasoning applies to the $`ES`$ and $`ESF`$ regions. Possibly, the most interesting behavior occurs in the $`EF`$ region. In general, as seen more clearly at finite $`T`$, the axial and shell condensations occur at different chemical potentials. However, in the case of an attractive axial-shell interaction, when the shell and axial energies per particle are similar, the shell and axial phases become cooperative and undergo a common pore filling transition.

We have examined thus far the case of an attractive axial-shell interaction. In the repulsive case, the inter-species interaction energy ($`ϵ_{sa}`$) is positive. Then, we have to take into account a new possibility, the transition from axial to shell phase (alone). Physically, this means that when the shell atoms are adsorbed, the axial phase, which has a lower density than the shell phase, is expelled by the repulsive axial-shell interaction. Therefore, we compare all the grand free energies $`\mathrm{\Omega }_a,\mathrm{\Omega }_s,\mathrm{\Omega }_f`$ with each other and the zero energy of the E phase. We present the resulting phase diagrams in $`(E_a,\mu )`$ and $`(E_s,\mu )`$ coordinates in $`Fig.4a`$ and $`4b`$. Both diagrams exhibit all phases and possible transitions $`EA,ES,AS,AF`$ and $`SF`$, but there is no $`EF`$ transition. There are several qualitative differences between this case, shown in $`fig.5`$, and the attractive interaction case, shown in $`fig.3`$. Missing in the repulsive case is $`EF`$; present in this case are $`EASF`$ and $`EAS`$ sequences (absent in the attractive case). The last two are associated with the appearance of $`S`$, at the expense of A atoms, in order to decrease $`\mathrm{\Omega }`$ by adding more particles.

## III FINITE TEMPERATURE ANALYSIS

In this section, we explore the phase transitions at finite $`T`$ for a gas within our pore. This is a 1D system in the thermodynamic limit of divergent length. To study this model, we use mean field theory. It is known that 1D systems do not exhibit phase transitions at any finite T. However, in the present mean field treatment, we obtain a spurious transition. The results of an exact calculation of the phase behavior in a square pore swift  were found to be $`qualitatively`$ similar to those of mean field theory, apart from a narrow regime of $`\mu `$ where spurious transitions occur in mean field theory; these are replaced by nearly discontinuous isotherms in the exact case. We note that gases in some nanoporous media (zeolites or nanotube bundles) may represent quasi-1D systems which can go through a genuine phase transition when molecules in adjacent pores are coupled. This transition has been studied recently in a number of models of gases in pores, by both simulations and exact modelsrad ; cole ; calbi ; fisher .

The occupation probabilities of axial and shell sites are called $`n_a`$ and $`n_s`$, respectively. We construct the grand free energy of the system and minimize it with respect to $`n_s`$ and $`n_a`$. The same procedure was used in Refs.8 and 9 for analyzing layering and wetting phase transitions. The energy $`U`$ of the system is a generalization to finite T of the calculation in Section $`2`$. Specifically, the energy is:

$$U=N_sn_s(\frac{z_s}{2}n_s+V_s)+N_an_a(\frac{z_a}{2}n_a+V_a)+N_sn_s(z_{sa}n_aϵ_{sa})$$
(17)
and the entropy is written as:

$$S=N_s[n_s\mathrm{ln}n_s+(1n_s)\mathrm{ln}(1n_s)]N_a[n_a\mathrm{ln}n_a+(1n_a)\mathrm{ln}(1n_a)]$$
(18)
The minimization of the grand free energy $`UTS\mu N`$ with respect to the occupation numbers $`n_a`$ and $`n_s`$ yields two coupled equations, as found in reference :

$`n_s`$ $`=`$ $`{\displaystyle \frac{1}{1+\mathrm{exp}(\beta (\mu V_sz_sϵ_sn_sz_{sa}ϵ_{sa}n_a))}}`$
$`n_a`$ $`=`$ $`{\displaystyle \frac{1}{1+\mathrm{exp}(\beta (\mu V_az_aϵ_an_az_{as}ϵ_{sa}n_s))}}`$ (19)
First, we consider the case where the shell-axial interparticle energy $`ϵ_{sa}=0`$, so that we are left with 2 decoupled Ising problems. It is known that a lattice gas can be regarded as a lattice of spins, with the conversion $`s=2n1`$, $`J=ϵ/4`$ and the magnetic field $`h=(\mu V)/2zϵ/4`$. One can find the chemical potential of condensation from the condition for the magnetic transition $`(h=0)`$, and the mean field critical temperature $`T_c`$ in the Ising model: $`\beta _czJ=1`$, where $`\beta _c=(k_BT_c)^1`$. In the following, we take Boltzmann’s constant $`k_B=1`$. Thus, $`T_c=zϵ/4`$. Therefore, in the decoupled case, the shell and axial critical temperatures are $`T_{cs}=z_sϵ_s/4`$ and $`T_{ca}=z_aϵ_a/4`$, respectively. For simplicity, we again use the same axial and shell intra-species interaction $`ϵ_s=ϵ_a=ϵ`$, and scale the temperatures with respect to $`ϵ`$ . Considering a square shell lattice $`(z_s=4)`$ and a $`1D`$ axial lattice $`(z_a=2)`$, we obtain $`T_{cs}=1`$ and $`T_{ca}=0.5`$.

Let us consider the effect of turning on the axial-shell interaction. The mean field results are shown in $`fig.6`$ for $`ϵ_{sa}=1`$. The chemical potential of condensation is found by a Maxwell (equal-area) construction. For a large difference between the energies (per particle) $`E_a=(V_az_a/2)`$ and $`E_s=(V_sz_s/2)`$, the shell and axial species behave as in the decoupled case; two distinct transitions occur and the transition which occurs first (at lower $`\mu `$) corresponds to a lower free energy. However, in the case of similar energies, the two species exhibit a common transition. $`T_c>1`$ in this case because the cooperative system behaves like a single species of atoms, with a larger coordination number.

In order to compare our analysis at finite $`T`$ with that at $`T=0`$, we keep $`V_s`$ (or $`E_s`$) fixed and vary $`V_a`$ (or $`E_a`$), so that we move on a line parallel to the $`E_a`$ axis. In the finite $`T`$ case, we watch the resulting evolution of the axial and shell critical transitions. There arises a convenient quantity for characterizing this dependence; this is called $`\delta `$, defined by:

$`\delta =(E_sϵ_{sa}z_{sa}/2)(E_aϵ_{sa}z_{as}/2)`$ (20)
The evolution of these transitions with $`\delta `$ is shown in $`Fig.7`$ for three different interaction strengths. Consider first the strong attractive case $`(ϵ_{sa}=1)`$. For small axial energies per particle $`(\delta <4)`$, the shell condensation occurs at a lower value of $`\mu `$ than that associated with full condensation. The axial and shell critical temperatures are the same as in the decoupled case ($`0.5`$ and $`1`$). This corresponds to the $`ESF`$ region in $`fig3`$. When $`\delta =4`$, the effect of interaction between species becomes significant and the two transitions merge. As $`|\delta |`$ approaches $`0`$, the common transition’s critical temperature increases to the value $`1.45`$ (an increase of $`45\%`$ ) at $`\delta =0`$. When $`\delta `$ increases from zero to $`4`$, $`T_c`$ decreases symmetrically with the case $`\delta <0`$. This corresponds to the $`EF`$ region of $`(Fig.3)`$. A similar critical temperature dependence on the difference between site binding energies was observed in Monte Carlo simulations of benzene condensation in Na-X zeolites machta . The difference was in that case, $`T_c`$ dropped abruptly to zero when $`\delta `$ exceeded a threshold corresponding to a decoupling of the two transitions (since neither species in that case had an infinite connected path of its own). When $`\delta >4`$ , the system returns to the case of two separate axial and shell transitions. As the axial-shell atractive interaction is reduced, the range of $`\delta `$ values corresponding to cooperative behavior decreases, as shown in $`Fig.7`$. Note that the maximum value of $`T_c`$ for the case $`ϵ_{sa}=0.5`$ is only $`15\%`$ greater than that of the decoupled shell transition. When $`ϵ_{sa}`$ becomes very small (0.1 in $`Fig.7`$), a single transition occurs for small $`|\delta |`$, but the transition critical temperature equals that of the shell phase alone.

We have also considered the finite $`T`$ case of a repulsive interaction, $`ϵ_{sa}<0`$. Again, we study the behavior with $`E_s`$ constant and vary $`E_a`$, so we move on a line parallel to the $`E_a`$ axis in $`Fig.5`$. The resulting isotherms, corresponding to several different regions in $`Fig.5`$, are shown in $`Fig.8`$. A variety of scenarios can be seen, including those with $`A`$ either preceding or following $`S`$. The behavior as a function of $`E_s`$ is a logical correlate of that shown in $`Fig.5`$ at $`T=0`$. In contrast with the attractive case, there is no $`EF`$ region, even for similar axial and shell energies because the shell atoms, which have a higher density, expel the axial atoms. However, there occurs a qualitative similarity of the $`T_c`$ behavior. At low $`\mu `$, the axial atoms condense first. Then, at higher $`\mu `$, the shell is occupied while the axis is emptied. This transition occurs at the same $`T_c`$ as the cooperative transition in the attractive case. When the external pressure (i.e. $`\mu `$) is sufficiently high to overcome the axial-shell repulsive interaction, a full condensation occurs. These features are expressed in the ($`T_c,\mu `$) diagram for various values of $`ϵ_{sa}`$ and $`\delta =0`$ ($`Fig.9`$).

## IV REAL GASES IN CARBON NANOTUBES

We have discussed so far a simple and general theoretical model for adsorption of gases in a nanopore. Now, we consider the model’s prediction for a specific case - various gases adsorbed in C nanotubes. In the spirit of the model, we employ a number of simplifying assumptions. The adsorption potential we use is described in stan ; it is a sum of Lennard-Jones (LJ) two-body interactions between the C atoms (spread into continuous matter) and the adsorbate. The energy and distance parameters of this pair potential are obtained from semiempirical combining rules involving the LJ parameters of the C atoms $`(ϵ_{CC},\sigma _{CC})`$ and the adsorbate $`(ϵ_{gg},\sigma _{gg})`$ steele ; stee ; scoles :

$`ϵ_{gC}`$ $`=`$ $`\sqrt{(}ϵ_{gg}ϵ_{CC})`$
$`\sigma _{gC}`$ $`=`$ $`(\sigma _{gg}+\sigma _{CC})/2`$ (21)
The potential in the nanotube interior at distance $`r`$ from the axis of the cylinder is george :

$$V(r,R)=3\pi \theta ϵ_{gC}\sigma _{gC}^2[\frac{21}{32}(\frac{\sigma _{gC}}{R})^{10}M_{11}(\frac{r}{R})(\frac{\sigma _{gC}}{R})^4M_5(\frac{r}{R})]$$
(22)
where $`R`$ is the nanotube radius, $`\theta =0.32A^2`$ is the surface density of graphene $`C`$ atoms and

$$M_n(x)=_0^\pi \frac{d\varphi }{(1+x^22x\mathrm{cos}(\varphi ))^{n/2}}$$
(23)
The adsorption model is simple: the adatoms condense in a close-packed configuration, in both the shell and axial phases. We are excluding the case of very large $`R`$, which would result in the possibility of several concentric shells. As discussed in sections $`2`$ and $`3`$, our model has $`4`$ parameters: the shell and axial energies, the ratio of densities $`(\gamma )`$ and the inter-species interaction $`(ϵ_{sa})`$. They are not completely independent. One can readily identify the axial potential energy as $`V_a=V(0,R)`$. To find the shell potential, one should examine the form of potential. If $`R`$ is large, $`V(r,R)`$ has a minimum for a radius $`R_0`$ larger than the hard-core adsorbate radius $`\sigma _{gg}`$; then it is logical to assume that the gas atoms will be adsorbed in the shell phase at this distance $`(R_s=R_0)`$ and the shell potential is $`V(R_0,R)`$. If the pore radius is small ($`R_0<\sigma _{gg}`$), it is convenient to identify $`R_s=\sigma _{gg}`$ and the shell potential $`V_s=V(\sigma _{gg},R)`$. Geometrical calculations show that this is a good approximation, assuming that shell atoms sit near the optimal distance $`r_{min}=2^{1/6}\sigma _{gg}`$ from axial atoms. There is arbitrariness in these assignments, a situation which is inherent in any lattice model. $`V_a`$ and $`V_s`$ lead easily to the axial and shell energies per particle $`E_a=(V_az_a/2)`$ and $`Es=(V_sz_s/2)`$.

The intra- and inter-species interactions are found using Lennard-Jones parameters for the specific gas. The intra-species interaction energy is taken as $`ϵ_{gg}`$ and the inter-species energy is the adsorbate-adsorbate interaction at $`r=\sqrt{R_s^2+(r_{min}/2)^2}`$.

$$ϵ_{sa}=4ϵ_{gg}((\frac{\sigma _{gg}}{r})^{12}(\frac{\sigma _{gg}}{r})^6)$$
(24)
The number of shell atoms contained in a ring of radius $`R_s`$ is $`2\pi R_s/\sigma _{gg}`$ and the corresponding number of axial atoms is 1. Thus, an estimate of the ratio of densities is:

$`\gamma ={\displaystyle \frac{N_a}{N_s}}={\displaystyle \frac{\sigma _{gg}}{2\pi R_s}}`$ (25)
Table $`1`$ presents the resulting values of the various parameters for $`H_2`$ and $`Xe`$ inside nanotubes of various radii. The sequence of transitions is based on data in $`Fig.3`$. We note several features of these results. First, the only predicted transition scenarios are $`ESF`$, $`EF`$, $`EA`$ and no transition. The $`ES`$ and $`EAF`$ sequences are not found for $`H_2`$ or $`Xe`$. Physically, $`ES`$ corresponds to an attractive shell potential (negative $`V_s`$) but a repulsive axial potential (positive $`V_a`$); and $`EAF`$ corresponds to very attractive axial potentials and less attractive shell potentials. These do not occur in our model of nanotubes. We do find $`EA`$ and $`ESF`$ transitions for a relatively large range of nanotube radii. The cooperative behavior $`EF`$ occurs for a very small range of parameters because the gas-gas interaction strength is weak in comparison with the nanopore attraction. However, in the case of $`Xe`$, which has a much bigger cohesive energy ($`ϵ_{gg}=221K`$) than $`H_2`$ ($`ϵ_{gg}=37K`$), the mutual transition is more common. The $`H_2`$ gas undergoes the $`ESF`$ transitions for nanotubes with $`R>6`$ $`\stackrel{̊}{A}`$ , whereas $`Xe`$ goes through these transitions only for $`R>7.7`$ $`\stackrel{̊}{A}`$. This is due to the difference between these molecules’ sizes and interaction strengths. For $`R<7.3`$ $`\stackrel{̊}{A}`$, $`Xe`$ can accommodate only the axial phase, whereas the $`H_2`$ gas would go in the axial phase for $`R<5.8`$ $`\stackrel{̊}{A}`$. For very small $`R`$ (3.5 $`\stackrel{̊}{A}`$ for $`Xe`$, 3 $`\stackrel{̊}{A}`$ for $`H_2`$), gas does not adsorb at all in nanotubes because the pore gas potential becomes repulsive .

Hartree model calculations and path integral simulations were previously performed for adsorption of $`H_2`$ in $`C`$ nanotubes of radii $`6,7`$ and $`8`$ $`\stackrel{̊}{A}`$ gati . Our classical results are in qualitative agreement with these results. The previous study also found the $`ESF`$ for this range of nanotube radii. However, their quantum calculations allowed them to investigate the delocalization of the axial state. For $`R=8`$ $`\stackrel{̊}{A}`$ the axial state’s probability density is no longer confined to the immediate vicinity of the axis, exhibiting a maximum near $`r=2`$ $`\stackrel{̊}{A}`$. This is actually not an axial phase, but rather a second shell phase, of small radius. In our calculations, the axial phase is confined to the nanotube axis and such a second shell phase is not considered.

## V SUMMARY AND CONCLUSIONS

We have investigated the adsorption of gases in nanopores, employing a lattice model, which we solved exactly at $`T=0`$ and approximately at finite $`T`$. Various regimes of transition behavior were found, corresponding to a range of interaction strengths. The sequence of transitions as a function of $`\mu `$ depends on both the axial-shell interaction energy and the difference between the axial and shell energies per particle. When this difference is large, the two species condense independently, i.e. the two species are essentially decoupled. When this difference is small, the behavior depends on the sign of the axial-shell interaction. For $`ϵ_{sa}>0`$ (attractive case), the axial and shell phases undergo a common transition at a higher critical temperature. For $`ϵ_{sa}<0`$, an increase of the critical temperature occurs, corresponding to an $`AS`$ transition.

The most important parameter is the radius of the nanotube or, specifically ,the ratio $`R^{}`$ discussed in the introduction. Even though its value does not appear explicitly in section $`2`$ and $`3`$, it determines most of the other parameters. This is discussed in section $`4`$, where the $`R`$ dependence of the behavior is explored. Depending on the adsorbate size and interaction strength, we find typically that $`EA`$ occurs for small $`R^{}`$, the $`ESF`$ occurs for large $`R^{}`$ and the coupled condensation ($`EF`$) occurs for a small range of intermediate $`R^{}`$.

Our approach certainly oversimplifies the real situation in nanopores. First, the lattice gas model constrains the atoms to artificial sites that must be identified only by a very approximate ansatz, discussed in Section 4. For light gases, such as $`H_2`$ and $`He`$, quantum effects (such as zero point motion) are very important, yet they are neglected here. Nevertheless, we think that our model yields the principal qualitative features of the adsorption’s dependence on the various interactions present in this problem. Thus it should help us understand the evolution of adsorption phenomena as a function of adsorbate and pore radius.

This research has been supported in part by grants from the Petroleum Research Fund of the American Chemical Society and the Army Research Office.

1. Schematic transverse section of a nanotube, showing occupied and unoccupied axial and shell sites.

2. $`T=0`$ phase diagram in the case of an attractive axial-shell interaction. $`\mu `$ is the chemical potential and $`E_s`$ is defined in Eq.5. Both of these energies are scaled to the intra-species interaction $`ϵ`$. The dashed line is the chemical potential of bulk condensation. We distinguish two cases: (a)when the $`SF`$ transition is present $`(E_a+ϵ_{sa}/\gamma >3)`$ and (b)when the $`SF`$ transition is absent.

3. $`T=0`$ phase diagram showing the sequence of transitions as a function of shell and axial energies, in the case of an attractive axial-shell interaction. Arrows indicate direction associated with increasing $`\mu `$.

4. $`T=0`$ phase diagram in the case of a repulsive axial-shell interaction: a) as a function of $`E_s`$ and $`\mu `$, with $`E_a`$ fixed and b) as a function of $`E_a`$ and $`\mu `$, with $`E_s`$ fixed

5. $`T=0`$ phase diagram of possible transitions as a function of interactions, in the case of a repulsive axial-shell interaction.

6. Adsorption isotherms in the attractive case: (a) and (c) two transitions $`T_{ca}=1`$, $`T_{ca}=0.5`$ (as in the decoupled case) occur for a large difference between axial and shell energies; the phase which is first occupied corresponds to a lower energy: axial for (a), shell for (c); (b) a cooperative transition at a higher $`T_c`$ occurs when the axial and shell energies are similar.

7. Dependence of the axial and shell critical temperatures on the difference between axial and shell energies. The two transitions for different $`\mu `$ occurring at large $`\delta `$ merge into one common transition when $`|\delta |<4ϵ_{sa}`$. The width of the cooperative behavior regime is proportional to $`ϵ_{sa}`$.

8. Isotherms at finite T in the case of repulsive axial-shell interaction: (a) and (c) two transitions at the decoupled critical temperatures occur for a large difference between the axial and shell energies. The phase which occurs at lower $`\mu `$ corresponds to a lower energy per site. In (b) three different transitions occur when the axial and shell energies are similar.

9. Transition curves in $`\mu T`$ plane at $`\delta =0`$ for various values of $`ϵ_{sa}`$, in the case of a repulsive axial-shell interaction. The axial sites are filled first; then, when the shell gets filled, axial atoms are expelled and finally, as $`\mu `$ increases, the full phase occurs. As in the attractive case, the critical temperature is enhanced by the coupling.