MOLECULAR PHYSICS, 1985, VOL. 55, NO.

2, 463-473

Q u a n t u m v i b r a t i o n a l c h a o s in t h e ArHCI v a n d e r W a a l s molecule
by J O N A T H A N T E N N Y S O N Science and Engineering Research Council, Daresbury Laboratory, Daresbury, Warrington W A 4 4AD, England

(Received 3 ffanuary 1985 ; accepted 7 February 1985)

Quantum mechanical ro-vibrational calculations are presented for the ArHC1 van der Waals complex using Hutson and Howard's empirical M5 potential. Analysis of the nodal structures, second differences and overlapping avoided crossings suggests that the higher bound states of ArHC1 are chaotic. This chaos is made evident by perturbing the angular part of the kinetic energy term, e.g. by isotopic substitution or vibrational excitation of HC1. Calculations with J > 0 show increased level crossings but no significant increase in chaos because of an extra nearly good quantum number. The low-lying states of ArHC1 appear to be poorly modelled by either the harmonic oscillator or free rotor approximations. Comparison with other molecules for which vibrational chaos has been predicted are made.

1. INTRODUCTION In a recent series of papers [-1-3] T e n n y s o n and Farantos studied the onset and nature of vibrational chaos in the floppy K C N and L i C N molecules. T h e y did this by performing quantum and classical calculations on realistic (ab initio) potential energy surfaces. Quantum chaos was identified by using a variety of previously proposed criteria [-4] including nodal structure [5], spectral distributions [.6], second differences [-7] and the occurrence of overlapping avoided crossings [8]. While no criterion was found to give a complete solution to the problem of characterising q u a n t u m chaos, the combination of indicators allowed chaos to be identified. Qualitative agreement was also obtained between classical and quantum calculations, although some quantum sluggishness was observed. The unusually early onset of chaos in both K C N and L i C N was found to be closely associated with the presence of low-lying barriers in the bending coordinate [-3]. Many van der Waals complexes have low-lying barriers in their intermolecular bending coordinate(s). Furthermore there is evidence from both classical calculations [-9] and experiment [-10] that Ar clusters behave chaotically. As the low dissociation energy of van der Waals systems means that most or all of their vibrational levels are thermally occupied, they would appear promising candidates for the experimental study of chaos. T h e simplest van der Waals complexes that could display chaos are a t o m diatom systems. Complexes formed by light diatomics, especially H2, have only small barriers in the bending coordinate. Such systems have been studied by L e R o y and co-workers [11], who were able to obtain entire anisotropic potentials for such systems by inversion of (welt resolved) infra red spectra. T h e isotropic

464

J. T e n n y s o n

nature of these systems means that they are very well represented by the free rotor approximation. Indeed a model based on this approximation has been successfully used for the analysis of H 2 X ( X = rare gas) hyperfine spectra [12]. Vibrational calculations on H 2 X van der Waals complexes using free rotor basis functions show that individual states are generally dominated by one basis function [13] these states can thus be assigned regular (or ' m o d e localized') by the dominant coefficient criteria of Hose and Taylor [14]. Conversely, van der Waals complexes involving heavy diatomics show considerable anisotropy. Their infra red spectra are complicated envelopes (for example references [15, 16]) which require sophisticated averaging procedures to be reproduced theoretically [17]. Without resolving the mass of competing transitions only limited information about the potential can be obtained from these spectra. However, empirical potentials can be obtained for such systems by the study of scattering data, for example [18, 19]. T h e ArHC1 van der Waals system is an interesting example of a complex with a strong anisotropic component. It has been much studied theoretically [17-22] due, at least in part, to the accurate empirical potentials obtained by Hutson and Howard [18, 19]. In particular, their M5 potential [19] has been used successfully for theoretical calculations [17, 22]. This potential predicts minima for both linear structures of the ArHC1 complex, separated by a barrier of 76 cm 1. As this is qualitatively the shape of potential which has been found to support chaos in L i C N [2, 3], the purpose of this paper is to ask whether some of the vibrational states of ArHC1 are chaotic and if so how they might effect the predicted behaviour of the molecules.

2. CALCULATIONS ArH35C1 ON T h e hamiltonian for an atom-diatom complex can conveniently be written in body-fixed coordinates as [23] H - 2#1R-------- OR R2 ~ 5 2#2 r 2 ~r r2 ~r q- 2#2 r 2 + - - 2 # R q- V(R, r, 0), 2

(1)
where #a and #2 are the reduced masses, and J and j are-the total angular m o m e n t u m operators of the complex and diatom respectively; r is the diatomic bondlength, R the separation of the atom from the diatom centre of mass and 0 the angle between t and R. 0 is 0 ~ for linear ArHC1 and 180 ~ for ArC1H. The M5 potential, V, of Hutson and Howard [19] is only a two dimensional function of R and 0. Following other workers [17, 20-22], the Hamiltonian (1) was initially solved with r frozen at the equilibrium value of 2"435 a 0 . Variational solutions of (1) were obtained using program A T O M D I A T [24] with the G E N P O T addendum [25]. This method, due to T e n n y s o n and Sutcliffe [26], uses a basis expansion of Morse-like oscillators for R and associated Legendre functions (free rotor functions) for 0. Trial calculations showed that 21 Morse functions with R1 = 9"8a0, D1 = 0"0004Eh and o51 = 5 x 10 4E h and 12 Legendre functions (for J = 0) converged 15 bound states for ArH35C1 to within 0"05cm -1 for the highest states and considerably better for the lower ones. Whilst the existence of further bound states cannot be ruled out on the basis of a

Q u a n t u m chaos in A r H C l

465

12 Groundstate 1st Excitedstate

6-

rr 12

60

8m E x c i t e ~
9o 180 0 9o 180

8/~

Figure 1. Amplitudes of 4 vibrational states of ArH35CI with J = 0. The contours link points where the wavefunction has 4%, 8%, 16%, 32% and 64% of its maximum amplitude. Solid contours enclose regions of positive amplitude and negative contours regions of negative amplitude.

variational calculation, these are only likely with very low binding energy and large ( R ) . Additional states of this type will have little effect on the conclusions drawn below. Figure 1 shows plots of 4 typical ArH35C1 wavefunctions for J = 0 vibrational states. While the ground state shows some delocalization, it is substantially localized about the ArHC1 minimum. Conversely, the first excited state, a bending excitation, is clearly delocalized. Higher excited states are characterized by complicated nodal patterns at short R and simple delocalized behaviour at large R. These states cannot meaningfully be assigned quantum numbers by inspection which is one indication of chaos [5]. T h e stability of levels with respect to a small perturbation is another means that has successfully been used"to detect q u a n t u m chaos. P o m p h r e y ' s use of second differences [7] and Marcus et a r s overlapping avoided crossings [8] are based on this. In a real problem such as this, the appropriate perturbation is not readily apparent. We thus chose to study 5 perturbations which in turn affect all parts of the Hamiltonian (1). T h e parameters varied were mAr , the mass of Ar, and r, ~the HC1 separation, which perturb the kinetic energy operator, and e, Ael and Ae2 which between them perturb all parts of the potential [19] and are

466 Table 1.

J. T e n n y s o n Second differences for five parameters (see text) for the bound states of ArH3SC1 with J = 0. Parameter P0 Ap State 1 2 3 4 5 6 7 8 9 10 11 12 13 14 0-018 0.017 0.043 0.037 0'050 0-026 0.053 0.055 0.035 0.049 0.048 0.030 0.053 0.024 0'001 0"039 0"013 0'022 0"007 0"021 0.071 0.087 1"177 0.268 0.208 0.313 0-333 0-417
mar 40 amu 2 amu r 2-35 a 0 0.05 a o go ) 0"025 Agl ) 0.02 Ag2

0"04

AJcm - 1 0"005 0'008 0"013 0-026 0'045 0.012 0"058 0-002 0'003 0"024 0.075 0'009 0.156 0.047 0'035 0-015 0'007 0"004 0'037 0-012 0"019 0"013 0'092 0-039 0'023 0"005 0'014 0.006 0"004 0'044 0-014 0"017 0"004 0'004 0-024 0'017 0"020 0'001 0.004 0"003 0 0'001

t T h e potential parameters, which are functions of O, are as defined by reference [19]. They were scaled in the perturbed calculations by (1 + Ap).

i n c r e a s i n g l y anisotropic. T a b l e 1 shows second differences o b t a i n e d for the ith state as a f u n c t i o n of p a r a m e t e r p u s i n g the f o r m u l a [7] A i = ] (El(P0 + Ap) -Ei(Po)) (Ei(.Po) -- E~(Po --

Ap)) [.

(2)

Values of Ap were chosen so as to give second differences for the lower states of a p p r o x i m a t e l y the same m a g n i t u d e . F o r one p e r t u r b a t i o n , r, the second differences s h o w n in table 1 are significantly larger for the u p p e r 7 states than the lower states. T h i s is indicative of chaos [7]. F i g u r e 2 shows the e n e r g y levels of the A r H C 1 p r o b l e m p l o t t e d as a f u n c t i o n of r. I n s p e c t i o n of the figure reveals that states b o u n d b y less t h a n 4 0 c m -1 u n d e r g o m a n y avoided crossings. T h i s again indicates that these states are chaotic [81. C o n v e r s e l y , plots of e i g e n e n e r g y as a f u n c t i o n of the other p a r a m e t e r s considered in table 1 show n o such erratic b e h a v i o u r a n d i m p l y that all states are r e g u l a r w i t h respect to these p e r t u r b a t i o n s . I n g e n e r a l the d e n s i t y of states of a s y s t e m increases with total a n g u l a r m o m e n t u m , J. T h i s has led to suggestions that chaos will m a n i f e s t itself m o r e s t r o n g l y for r o t a t i o n a l l y excited states b e c a u s e of the increased p r o b a b i l i t y of n e a r - r e s o n a n t interactions. F i g u r e 3 depicts the J = 1 e a n d J = 2 r where e denotes t h e p o s i t i v e p a r i t y c o m b i n a t i o n [271, levels as a f u n c t i o n of r. T h e s e figures again s h o w m a n y (overlapping) avoided crossings i n the high e n e r g y region. A n a d d i t i o n a l i n d i c a t o r of chaos w h i c h has p r o v e d useful in p r e v i o u s calculations is the use of spectral d i s t r i b u t i o n s [4, 61. T h i s m e a s u r e is based on the shape of h i s t o g r a m s of the spacings b e t w e e n levels of the same s y m m e t r y . F o r good statistics, however, m a n y levels are r e q u i r e d . W i t h less t h a n 15 levels in the chaotic r e g i o n a n d fewer below, even for J = 2 e, A r H C 1 s u p p o r t s i n s u f f i c i e n t levels to m a k e a d i s t r i b u t i o n a l analysis useful.

Quantum chaos in ArHCI

Ar HC[ 0 J=0

467

-40 -

7 E

-80 -

-120 2.0

t re rHC [ / a o

2.8

Figure 2.

V i b r a t i o n a l e n e r g i e s as a f u n c t i o n of H C I s e p a r a t i o n for ArH35C1 w i t h J = 0.
Ar HC!. J=l e 0

Ar HCL J = 2 e

-40

-40 -

'T

m-

-80-

-80

"f20

120-

2.0

re rHC [ / a o

2.8

2.0

re rHC t / a o

2.8

(a)

(b)

Figure 3.

Vibrational energies as a function of HC1 separation for ArH35C[ with (a) J = 1 e a n d ( b ) J = 2 e.

468

J. T e n n y s o n
3. D I s c u s s i o N

T h e calculations presented in the previous section strongly imply that the higher bound vibrational states in the M5 ArHC1 potential are chaotic. Not only are these states too irregular to make the assignment of quantum numbers on the basis of their nodal structure meaningful, but also they behave erratically when perturbed by changing r, the HC1 bondlength. The implication of this is that vibrational chaos in ArHC1 is not induced by the potential as has been predicted for K C N [1] and L C N [2, 3] but by the kinetic energy operator. As a check on the effect of perturbing the kinetic energy operator in these systems, calculations were performed for K C N as a function of C N bondlength, r. T h e results are given in figure 4, which, although it shows an increasing n u m b e r of avoided crossings, does not show the large n u m b e r of resonances from 4 0 0 c m -1 above the gound state upwards, displayed when a perturbation of the potential was used

[i].
Chaos is usually understood both in classical and quantum mechanics through the partitioning of a given problem into a separable (non-chaotic) zeroth order problem, H0, which is then coupled by some chaos inducing perturbation. I n d e e d this concept is fundamental to both K A M theory and Hose and Taylor's ' Q u a n t u m K A M t h e o r y ' [28]. In conventional (near rigid) molecules the harmonic oscillator model provides a good H 0 which usually allows many vibrational states to be assigned. For example, this model provides a good description of the lowest (regular) states in K C N [29] and L i C N [30], although in the floppy molecules it soon breaks down [1, 2, 31].
KCN J =O

1000

7~.Eo 500

3-

2.0

re

28

rCN/ao
Figure 4. Vibrational energies as a function of CN separation for KCN with J = 0.

Q u a n t u m chaos in A r H C I

469

In a t o m - l i g h t d i a t o m van d e r W a a l s d i m e r s , such as H 2 X , ( X = H [13], N o b l e gas [11, 26]) or H e H F [32], the free r o t o r m o d e l p r o v i d e s a g o o d H 0. W o r k on a h e a v i e r c o m p l e x , t h e n i t r o g e n d i m e r , has s h o w n t h a t b o t h the h a r m o nic o s c i l l a t o r [33] a n d free r o t o r [34] m o d e l s p r o v i d e a p o o r d e s c r i p t i o n of the m o l e c u l a r v i b r a t i o n s , a n d t h a t even the lowest states m u s t b e r e g a r d e d as solutions i n t e r m e d i a t e b e t w e e n t h e s e m o d e l s [35]. I n s p e c t i o n of the l o w e s t v i b r a t i o n a l w a v e f u n c t i o n s of A r H C 1 suggests a p i c t u r e s i m i l a r to t h a t f o u n d for (N2) 2 . T h e g r o u n d state is s u b s t a n t i a l l y localized a b o u t 0 = 0 ~ a l t h o u g h s o m e d e l o c a l i z a t i o n (and for this state t u n n e l l i n g ) can be o b s e r v e d , see figure 1. T h e first e x c i t e d state is a single b e n d i n g e x c i t a t i o n a n d is delocalized. T h e s e c o n d e x c i t e d state is, largely, a single s t r e t c h i n g excitation localized a b o u t A r H C 1 (0 = 0~ T h e t h i r d e x c i t e d state is a c o m b i n a t i o n b e t w e e n a d e l o c a l i z e d d o u b l e b e n d i n g e x c i t a t i o n and a single s t r e t c h i n g excitation localized a b o u t A r C 1 H (0 = 180~ A b o v e these it b e c o m e s i n c r e a s i n g l y difficult to assign states b y i n s p e c t i o n . T h i s t r e n d a p p e a r s to be u n i f o r m a n d s u g g e s t that A r H C 1 is n e a r e r to K C N , w h e r e no r e g u l a r states c o u l d be a s s i g n e d or classical t r a j e c t o r i e s o b s e r v e d a b o v e t r a n s i t i o n to chaos [1], t h a n L i C N w h e r e b o t h r e g u l a r states a n d q u a s i p e r i o d i c t r a j e c t o r i e s were f o u n d over t h e e n t i r e r a n g e s t u d i e d [2, 3]. A r H C 1 t h u s a p p e a r s to be s t r o n g l y m o d e c o u p l e d . F i g u r e 3 s h o w s t h a t i n c r e a s i n g the r o t a t i o n a l e n e r g y of the s y s t e m does i n d e e d increase the n u m b e r of levels a n d h e n c e the n u m b e r of a v o i d e d crossings. H o w e v e r , c o m p a r i s o n of figure 2 a n d figure 3 gives little e v i d e n c e for the lower onset of chaos in the r o t a t i o n a l l y e x c i t e d systems. T h i s is b e c a u s e a l t h o u g h t h e r e are m o r e a v o i d e d c r o s s i n g s in these systems, m a n y of the c r o s s i n g s are o n l y w e a k l y a v o i d e d . T h i s is d u e to the p r e s e n c e of a n e a r - g o o d q u a n t u m n u m b e r , K , the p r o j e c t i o n of J a l o n g R, w h i c h m e a n s t h a t levels w i t h d i f f e r e n t K o n l y w e a k l y interact. T h i s b e h a v i o u r is well k n o w n in van d e r W a a l s s y s t e m s a n d has b e e n u s e d in a p p r o x i m a t i o n s w h i c h n e g l e c t C o r i o l i s i n t e r a c t i o n s [20, 21, 26]. O f c o u r s e the a b i l i t y to p e r t u r b the A r H C 1 c o m p l e x b y c h o o s i n g a value of the H C I b o n d l e n g t h , r, is one w h i c h is o n l y available to the t h e o r i s t . T h e r e are, h o w e v e r , w a y s in w h i c h s e n s i t i v i t y to r m i g h t m a n i f e s t itself e x p e r i m e n t a l l y . F i r s t l y , in t h e real A r H C 1 m o l e c u l e , the HC1 c o o r d i n a t e is n o t f r o z e n ; different v i b r a t i o n a l states of HC1 have different ( r ) . S e c o n d l y , i s o t o p i c s u b s t i t u t i o n in H C I p e r t u r b s t h e s a m e t e r m s in t h e H a m i l t o n i a n as c h a n g i n g r. T a b l e 2 gives e n e r g i e s of t h e v i b r a t i o n a l levels of t h e A r H C 1 m o l e c u l e relative to HC1 in its g r o u n d a n d first e x c i t e d state. F o r c o m p a r i s o n the results of a c a l c u l a t i o n w i t h HC1 fixed at its e q u i l i b r i u m s e p a r a t i o n are also given. T h e r d e p e n d e n t c a l c u l a t i o n s w e r e p e r f o r m e d u s i n g an e m p i r i c a l l y d e r i v e d H C I p o t e n tial d u e to O g i l v i e [36]. T h r e e M o r s e o s c i l l a t o r - l i k e f u n c t i o n s w e r e u s e d to r e p r e s e n t this c o o r d i n a t e w i t h r z = 2"465 a 0 , (-o2 = 0"012 E h a n d D2 = 0"1045 E h [24]. T h i s basis r e p r o d u c e d t h e o b s e r v e d HC1 v i b r a t i o n a l f u n d a m e n t a l to w i t h i n 0-01 p e r c e n t (0"2 c m - 1). N o p o t e n t i a l c o u p l i n g b e t w e e n r a n d (R, O) was a l l o w e d for. P r e v i o u s c a l c u l a t i o n s on t h e b i n d i n g e n e r g y of van d e r W a a l s d i m e r s as a f u n c t i o n of m o n o m e r v i b r a t i o n a l state have b e e n p e r f o r m e d on t h e H e H F m o l e cule [32]. T h i s c o m p l e x , w h i c h is h i g h l y isotropic, s h o w e d s y s t e m a t i c ( b u t small) increases in b i n d i n g e n e r g y as firstly t h e H F c o o r d i n a t e was u n f r o z e n a n d seco n d l y H F v i b r a t i o n a l e x c i t a t i o n i n c r e a s e d . S i m i l a r b e h a v i o u r can b e seen for the l o w - l y i n g levels o f A r H C 1 s h o w n in t a b l e 2. T h i s is d u e to i n c r e a s e s in ( r ) w i t h HC1 v i b r a t i o n a l r e l a x a t i o n a n d excitation. H o w e v e r , t h e 6th state o f A r H C 1 is

470

J. T e n n y s o n

T a b l e 2. V i b r a t i o n a l e n e r g y l e v e l s (in c m - 1 ) r e l a t i v e t o fre e A r a n d H a s C I ( v ) for A r H 3 5 C I as a f u n c t i o n o f H C I v i b r a t i o n a l s t a t e v. R e s u l t s for a f i x e d n u c l e i c a l c u l a t i o n a re g i v e n fo r c o m p a r i s o n . States 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Fixed~ -t17.24 --92'33 - 83.76 -- 6 5 - 0 4 -- 5 8 ' 7 0 --47"88 --40'56 --36-60 --24'98 --22"01 -- 16-81 --11.09 --6'68 --5-17 --0'36 v = 0 -117.30 9 - 92'38 - 85-80 -- 6 5 ' 0 7 -- 58"76 --47'71 --40.58 --36'65 --24.93 --22.10 -- 16-73 --11"17 --6.66 --5"28 --0"43 v= 1 -117-49 -92-61 - 83 '98 -- 65"42 -- 58"97 --48.85 --40'95 --36.89 --25.64 -22"19 -- 17-49 --11'30 --7"22 --5'27 --0'69

~" r = 2 . 4 3 5 a 0.

actually avoided states

less bound crossing

in

the

full erratic

calculations, behaviour (e.g.

this with

must

be

associated

with

the this

undergone

b y t h i s s t a t e as r is v a r i e d , bound numbers

s e e f i g u r e 2. A b o v e excitation. 11) whilst state

level there

is i n c r e a s i n g l y markedly

vibrational 9 and

Some 14

become

more

actually has a slight decrease in binding.

T a b l e 3.

V i b r a t i o n a l e n e r g y l e v e l s (in c m -1 r e l a t i v e to f r e e A r + H C 1 ) f o r t h e m a j o r i s o t o p i c s p e c i e s of A r H C 1 w i t h J = 0. States 1 2 3 4 5 6 7 8 9 10 11 12
13

ArH3SC1 -117"24 --92.33 - 83-76 -- 6 5 . 0 4 -- 58"70 --47'88 --40-56 - 36.60 -- 2 4 ' 9 8 --22.01 -- 16"81 -- 11.09 --6"68 --5-17 - - 0-36

ArH37C1 --117.53 --92.58 -- 84"40 -- 6 5 ' 5 5 -- 59-48 --48'37 --41-31 -- 37-45 -- 2 5 ' 7 4 --22"83 -- 17"57 -- 11 '75 -- 7-51 --5'71 -- 0-99

ArD35C1 --125"13 --98"64 -- 91 '01 -- 80"08 -- 69-42 -- 61-74 --55-84 --47'15 - 44"56 --37'31 -- 3 3 ' 3 4 -- 25.44 -- 24"06 -18"77 -- 15"68 --12"22 -- 8'65 --5" 83 --3"70 -- t "77 --0"13

ArD37C1 --125'46 --98"87 -- 91 "65 -- 8 0 ' 4 4 -- 70.01 -- 62"59 --56'32 --47.73 -- 45' 39 --38'19 -- 34-04 -- 26.33 -- 24"82 --19.49 -- 16-46 --12'91 -- 9.43 --6"35 --4.42 -- 2 ' 4 3 --0-79

14
15

16
17

18 19 20 21

Quantum chaos in A r H C l
Ar HCI J = 0

471

-40 -

T E o
L0

-80 -

-120-

1.0
mH/a.m.u.

2.0

Figure 5.

Vibrational energies as a function of hydrogen mass for ArH35C1 with J = 0.

This behaviour suggests that vibrational chaos in the higher states of ArHC1 could be observed experimentally by studying the spectrum as a function of HC1 excitation. However, the relatively small fluctuations in binding predicted will require experimental resolution well beyond that which has been achieved for these systems. Table 3 gives the vibrational levels of the major isotopic species of the ArHC1 complex. T o illustrate any erratic behaviour with respect to isotopic substitution, figure 5 shows the correlation of ArH35CI levels with those of ArD35C1 obtained by systematically increasing the mass of hydrogen. T h e figure is qualitatively similar to figure 2 and suggests that one would indeed expect erratic isotope shifts for the weakly b o u n d levels of the complex. This is in contrast to calculations of K C N which indicate that the isotope shift is likely to be regular [2].

4. CONCLUSIONS

Calculations performed on the ArHC1 van der Waals molecule indicate that the vibrational states which are bound by less than 4 0 c m -1 are chaotic. The transition to chaos thus occurs at about 2/3 of the way dissociation, this is similar to the figure suggested for conventional molecules, such as SO 2 [37], on the basis of classical calculations, but considerably higher than the transition in the floppy K C N and L i C N molecules [1, 2]. Chaos in ArHC1 appears to be driven by the kinetic energy operator. This is in contrast to K C N and L i C N where chaos was found to be driven by the

472

J. T e n n y s o n

potential [-1, 2]. Although model calculations have been p e r f o r m e d on problems where chaos is caused by kinetic coupling [8], we know of no previous case where this has been predicted for a physical system. F r o m the point of view of experiment, this kinetically driven chaos would appear to have the advantage that there are distinct mechanisms by which chaos may be identified, namely erratic behaviour with respect to isotopic substitution and the degree of HC1 excitation. However, the complexity of the ArHC1 spect r u m is such [17], that the resolution required to resolve such erratic behaviour may prove difficult to achieve. T o this end further work is required on the occurrence of vibrational chaos in van der Waals systems, firstly to determine whether its occurrence can be predicted in any systematic way and secondly to find experimentally favourable cases for investigation. I am grateful to Dr. Stavros Farantos and Joaquin Camacho for m a n y helpful discussions during the course of this work.

[1] [2] [3] [4] [5] [6] [7] [8]

[9] [10] [11]

[12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27]

REFERENCES TENNYSON,J., and FARANTOS,S. C., 1984, Chem. Phys. Lett., 109, 160. FARANTOS,S. C., and TENNYSON,J., 1985, J. chem. Phys., 82, 800. TENNYSON,J., and FARANTOS,S. C., 1985, Chem. Phys., 93, 237. REINHARDT,W. P., 1984, The d]4athematical Analysis of Physical Systems, edited by R. Mickens (Van Nostrand). STRATT,R. M., HANDY, N. C., and MILLER, W. H., 1979, J. chem. Phys., 71, 3311. MATSUSHITA,T., and TERASAKA,T., 1984. Chem. Phys. Lett., 105, 511. POMPHREY,N., 1974,~. Phys., 7, 1909. NOID, D. W., KOSZYKOWSKI,M. L., and MARCUS, R. A., 1980, Chem. Phys. Lett., 73, 269; J. chem. Phys., 1983, 78, 4018. MARCUS, R. A., 1983, ~. chem. Soc. Faraday Discuss., 75,103. FARANTOS,S. C., 1983, J. phys. Chem., 87, 5061. STACE,A. J., 1983,J. phys. Chem., 87, 2286. LE Roy, R. J., and VAN KRANENDONK,J., 1974, ~. chem. Phys., 61, 4750. KREEK, H., and LE RoY, R. J., 1975, J. chem. Phys., 63, 338. LE RoY, R. J., and CARLEY,J. S., 1980, Adv. chem. Phys., 42, 353. VERBERNE,J., and REUSS, J., 1980, Chem. Phys., 50, 137; 1981, Chem. Phys., 54, 189. WAAIJERS, M., JACOBS, M., and REUSS, J., 1981, Chem. Phys., 63, 257. WAAIJERS, M., and REUSS, J., 1981, Chem. Phys., 63, 263. TENNYSON,J., 1981, Chem. Phys. Lett., 86, 181. HOSE, G., and TAYLOR, H. S., 1982, J. chem. Phys., 76, 5356. RANK, D. H., RAO, B. S., and WICGENS,T. A., 1962,J. chem:Phys., 39, 2673. MtZlOLEK,A. W., and PIMENTEL, G. C., 1976, J. chem. Phys., 65, 4462. BERNSTEIN,L. S., and WORMHOUDT,J., 1984,J. chem. Phys., 80, 4630. HUTSON,J. M., and HOWARD,B. J., 1981, da/lolec. Phys., 43, 493. HUTSON,J. M., and HOWARD,B. J., 1982, Molec. Phys., 45,763. KIDD, I. F., BALINT--KuRTI,G. G., and SHAPIRO, M., 1981, J. chem. Soc. Faraday Discuss., 71,287. ASHTON, C. J., CHILD, M. S., and HUTSON, J. M., 1983, J. chem. Phys., 78, 4025. HUTSON,J. M., 1984, J. chem. Phys., 81, 2357. BROCKS, G., VAN DER AVOIRD, A., SUTCLIFFE,B. T., and TENNYSON,J., 1983, Molec. Phys., 1025. TENNYSON,J., 1983, Comput. Phys. Commun., 29, 307. TENNYSON,J., 1984, Comput. Phys. Commun., 32, 109. TENNYSON,J., and SUTCLIEEE,B. T., 1982, ft. chem. Phys., 71, 4061. BROWN, J. M., HOIJCEN, T. J., HURER, K.-P., JOHNS, J. W. C., Kopp, I., LEEEBVREBRmN, H., MERER, A. J., RAMSAY, D. A., ROSTOS, J., and ZARE, Z. N., 1975, A~. molec. Spectrosc., 55,500.

Quantum chaos in A r H C l

473

[28] HOSE, G., and TAYLOR, H. S., 1983, Phys. Rev. Lett., 51, 947. HOSE, G., TAYLOR, H. S., and TIP, A., 1984, J. Phys. A, 17, 1203. [29] TENNYSON, J., and SUTCHEEE, B. T., 1982, Molec. Phys., 46, 97. [30] BROCKS,G., and TENNYSON, J., 1983, J. molec. Spectrosc., 99, 263. [31] TENNYSON, J., and VAN DER AVOIRD,A., 1982, J. chem. Phys., 76, 5710. [32] TENNYSON, J., and SUTCLIEFE,B. T., 1983, J. chem. Phys., 79, 43. [33] VAN DER AVOIRD, A., 1982, J. chem. Soc. Faraday, Discuss., 73, 33. [34] BRIELS, W. J., TENNYSON,J., CLAESSENS,M., VAN DER LEE, TH., and VAN DERAVOIRD, A., 1983, Int. J. quantum. Chem., 23, 1091. [35] TENNYSON,J., and VAN DER AVOIRD,A., 1982, J. chem. Phys., 77, 5664. [36] OGILVIE, J. F., 1981, Proc. R. Soc. A, 378, 287. [37] FARANTOS,S. C., and MURRELL,J. N., 1981, Chem. Phys., 55,205.