MOLECULAR PHYSICS, 1986, VOL. 58, NO.

6, 1067-1085

Highly rotationally e x c i t e d states of floppy m o l e c u l e s : H2 D+ with J ~< 20.

by J O N A T H A N T E N N Y S O N D e p a r t m e n t of Physics and Astronomy, University College London, Gower Street, L o n d o n W C 1 E 6BT, England and B R I A N T. S U T C L I F F E Chemistry Department, University of York, Heslington, York YO1 5DD, England
(Received 12 March 1986 ; accepted 28 March 1986)

A partitioning of the generalized triatomic hamiltonian of the preceding paper is developed which allows the calculation of highly-excited rotational states, without approximation, in a two-step variational procedure. Iterative diagonalization techniques are found to be particularly useful for the second variational step. The rotationally-excited states of HzD + are studied with J ~< 20, well into the region where the ground and excited state manifolds overlap. Comparison of results for two different ab initio potentials and convergence considerations suggest that pure rotational transition frequencies obtained from our results should be accurate to about 1 cm- 1 for J ,~ | 5.

1. INTRODUCTION T h e a priori computation of ro-vibrational spectra of small molecules, mainly triatomic, has made significant progress over the last decade, but has been largely confined to low values of the total angular m o m e n t u m q u a n t u m number, J. T h e reasons for this are twofold, firstly most experimental information has come from transitions between moderately low values of J (although often much higher than has been calculated) and secondly, and more crucially, the size of a fully coupled ro-vibrational calculation incleases rapidly with J and soon become intractable. Fully coupled calculations have generally been limited to J ~< 4 [1-5]. This lack of work on highly excited rotational states does not mean that these states are without interest. T h e y are, for example, crucial for testing and refining our ideas on model hamiltonians [6] based as they are on perturbation coupling schemes which may cease to be valid in the high J limit. In such a coupling scheme, it is usual to regard the rotational levels of a system as a sub-manifold of a particular vibrational state. Although coupling between rotational levels of different vibrational manifolds through Coriolis interactions is well-known, it is generally regarded as a (small) perturbation. Many theoretical analyses of large J states have ignored this interaction (e.g. [7]). We will call the region where this approximation is valid the low J regime, while realizing that for heavy molecules this regime may include J values of several

1068

J. T e n n y s o n and B. T. Sutcliffe

hundred. A semi-quantitative definition of the range of the regime is given by considering the ratio of the rotational and vibrational splittings, R j , which can be approximated by
R j "~ [ A -- ( B + C)/2]J2/~o,

(1)

where A, B and C are the usual rotational constants and o~ the lowest vibrational fundamental for the molecule. In the low J regime R j is very m u c h less than unity. However, as J increases so does the width of the rotational manifold that is the difference between levels with z = - - J and z = + J for an asymmetric top, or K = 0 and K = J for a symmetric top. For higher J, R 1 will approach unity and at this point rotational sublevels of the ground vibrational state will begin to overlap the rotational manifold of the lowest vibrationally-excited state. This we call the intermediate J region. For high enough J, the situation will arise where the rotational splittings are much larger than the spacing between vibrational levels, R s >> 1. In the extreme, this would result in the re-ordering of the q u a n t u m numbers (or perturbative coupling scheme) so that levels with low K, in the symmetric top case, will be preferred and the vibrational parentage of a state will become the small perturbation. This recoupling for large values of the total angular m o m e n t u m is wellknown in nuclei [8] where the study of ' h i g h spin states' is an area of considerable activity. T o our knowledge, such recoupling has yet to be observed in molecular systems, but, as we demonstrate, is not outside the scope of current experiments. In this paper we propose a tractable procedure for the ab i n i t i o calculation of highly excited rotational states with full ro-vibrational coupling. This procedure, based on the use of a secondary variational step in the calculation, is similar to the method used recently by Chen et al. [-9] for calculating the low-lying states of H 2 0 with J ~< 10. However, it differs in one respect which we expect to be important for the accurate calculation of the highly-excited states considered here. Light systems, with large rotational constants, will tend to display the high J effects at lower values of the total angular m o m e n t u m than heavier systems. H~-, the lightest (and electronically simplest) polyatomic system thus makes a suitable starting point for such a study. T h e low-lying ro-vibrational states of H~- and its isotopomers have been the subject of m u c h recent study, both experimentally and theoretically, and a fair measure of understanding has been achieved for these states [-4]. In particular, HE D+ is known to be a highly-asymmetric top, K - --0"07, whose vibrational levels show strong Coriolis coupling due to the splitting of levels degenerate in H~ [2]. However, all the calculations on H2D + have concentrated on states with low J(~<4), and the published experiments have been confined to J ~< 7 [2, 10-13]. There is, however, evidence to show that for H2 D+ transitions involving large values of J, in the range 20-30, cannot be interpreted using the rotational constants determined from the study of low J states [,-14]. For these high J levels one might anticipate an R s significantly greater than one. In this work we consider the ro-vibrational states of H2 D+ with J ~< 20 in a first attempt for a realistic system to analyse theoretically the breakdown of rovibrational structure. T h e accurate knowledge of the electronic potential for H~gives us some confidence in the reliability of our calculations, although we also test this by comparing results obtained using different potentials.

Rotationally excited states of H 2 D +

2. T H E O R Y

1069

I n t h e p r e v i o u s p a p e r [-15], h e r e a f t e r r e f e r r e d to as I, we d e v e l o p e d a g e n e r alized r o - v i b r a t i o n a l h a m i l t o n i a n for t r i a t o m i c s in a n y i n t e r n a l c o - o r d i n a t e s y s t e m w h i c h c o n s i s t s o f t w o l e n g t h s a n d an angle. T h i s h a m i l t o n i a n was w r i t t e n

/-/= tdv'+ ~ v ~ + ~

+ ~

+ v,

(2)

w h e r e t h e K v t e r m s are p u r e v i b r a t i o n a l k i n e t i c e n e r g y o p e r a t o r s , a n d the KvR s are v i b r a t i o n - r o t a t i o n k i n e t i c e n e r g y o p e r a t o r s , w h i c h are zero for J = 0. T h e t e r m s s u p e r s c r i p t e d 2 are t h o s e i n t r o d u c e d b y t h e g e n e r a l i z a t i o n o f t h e coo r d i n a t e s f r o m a t o m - d i a t o m s c a t t e r i n g c o - o r d i n a t e s . V is t h e e l e c t r o n i c p o t e n t i a l . I n this w o r k we first d i a g o n a l i z e a h a m i l t o n i a n for w h i c h k, t h e p r o j e c t i o n o f J o n t o the b o d y - f i x e d z axis, is a g o o d q u a n t u m n u m b e r , a n d t h e n we tackle the full p r o b l e m . I n this way, we a i m to r e d u c e t h e size o f t h e full p r o b l e m t h a t n e e d b e c o n s i d e r e d . A s o l u t i o n of t h e h a m i l t o n i a n

n.,~ = ~
w i t h e i g e n v a l u e ei k can b e w r i t t e n J'

+ ~ v~ + a~k,/~v~. + V, ~

(3)

c~Ji,k = ~ ci,-J'm,k'i. Hm(rl)H,(r2)Ojk(O)D~k(Ot, fl, ~)

j , tn, n

(4)

in t e r m s o f t h e basis fur, c t i o n s d e v e l o p e d in I. W e n o t e t h a t t h e e i g e n v a l u e s are i n d e p e n d e n t of t h e sign o f k. T h e s e e i g e n v e c t o r s can t h e n be u s e d as a basis set for t h e full h a m i l t o n i a n (2). T h e m a t r i x e l e m e n t s for this s e c o n d s t e p are

<k', i ' [ H l k , i>

6k,kOi,iel 'k + f ( k ,

'

+
jmn j'ra'n'

e j, m,

Cj'm'n"

aj,ia.,.Cj<m[2g,r~ Im>
m

,1__!__

+ a,,,,+, a,,2#12+k rE1[ m>[(j + 1)<n'[ r-21 + <n'] ~r2 ] ] <m'[ In> n>d
+ 3 j ' , , - 1 2#12

bJ'+-k<m" r-7 [m>[J<n'' r'~ ]n>-<n'] ~d 1 1

k,k'>O or k'=k=O, k = 0, k' = 1 o r k = 1,

in>

3} ,

(5)

for z e m b e d d e d a l o n g r I ( a n d t h e s a m e w i t h r2~-+rl, ~u1*-~#2 a n d m~-+n i n t e r c h a n g e d for z e m b e d d e d a l o n g r2). T h e factors aj, k a n d bj, k are d e f i n e d in I a n d

f(k,k')=

1,
= 21/2,

~. k' = 0,

(6)

is i n c l u d e d to a c c o u n t for t h e s y m m e t r i z a t i o n o f t h e basis w i t h r e s p e c t to t h e t o t a l parity :

1 Ik, i) =~-~(,/,l.'+(-1)p,~,J.-k),
=~bi
d,k

p = 0 , 1;
p=O,

k>0,
k=0,

(7)

w h e r e , b y c o n v e n t i o n , p = 0 for t h e e b l o c k a n d p = 1 for t h e f b l o c k . T h e t o t a l p a r i t y is g i v e n b y ( - 1 ) j+p. W e n o t e t h a t no m a t r i x e l e m e n t s a p p e a r in (5) for w h i c h [ k -- k ' l is g r e a t e r t h a n one.

1070

J. T e n n y s o n and B. T. Sutcliffe

Clearly, if all the solutions of hamiltonian (3) are used to diagonalize the full hamiltonian (2), then the results should be identical to those obtained by letting the full hamiltonian act on the untransformed basis functions. However, it is possible that not all the solutions of Ha, k are needed if one is only interested in a few, low-lying levels of H. Furthermore, as the secular equation method is variational, convergence from above can, in general, be demonstrated. T h e secondary variational procedure outlined here has one important difference to the method used for their calculations on water by Chen et al. [-9]. T h e hamiltonian of their first variational step, which was actually expressed in normal displacement co-ordinates, omitted the term equivalent to the diagonal part of /~VlR which we include. This has the advantage that their first variational step is ) independent of J and hence the J = 0 vibrational wavefunctions (for J = 0, H j , k is the exact hamiltonian) can be used as the basis for all J states. However, these basis functions will not allow for the shifts in geometry caused by the centrifugal terms in the potential, which, as we will show, are large in the high J region. Chen et al.'s calculations, although considering J up to 10, were entirely confined to the low J, R j ~ 1 region. A similar procedure has also recently been used by Spirko et al. on H~ and H2 D+, but only for J ~ 4 [5]. T h e theory given here is for the generalized co-ordinates of I ; in this work we consider H2 D in scattering co-ordinates. That is a system with r as the H 2 bondlength, R joining the H 2 midpoint with D and 0 the angle between r and R. This co-ordinate system is the best alternative within this formalism for the H f isotopomers as shown by the calculations on D2 H in I. Furthermore, we will embed the z axis along R, making r I = R and r 2 = r in the above analysis. Test calculations and previous experience [1-3] having shown this to be the best embedding for this system.

3. PRACTICALCONSIDERATIONS If the procedure outlined above is to work three problems must be borne in m i n d : convergence of the first variational step, convergence of the second variational step and the computational tractability of the procedure, especially for large values of J. T h e first variational step is very similar to the pure, J = 0, vibrational p r o b l e m - - t h e centrifugal distortion terms can be considered as extra isotropic terms in the potential. T h e r e is considerable experience in converging these vibrational problems [16] and the only added problem is that of developing a basis appropriate for a range of k values. Table 1 demonstrates the convergence of the second variational step for the low-lying states of H2D with J = 4. The symmetry block is that with even total parity and even (para) with respect to interchange of the two H atoms. For comparison, the ' e x a c t ' variational results are also given, that is the result obtained by directly diagonalizing the full ro-vibrational problem. These results are the same as those obtained by including all the eigenfunctions of the first step in the basis used for the second step, which demonstrates the numerical stability of our procedure. However, it is clear from table 1 that, at least for low J, only a fraction of these functions are needed to converge the second variational step. T h e matrices obtained in the second variational step have a structure which means that they become increasingly sparse with J. T h e only non-zero elements are the purely diagonal ones in the diagonal block where k = k', and all those in

Rotationally excited states of H2 D+

1071

M J
o,- ~ o0 O', r

O~ O~ r

O 0 -r,.)

..~ [.-,
o ~..~ 0~.-~ 0

',D

,7
r

"~

o0 O~ oo

,7 r
~.~
'4D

o0

.~,
O',

6
o0

o
r O

'IN

t"q

~
[-.

II

1072

J. T e n n y s o n a n d B. T . Sutcliffe

t h e l e a d i n g o f f - d i a g o n a l b l o c k s w i t h k = k' _ 1. I f N s o l u t i o n s o f the first v a r i a t i o n a l s t e p are u s e d , t h e s e c u l a r m a t r i x has o n l y ( J - p ) N ( N + 1 ) - N 2 u n i q u e e l e m e n t s o u t o f a total of ( J - p + 1)2N2. T a b l e 2 c o m p a r e s t h e p e r f o r m a n c e o f 3 d i a g o n a l i z e r s on a p r o b l e m w i t h J = 10 e a n d N = 8 2 - - t h e l a r g e s t p r o b l e m for w h i c h t h e e n t i r e m a t r i x c o u l d b e h a n d l e d in core. T h e m o s t n o t a b l e f e a t u r e of t a b l e 2 is t h e w i d e v a r i a t i o n in m e m o r y r e q u i r e d b y t h e t h r e e d i a g o n a l i z e r s . T h e first d i a g o n a l i z e r , w h i c h r e t a i n e d t h e e n t i r e m a t r i x in core, a s s u m e d o n l y t h a t it was s y m m e t r i c . T h e s e c o n d d i a g o n a l i z e r t r e a t e d t h e m a t r i x as b a n d e d a n d s y m m e t r i c , a n d t h u s r e q u i r e d a p p r o x i m a t e l y t w i c e t h e m i n i m u m a m o u n t o f s t o r a g e as t h e b a n d w i d t h is 2N. T h e t h i r d d i a g o n a l i z e r uses an i t e r a t i v e a l g o r i t h m d e s i g n e d for s p a r s e m a t r i c e s . Because o f the k n o w n s t r u c t u r e o f t h e m a t r i x it was p o s s i b l e n o t o n l y to retain t h e m i n i m u m n u m b e r o f m a t r i x e l e m e n t s , b u t also to use this s t r u c t u r e to s i m p l i f y t h e v e c t o r m a t r i x m u l t i p l i c a t i o n r e q u i r e d on each i t e r a t i o n . C a r e was t a k e n to e n s u r e t h a t this m u l t i p l i c a t i o n was v e c t o r i z e d . T h e i t e r a t i o n s w e r e started from unit vectors determined by the ordering of the diagonal elements and c o n v e r g e d to a t o l e r a n c e w h i c h gave t h e e i g e n v a l u e s a c c u r a t e l y to 0"01 c m - 1 . A l l t h e d i a g o n a l i z e r s a g r e e d to t h i s a c c u r a c y . B o t h t h e full a n d b a n d e d d i a g o n a l i z e r s w e r e t a k e n f r o m a p a c k a g e t h a t has b e e n v e c t o r i z e d [17]. A s can be seen f r o m t a b l e 2, t h e b a n d e d m a t r i x d i a g o n a l i z e r was t h e slowest. T h e i t e r a t i v e p r o c e d u r e was f o u n d to b e t h e m o s t efficient, b o t h in c o r e a n d C P U time. F o r J = 10, t h e t i m e t a k e n for t h e s e c o n d d i a g o n a l i z a t i o n is m o d e s t c o m p a r e d to s o l v i n g e l e v e n 504 d i m e n s i o n a l b a s e p r o b l e m s , w i t h k e q u a l s 0 to 10 inclusive, a n d s i m i l a r to t h a t t a k e n to c o n s t r u c t t h e final s e c u l a r m a t r i x . H o w e v e r , t h e t i m e t a k e n for b o t h these steps i n c r e a s e s o n l y l i n e a r l y w i t h J. O u r b i g g e r c a l c u l a t i o n s , the l a r g e s t of w h i c h was for a m a t r i x o f d i m e n s i o n 3780, d e p e n d e d s t r o n g l y on t h e t i m e t a k e n for t h e final d i a g o n a l i z a t i o n . U s i n g the i t e r a t i v e d i a g o n a i i z a t i o n p r o c e d u r e a n d an e i g e n v a l u e t o l e r a n c e of 0"01 c m -1, we n e x t c o n s i d e r e d the c o n v e r g e n c e c h a r a c t e r i s t i c s o f t h e t w o v a r i a t i o n a l s t e p s for h i g h e r v a l u e s o f J. T e s t c a l c u l a t i o n s s h o w e d t h a t t h e basis set o p t i m i z e d b y us p r e v i o u s l y for low J c a l c u l a t i o n s [1], a n d u s e d in t a b l e 1, gave a p o o r r e p r e s e n t a t i o n o f states w i t h large k, p a r t i c u l a r l y k > 10. F o r t h e s e states, t h e c e n t r i f u g a l t e r m s are large a n d it was f o u n d n e c e s s a r y to i n c r e a s e t h e flexTable 2. Comparison of computational requirements for three diagonalization procedures for the 902 dimensional secular problem given by J = 10 ~ and N = 82. 17 eigenvalues and eigenvectors were obtained for the same secular matrix which took 8-2 s to construct. Requirements for the base problems, the first variational step, are shown for comparison. Diagonalization method Full matrix [17] Banded matrix [18] Sparse matrix 119] Base Problem [20] 200 x 200 504 x 504 Storage (words) 849,424 183,748 103,973 76,668 285,979 Time (Cray-1/s) 21"58 59"26 11'75~ 11 x 2"10 11 x 15"85

Tolerance 10-3, giving 8 figure (0.01 c m - t ) accuracy in the eigenvalues.

Rotationally excited states of H2 D+

1073

T a b l e 3. Convergence of 4 typical calculations which neglect Coriolis interactions with increasing basis set size. Energies are relative to the D + + H 2 dissociation limit in
cm -1

Wavenumbers/cm- 1 mmaX~ 4 4 4 4 6 8 10 Optimized 8 nmax~ 4 4 6 8 4 4 4 6 j~a~ j~x j~ax + 4 j~a~ j~ax j~ax
jmax

J=0, k=0 j~ax : 14 -- 32953-095 --32953.097 --32953.218 --32953-222 --32961.327 --32962.111 --32962.178
-- 32962.240

J=20, k=0 j~ax = 14 --23123-595 --23123"595 --23123"910 --23123"933 --23140-856 --23142-538 --23142"706 --23142"888

J=20, k=20 j~ax = 30 --19056"013 --19056'013 --19056'108 --19056.109 --19056"908 --19056-932 --19056"934 --19057.021

J=30, k=30 j~ax : 40 --8263.127 --8263-127 --8264"003 --8264.004 --8288.554 --8289-119 --8289.376 --8291.499

j~
j~ax

Morse-like functions H,,(r) with m = 0 to m max and r e = - 2 . 2 a 0 , ~oe = 0"007E h and D e = 0.07E h [20] 3~ Morse-like functions H'.(r) n = 0 to n ma* and R e = 1-55a0, 09e = 0 . 0 0 8 E h and D e = 0.215 E h [20] w Associate L e g e n d r e polynomials Oj,(0) w i t h j = k to3 ~ax.

i b i l i t y o f t h e r a d i a l basis f u n c t i o n s to a l l o w f o r r o t a t i o n a l d i s t o r t i o n s . I t w a s also f o u n d n e c e s s a r y to i n c r e a s e jmax, t h e o r d e r o f t h e h i g h e s t L e g e n d r e f u n c t i o n in t h e basis, a l t h o u g h t h e c o n d i t i o n t h a t j > / k m e a n s t h a t t h i s d i d n o t l e a d to an i n c r e a s e in t h e size o f t h e a n g u l a r basis. T a b l e 3 p r e s e n t s r e s u l t s f o r o u r r e - o p t i m i z e d b a s i s and demonstrates convergence for a selection of vibrational calculations. U s i n g t h e o p t i m i z e d b a s i s f o r t h e first v a r i a t i o n a l s t e p g i v e n in t a b l e 3, t a b l e s 4, 5 a n d 6 s h o w t h e c o n v e r g e n c e o f c a l c u l a t i o n s w i t h J = 10, 15 a n d 20 w i t h i n c r e a s i n g basis. A l l t h e s e c a l c u l a t i o n s a r e e p a r i t y w i t h j e v e n as t h i s s y m m e t r y gives the densest spectrum and hence the slowest convergence properties. The l e v e l s a n a l y s e d c o r r e s p o n d to t h o s e t h a t m i g h t b e t h o u g h t o f as s t e m m i n g f r o m t h e g r o u n d a n d first t w o v i b r a t i o n a l l y - e x c i t e d s t a t e s (v 2 = 1 a n d v3 = 1), d e t e r m i n e d s i m p l y o n e n e r g y o r d e r i n g . I t c a n b e s e e n t h a t in all c a s e s t h e r e s u l t s a r e c o n v e r g i n g , a l t h o u g h t h i s c o n v e r g e n c e is s l o w e r as J i n c r e a s e s . T h e c o n v e r g e n c e

T a b l e 4. Convergence of some levels with J = 10 e ( j even) with increasing vibrational basis, N. Energies, in c m - 1 , are all relative to E 0 = --32962.24. k, the projection of J along R, values are taken from the N o - C o r i o l i s calculations. Wavenumbers/cmLevel n u m b e r k= N o Coriolis N = 40 80 120 140 160 180 1 0 2928"04 1982"24 1977-14 1976"66 1976"53 1976-53 1976-52 4 6 3575-06 3182"15 3181"48 3181"40 3181"39 3181"39 3181"39 7 1 4993"32 4192"20 4191"37 4191"35 4191"34 4191"34 4191"34 10 2 5255"81 4914"70 4908"68 4907"86 4907-26 4907-19 4907"11
1

13 6 5793-80 5274"42 5270"12 5269"14 5269"07 5269"02 5268"98

16 10 6411"49 5705"53 5702-15 5701"30 5701"25 5701"21 5701"17

1074 Table 5.

J. T e n n y s o n a n d B. T . Sutcliffe Convergence of some J = 15e (j even) levels with increasing N. See legend to table 4 for further explanation. Wavenumbers/cm- 1

Level number k= No Coriolis N = 40 80 120 160 180 200

1 0 6018-88 4154.92 4128"18 4126-30 4123"27 4123"13 4123"04

4 6 6799"41 6047-04 5932-57 5922"71 5904"88 5904-20 5903"39

7 10 7861-42 6609.22 6554.57 6549-38 6539.20 6538.34 6537.62

10 2 8337-03 7173.86 7103.85 7092-55 7084"78 7083.89 7083"23

13 4 8614-36 7698"90 7660"20 7650-89 7647-86 7647"35 7646"19

16 0 9072.26 8099"87 7979"43 7973-82 7969"43 7969"02 7968"62

Table 6.

Convergence of some J = 20 e (j even) levels with increasing N. See legend to table 4 for further explanation. Wavenumbers/cm- 1

Level number k= No Coriolis N = 40 80 120 160 180

1 0 9819'4 7039'5 6981"2 6968"4 6958-5 6957"2

2 2 9927"2 8083-5 8032"4 8024"4 8012"7 8011"8

4 6 10729-4 8896.3 8825.9 8819.8 8809-3 8808.6

6 1 11351.3 9503-9 9445"8 9439.0 9429.5 9428"6

8 10 12049"6 10012"6 9886"0 9881"5 9874-0 9870"9

10 12 12762-1 10189"3 10132"8 10127-1 10119"8

w i t h t h e r e - o p t i m i z e d basis is also slower t h a n that o b s e r v e d b y us in test calculations u s i n g the s m a l l e r basis of table 1. T h i s is b e c a u s e the s p e c t r u m of v i b r a tional levels given b y the larger r e - o p t i m i z e d basis is d e n s e r . A feature s h o w n b y a n a l y s i n g c o n v e r g e n c e rates is that the lower levels do n o t necessarily c o n v e r g e q u i c k e r - - f o r example, c o m p a r e the lowest level in table 4 w i t h level n u m b e r s 4 a n d 7. T h i s is b e c a u s e the Coriolis i n t e r a c t i o n s for states w i t h low k are c o n s i d e r ably s t r o n g e r t h a n those w i t h h i g h k, d u e to the a n g u l a r coefficient Cfk, see I. A n o t h e r o b v i o u s feature is that n e g l e c t i n g the Coriolis i n t e r a c t i o n s is a poor a p p r o x i m a t i o n for H 2 D + . T h e tables show that for N = 180, the J = 10 e levels are c o n v e r g e d to a b o u t 0"1 c m -1, J = 15 e to a b o u t I c m -1 a n d the J = 20 e levels to a b o u t 5 c m - t. A l t h o u g h we w o u l d like to c o n s i d e r Js h i g h e r t h a n 20, this m u s t await a t i m e w h e n this level of c o n v e r g e n c e can be i m p r o v e d u p o n .

4. RESULTS C a l c u l a t i o n s were p e r f o r m e d u s i n g the o p t i m i z e d basis of table 3 for the first v a r i a t i o n a l step. T h e a n g u l a r basis set p a r a m e t e r j ~ x was i n c r e m e n t e d f r o m 14 for k = 0 to 34 for k = 20. T h u s for each J it was necessary to diagonalize J + 1 secular p r o b l e m s of d i m e n s i o n 504 as c a l c u l a t i o n s w i t h p = 0 a n d p = 1 (e a n d f ) use the same basis. F o r the s e c o n d v a r i a t i o n a l step N = 180 was u s e d for all J. T h i s was d o n e for c o n s i s t e n c y , e v e n t h o u g h for lower J values it gave c o n v e r g e n c e c o n s i d e r a b l y b e t t e r t h a n r e q u i r e d . F o r each J value a n d s y m m e t r y

Rotationally excited states of H z D +

1075

b l o c k , the d i a g o n a l i z a t i o n was c o n v e r g e d to 0-01 c m -1 for sufficient levels to c o v e r a p p r o x i m a t e l y , t h e r o t a t i o n a l m a n i f o l d o f t h e l o w e s t t h r e e v i b r a t i o n a l states. T h r o u g h o u t this w o r k t h e p o t e n t i a l of S c h i n k e , D u p u i s a n d L e s t e r [ 2 1 ] h a s b e e n u s e d , for p r e v i o u s w o r k h a d s h o w n it to p r o v i d e a v e r y g o o d r e p r e s e n t a t i o n of t h e l o w - l y i n g r o t a t i o n a l states, r e p r o d u c i n g e x p e r i m e n t to a b o u t 0"1 p e r c e n t [12, 22]. H o w e v e r o u r p r e v i o u s c a l c u l a t i o n s h a v e s h o w n t h a t t h e B V D H p o t e n t i a l fitted b y M a r t i r e a n d B u r t o n [23] to t h e ab initio d a t a o f B u r t o n et al. [ 2 4 ] gives b e t t e r r e s u l t s for t h e v i b r a t i o n a l e x c i t a t i o n e n e r g i e s t h a n does t h e S D L p o t e n t i a l . It was t h e r e f o r e t h o u g h t a p p r o p r i a t e to c o m p a r e t h e effectiveness of t h e s e t w o p o t e n t i a l s in h i g h J calculations. T h e r e s u l t s o f s u c h a c o m p a r i s o n , for J = 16 e, are s h o w n in t a b l e 7. T a b l e s 8 to 11 give t h e c a l c u l a t e d levels for H 2 D + w i t h J u p to 20 for t h e f o u r s y m m e t r y b l o c k s u s i n g t h e S D L p o t e n t i a l a n d t a b l e 12 c o m p a r e s o u r l a b e l l i n g o f the s y m m e t r y b l o c k s w i t h o t h e r l a b e l l i n g s c h e m e s . I n all t h e t a b l e s 7 to 11, t h e f r e q u e n c i e s of t h e levels are given relative to t h e J = 0 v i b r a t i o n a l g r o u n d state o f H 2 D +. F r o m t h e s e a n d t h e a p p r o p r i a t e selection rules ( A J = 0, __+1 ; A K a = 0, 2 . . . . ; A K c = 1, 3, . . . ) a list o f p r e d i c t e d t r a n s i t i o n f r e q u e n c i e s has b e e n c o n s t r u c t e d , c o p i e s of w h i c h can b e o b t a i n e d f r o m t h e a u t h o r s . I t was h o w e v e r n o t p o s s i b l e to label all states w i t h v a l u e s of ( K a , Kc). T h i s is b e c a u s e of t h e i n c r e a s i n g o v e r l a p b e t w e e n r o t a t i o n a l m a n i f o l d s of d i f f e r e n t v i b r a t i o n a l states. T h i s b e h a v i o u r is also reflected in the k v a l u e s of t h e N o C o r i o l i s r e s u l t s p r e s e n t e d in t a b l e s 4 to 6. Table 7. Comparison of the J = 16 e rotational levels for two ab initio potentials. Wavenumbers/em- 1 j even State number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 SDL 4637.44 5548-71 6225"05 6396'56 6708-13 6974"50 7047"51 7410-17 7424'76 7600"36 7881'93 8031-74 8217-49 8332"45 8434-39 8538'20 8637-12 8723-24 8812"47 8867-55 9147.64 9171-11 9196"02 9335"83 BVDH 4631"65 5543.06 6221"07 6407.87 6705.12 6973-50 7060.82 7411"04 7427.91 7593-25 7898.16 8030.82 8218.32 8349.57 8452.08 8533"10 8668.04 8723-49 8813.61 8891"82 9142"84 9176-04 9196"27 9356.46 A 5.79 5"75 3"98 --11-31 3-01 1'00 --13'31 --0"79 -- 3-15 7"11 -- 16"77 0"92 --0-83 -- 17.12 --17"69 5"10 --30"92 --0"25 -- 1"14 --14"27 4"80 --4"93 --0"25 --20-63 SDL 4635-27 5548-69 6224.96 6384.25 6724.40 7045-34 7155-42 7420-40 7597.19 7708-41 7882.19 8217.33 8302"88 8373.36 8436-18 8538'54 8626.69 8787"67 8861-19 9059'71 9067.90 9155-02 9210-06 9323"17 j odd BVDH 4629"55 5543.05 6221'01 6395.78 6722-34 7058-78 7155-16 7424-55 7590"44 7707.83 7898"39 8218.21 8320"29 8372"65 8453-43 8533'70 8657-11 8799"54 8874-49 9069'81 9081'49 9160"86 9230-00 9325"22 A 5"72 5"74 3-95 --11"53 2"06 --13"44 0'26 --4'15 6'75 0-58 --16'20 --0-88 --17.41 0.71 --17-25 4.84 --30-42 --11-87 --13.30 --10"10 --13.59 --5.84 -- 19.94 --2"05

1076 T a b l e 8.

J. T e n n y s o n

a n d B. T . S u t c l i f f e

H z D + rotational levels w i t h j even a n d e (p = 0) total p a r i t y relative to the J = 0 g r o u n d state at --32962"24 c m - i. Wavenumbers/crn- 1 45"64 131.46 251"05 402-29 2944'04 585'41 3181"46 800'57 3271-57 1047'61 3564-66 1326'21 3725"94 4509'16 1635.99 4043"79 4921.34 1976"52 4191.34 5268-98 2347"32 4657'46 5729"33 2747-92 5152-90 6058"01 6780"03 3177"79 5598-21 6567"15 7255-41 3636-38 6055"12 7096"97 7683-51 4123-13 6538-35 7647-36 8196-43 4637"44 7047-51 8217"49 8812.47 9365-69 5178"70 7664.74 8806"26 9438"93 9944"34 5746"23 8384-57 9391.36 10079"35 10550-09 2225.09 223-60 375.86 580-70 2984.46 832-07 3217-21 1122.02 3466.17 1442.85 3782-35 1790.84 3884-21 4775.65 2165-93 4231.39 5146.54 2568-74 4390.44 5381-05 2999.31 4765.36 5884"83 3457-28 5168-09 6221.68 6852-22 3942.00 5677-05 6742.26 7322.84 4452-72 6229.03 7287-07 7689.22 4988.60 6807.99 7843.75 8260.90 5548.71 7410.17 8332.45 8867.55 9381.60 6132-12 7974-92 8850.99 9501-61 9960"99 6737-78 8552-47 9420.76 10156-29 10580.59 2377"45 2296"49 2393"31 778.10 1013"75 3556-47 1300"53 3499-66 1640"54 3840-47 2031"47 4128-33 2466-50 4504"47 5283-55 2937-04 4606-58 5545'93 3434-54 5009"63 5973"88 3953-06 5440"09 6424.91 4490'94 5897'33 6914'74 7463'98 5048'76 6380-60 7388-30 7901"44 5626"94 6889"12 7853"48 8514"22 6225-05 7424-76 8434"39 9147-64 6841"41 8047"29 9031"47 9689'98 10038-65 7457"07 8706'64 9641.60 10243'79 10688.41

J 1 2 3 4 5 6 7 8

2405"37 2558'92 2517'79 2671'87 1648-63 3787-93 1966-50 4034"95 2327-51 4229-03 2732-01 4617"08 3181'39 4907"11 5701-17 3677'37 5311"13 6149'88 4219-27 5712"34 6431"42 4801"85 6140-28 6963"63 5416-63 6597"27 7427"76 8017-14 5904-23 7083"90 7969"02 8591-38 6396"56 7600"36 8538'20 9171"11 6920"10 8146"50 9133'15 9785-69 7492-14 8721"76 9706-74 10417-12 10775-15

2465'88 2593"68 2751'09 2950.40 2856"36 3791'03 3071"57 4102'48 2799'75 4310-40 3194.69 4652'05 3626"44 4956-94 5802"02 4094.17 5352"80 6212"83 4597-18 5780"45 6571-11 5011"25 6290-14 6997-27 5442"76 6797-60 7524"11 8197"44 6055-23 7328.57 8119-61 8676-16 6708"13 7881"93 8637"12 9196"02 7371"06 8457-01 9157.43 9845.22 8043-50 9052"54 9753"54 10440-85

2796-70 2767-01 3003"91 3178"69 3437'39 4145"01 3317-61 4454"45 3594-53 4843"46 3902"35 5100"23 4241"07 5569-18 6272"99 4610-76 5807-36 6630"30 5135"71 6312-95 7142'23 5710"16 6865'45 7589.48 6322"58 7438'46 8147'37 8753'39 6974-50 8031.74 8723'24 9335-83 7581"63 8644-73 9338"39 9894"67 8141"66 9277-03 9966"26 10530-07

10

11

12

13

14

15

16

17

18

Rotationally excited states of H2 D+

Table 8 (continued). Wavenumbers/cm -1 19 6339.34 9122-25 9966-84 10734-13 11228.35 6957-24 9770.92 10597-10 11402.01 11908.55 12328.81 7364.71 9154-34 10046-28 10825.77 11253.45 8011-79 9875"63 10691-81 11438.62 11963-04 12426.94 8044.26 9325-20 10254-04 10827-83 11340"51 8652'67 9954.54 10864.73 11507"76 11982-20 8138.90 9396.01 10300-84 11014.84 11369"18 8808"63 10119.79 10940.45 11614'44 11998.39 8713"57 9667.73 10392'70 11065.06 11543'21 9328.80 10301"07 11049-83 11725-79 12206"70

1077

20

8739-88 9927"83 10606"77 11150"21 11589.29 9428.63 10566-90 11260"35 11789-88 12252"54

Table 9. J 1 2 3 4 5 6 7 8 9

H2 D+ rotational levels w i t h j even a n d f ( p = 1) total parity relative to the J = 0 ground state at --32962-24cm-1 W a v e n u m b e r s/ cm - 1 2383.71 218.41 354-33 530.63 744.08 3556.47 991-93 3504.52 1272.33 3837.81 1584-12 4105.06 1926-56 4481-31 5342.83 2299.06 4681.14 5698.25 2701.06 5087.06 6144.60 3131.98 5520-00 6329.34 3591-21 5979.48 6876.02 7701-47 4078.13 6464.96 7457.30 8175.28 4592.07 6975.96 8060.37 8670.13 2393.45 2517.44 777.76 1011-06 1289-47 3788.01 1610-42 4102.48 1970.44 4215.47 2365-77 4630.56 2792-97 4886.06 5770.96 3249.26 5317.79 6228.35 3732.61 5775.39 6622'45 4241.56 6257.82 7132-49 4774.99 6764.27 7524.11 8181.28 5331'91 7293"95 8119.64 8730.89 2486"64 2638.16 2676'26 2867-33 1648-62 3827.71 1966.36 4143'55 2326.68 4455.16 2728.58 4846'96 3170-49 5075-04 5802-33 3650.10 5541"46 6271-51 4164.29 5780-47 6713.07 4709.46 6312.93 7224.63 5281"85 6865.42 7676-13 8268"68 5878-02 7438-40 8253-43 8862-27

2796.63 2834-14 3068-50 3089.30 3341'67 4259"00 2799.75 4503-51 3194.69 4902.14 3626'41 5268.76 4093'99 5676-58 6606.44 4596-56 6025"05 6775-47 5133-13 6520-82 7311.67 5702.53 7024.72 7763-37 6303.09 7545.42 8331.38 8976.35

2942-59 3173"44 3334"84 3629-60 3624.25 4568.39 3936.88 4912.20 4191-34 5292"10 4651-69 5764'15 5053'53 6110.76 7018'64 5484'76 6581'69 7432-88 5945"15 7094"24 7872"05 6434"67 7639-60 8354'38

2984.86 3220"10 3447"42 3759-42 3952'18 4895'37 4302.73 5282"40 4279-44 5345"77 4657-49 5820.34 5152"92 6279.68 7118"93 5677"05 6819'90 7643.67 6229"03 7376"09 7883"66 6808"04 7949-20 8471"47

10

11

12

13

14

15

1078

J. T e n n y s o n

a n d B. T . S u t c l i f f e

Table 9

(continued).

Wavenumbers/cm- 1 16 5132-33 7511'95 8675.26 9188"27 5698'22 8074-08 9299"31 9734"96 10350.44 6288"98 8703.78 9930"28 10387"42 10927-94 6903'86 9384.30 10546-07 11065"12 11550-81 7542"06 10089-44 11169"69 11757-28 12235"87 5911-32 7845-82 8723"44 9308.44 6512'27 8419.50 9339'14 9911'03 7133'73 9014'55 9965.98 10540'60 11062"80 7774'75 9630"76 10594.76 11199'47 11680"95 8434'32 10267.79 11251'87 11894"22 12321'02 6495.02 8031"55 8852'75 9381.60 7130'62 8643'74 9396-38 10038.64 7783'12 9253"36 9970-26 10688"41 11100-60 8451"18 9872-46 10612-94 11340"51 11732-78 9133"70 10513-53 11274"73 11998"17 12383"19 6930'72 8089.99 8864"25 9475.52 7497'96 8660"57 9475"39 10105-89 8072"70 9277"91 10106"32 10751-73 8674"88 9928.34 10753'90 11391'89 11834.42 9303'98 10597.50 11418'34 12021.47 12465"13 6954.68 8209-66 8938'90 9580"80 7589'57 8801-55 9589-65 10208"56 8267-35 9413"66 10273.41 10795'53 8963'72 10045"16 10903.24 11421'14 9674.68 10694"93 11525"76 12098'01 12629.12 7413'25 8539'67 9088"72 9669"24 8042"68 9147"36 9726-84 10221-41 8653'71 9771"90 10305'40 10862.97 9262'20 10412.77 10973'51 11512"16 9892'72 11069'76 11677'78 12138"68 12704.62

17

18

19

20

T a b l e 10.

H2 D + rotational levels w i t h j o d d a n d e (p = 0) total parity relative to the J = 0 g r o u n d state at -- 32962-24 c m - 1. Wavenumbers/cm- 1 59"96 138'67 253"69 403.08 3135"56 585.61 3136"19 800"59 3427'21 1047'57 3568'83 1326'12 3885"67 4722'26 1635.84 4043.62 5046"91 1976"28 4390.18 5465.82 2346'96 4764'99 5674'10 2236-98 2300-69 457-82 644"77 875"41 3330-50 1146-34 3606-08 1453'94 3756'07 1795"06 4115'57 2167.31 4231-83 5120-45 2569-12 4606-66 5547-72 2999"40 4963"92 5919"44 2358-31 2452-19 2394-39 2517"95 1175"90 3365-21 1452-48 3639-32 1773"59 3925"37 2137"66 4287'40 2542-15 4500-18 5149"03 2983"72 4906-48 5560"91 3458-63 5009"59 5980"99

J 1 2 3 4 5 6 7 8

2544-51 2585"28 2751-99 2671"72 2855"99 3791-00 2191"52 3958"06 2548"67 4308"78 2945-72 4616"65 3381-80 4956-41 5879-26 3855"85 5310"74 6034"50

2629.24 2809'06 2949'98 3178.54 3070'93 4035.12 3316'58 4323"17 3468.14 4688.12 3899"31 5119"43 4237"75 5352.91 6201.25

2691'65 2889.44 3028.15 3282'39 3437.31 4310'99 3725"83 4662.25 3592"96 4730"13 3900-08 5183-00 4363'84 5577'67 6399'26

10

11

Rotationally excited states of H 2 D +

Table 10 (continued). Wavenumbers/cm 12 2747.36 5167.54 6194-16 6875"08 3176.98 5597-53 6635.58 7249.26 3635.22 6054-17 7199-88 7679-56 4121.53 6540.55 7778.62 8241.00 4635.28 7155.42 8302.88 8861-19 9365.69 5175.86 7801.25 8821.08 9507.61 9950-41 5742-59 8472.77 9418.26 10169"24 10537.74 6334-76 9143.50 10044.98 10807.10 11158.35 6951"61 9766.61 10690.35 11419.47 11848-46 12373.48 3457.29 5439.97 6403-97 3942.00 5897-26 6734.11 7377.90 4452.72 6380-39 7287.94 7908-98 4988-59 6888.53 7818.85 8441.02 5548-69 7420-39 8373.35 9059.70 6132-05 7975.00 8984.26 9671.93 9971.34 6737.65 8552.04 9610.52 10226.54 10625.72 7364.43 9175-45 10241.11 10837.80 11303.02 8011'27 9888.78 10848.33 11512.24 11976.66 3963-24 5463.75 6450-12 4494.40 5988.50 6905.21 7476"28 5049"62 6537-95 7366.52 8031.38 5627-02 7081"40 7855"32 8469.52 6224.96 7597.19 8436-18 9067-90 6840.80 8142.80 9032-15 9688.68 10187.50 7443.71 8717.70 9640.56 10327-68 10773.48 8024"76 9320.77 10255.07 10971.71 11365-94 8630-18 9950.05 10909.84 11609.74 11996.96
1

1079

4366-47 5711"47 6542-44 4911.62 6138"98 6945.76 5434"35 6595-41 7424"14 8124-09 5894.20 7111'53 7968"17 8607-79 6384"25 7708.41 8538.55 9155-02 6905-81 8327"91 9132.57 9696'51 7488-02 8969'11 9696.05 10348.70 10803.92 8138-26 9629"94 10298-79 11011.10 11441.80 8808"35 10291.41 10944-91 11625.58 12103.59

4606"07 5807.69 6556'56 5005-25 6290-43 6972-82 5488.90 6797'77 7546-68 6094"27 7328-70 8138.39 8667"05 6724-40 7882"19 8626.68 9210.06 7375"41 8457-43 9146-86 9828.40 8043.48 9053.61 9753-83 10438-50 8711-04 9671.41 10392"69 11035-84 11584-51 9324'47 10328.33 11049'56 11723.10 12202.07

4860-72 6061"01 6846-87 5389-11 6567"93 7081-49 5948"16 7096"99 7647'79 6533"64 7647-23 8156-68 8711'57 7045"34 8217"33 8787-68 9323"17 7579"50 8802.40 9427"58 9888-50 8138.90 9355'97 10074"85 10468"10 8738.14 9926.18 10732.50 11125.25 11688"42 9428'29 10522.88 11399.61 11780.62 12365-39

13

14

15

16

17

18

19

20

Table 11. J 1 2 3 4

H2D rotational levels with j odd and f (p = 1) total parity relative to the J ground state at -- 32962'24 c m - 1. Wavenumbers/em- 1 72-37 175-71 325.72 515.44 2256.86 2357.94 459.30 653.68

2543.57 2498.78 2668'90

2634.23 2831'92

2685-24 2869'64

3135"63

1080

J. T e n n y s o n T a b l e 11

a n d B. T . S u t c l i f f e

(continued).

W a v e n u m b e r s / c m -1 5 6 7 8 9 737"74 3330-73 989-74 3607"12 1271-66 3728"32 1583-94 4089'79 1926-53 4302"66 5123"07 2299.06 4681'04 5565"18 2701"08 4963-92 5921"61 3132"01 5463-73 6410"19 3591"27 5979-41 6818'79 7565"75 4078.21 6464.97 7377"02 8125-34 4592-18 6975'89 7950'89 8487.75 5132"48 7511-67 8541-22 9078.35 5698"41 8071.97 9148"54 9699.20 10341'30 6289"23 8656.29 9772.76 10337'15 10925'08 6904"18 9266"34 10413"73 11000.42 11524.85 7542"47 9999'52 11071-38 11684.29 902"86 3365'66 1204"37 3641"49 1551"43 3925-85 1935"61 4281-86 2348"73 4474"81 5335-45 2786'05 4883"62 5766.63 3246.90 5087-02 6049-07 3731-95 5520"00 6574"46 4241.44 5988"63 6932-19 7667.28 4774.99 6537'99 7485-41 8180-26 5331-92 7111"55 8066'46 8671.26 5911"34 7708-44 8670-71 9189.58 6512'28 8327.96 9293"93 9735-50 10349"10 7133"76 8968.92 9929.56 10359"79 11029-09 7774"81 9622"14 10551'61 11042-49 11682-22 8434"41 10265'73 11176.56 11736-45 1175"97 1453.14 3979"94 1776-93 3967"29 2149-28 4347"13 2571"97 4672"54 3043"36 5095-77 5959'93 3557.18 5317"02 6222-60 4104-92 5775"21 6704-02 4677"67 6257"91 7139"07 5268-24 6764.41 7730"90 8249-58 5873-67 7294"14 8295"67 8715.70 6494"26 7846-27 8861-32 9336-99 7130"80 8420"37 9400'98 9988-67 7783.34 9016.71 9972"16 10665"20 8451"32 9644'40 10600-00 11345"25 11699"75 9133"87 10326"32 11266'17 12017-43 2864"89 3088-58 2191"53 4258-47 2548"70 4567'56 2945"90 4776"97 3382"63 5247"73 3858-95 5548-27 6408-95 4375-85 6025"49 6885-63 4935"12 6520"05 7211'17 5537-21 7024.49 7750-73 6178'31 7545'47 8354.78 8847-06 6850"43 8090-04 8879"48 9459'46 7499"01 8659-91 9481-22 10086"09 8074-46 9254-74 10106"75 10728-95 8676"97 9873-50 10752"82 11396-92 11765.62 9306'37 10514"91 11417-49 12027-13 3076'21 3340.35 3341"50 4311-04 3624"27 4662-58 3468-14 4907'25 3899"36 5277"53 4363'84 5678-52 6538"87 4860"74 6111-68 7020'14 5389-22 6581"71 7391'03 5943.60 7093"62 7881-13 6435-25 7639"12 8373'09 9042"07 6953"73 8209-43 9018-67 9620-14 7545'77 8801.28 9679"25 10219-79 8250.68 9413.20 10306-71 10795"90 8961'34 10044"28 10904-81 11405"85 11835"06 9676.74 10693"44 11527'53 12110.53 3101-30 3394-36 3631"49 3952"53 4723"15 3937"00 5047'77 4279'63 5467"34 4652'00 6554'01 5053"93 6275-69 7037,03 5485"42 6635-58 7435'61 5951.09 7199.89 7925.05 6539-39 7778.67 8441.03 7161.28 8373-55 9067.07 9670'21 7816-93 8984.89 9692'93 10224'87 8509-18 9612.31 10325"20 10855"06 9235-99 10255"66 10970'14 11511-05 9892"81 10915'17 11624.20 12152-55

10

11

12

13

14

15

16

17

18

19

20

R o t a t i o n a l l y e x c i t e d states o f H z D +

1081

Table 12. Point group [7]

A1

Symmetry labels and sizes of the rotational manifolds (My) for HzD +.
v = 0w M~II

Parity of j r
e

Total parity~
e

Ka
2n - 2

Kc
J + 2 - 2n

v= 0
J/2 + 1

v2 = 1
J/2 + 1

v3 = 1
( J + 1)/2 J/2 + 1 ( J + 1)/2 J/2

A2
BI

o
e

e
f

2n - 1
2n

J + 2 -- 2n
J + 1 -- 2n

(J + 1)/2
J/2

(J + 1)/2
J/2

B2

2n -- 1

J + 1 -- 2n

(J + 1)/2

(J + 1)/2

e = even, o = odd. e i s p = 0, f i s p = 1. Total parity is (--1) a+v. w 2 . . . . . M~= 0 . II Manifold size using integer arithmetic.

5. D i s c u s s i o N F r o m the results s h o w n in table 7 it is possible to make an a s s e s s m e n t of the likely e r r o r in o u r calculations a r i s i n g f r o m the c h o s e n p o t e n t i a l . I n fact the a g r e e m e n t b e t w e e n the results o b t a i n e d f r o m the S D L a n d B V D H p o t e n t i a l s is fairly good, the largest difference b e i n g a b o u t 3 0 c m -1 for a few of the h i g h e r states. A detailed c o m p a r i s o n of the levels shows a n u m b e r of s y s t e m a t i c features w h i c h it is possible to u n d e r s t a n d f r o m a k n o w l e d g e of the results o b t a i n e d at low J w i t h each of the potentials. T h e f r e q u e n c i e s of the lowest 3 states w i t h j even or o d d a n d a n u m b e r of the h i g h e r ones (for example, b o t h states 16) are f o u n d to be 2 - 6 c m -1 h i g h e r for the S D L t h a n the B V D H potential. E x a m i n a t i o n of the w a v e f u n c t i o n shows that such states can, at least a p p r o x i m a t e l y , be associated with the v i b r a t i o n a l g r o u n d state. T h e p r e v i o u s c a l c u l a t i o n s [3] for low J s h o w e d that a precisely s i m i l a r d i s c r e p a n c y was o b s e r v e d in the g r o u n d v i b r a t i o n a l state results. T h e d i s c r e p a n c y m a y be t h o u g h t of as d u e to the d i s c r e p a n c y b e t w e e n the calculated r o t a t i o n a l c o n s t a n t s in each p o t e n t i a l a n d b e c a u s e the t e r m s in the e n e r g y p r o p o r t i o n a l to these c o n s t a n t s are m u l t i p l i e d b y j 2 , the difference will be m a g n i f i e d w h e n d e a l i n g with high J states. O n the o t h e r h a n d for c e r t a i n states (for e x a m p l e b o t h states n u m b e r 11) the S D L p o t e n t i a l gives f r e q u e n c i e s that are 1 0 - 2 0 c m -1 lower t h a n the B V D H potential. E x a m i n a t i o n of the w a v e f u n c t i o n s show that such states are in fact associated, a p p r o x i m a t e l y , w i t h the v2 a n d v3 v i b r a t i o n a l l y excited states. T h i s d i s c r e p a n c y is again to be expected f r o m p r e v i o u s c a l c u l a t i o n s w h e r e it was s h o w n that the S D L p o t e n t i a l gives v2 a n d v a f u n d a m e n t a l f r e q u e n c i e s w h i c h are a b o u t 2 0 c m - t too low. T h a t the d i s c r e p a n c y is g e n e r a l l y less t h a n this is due to a c a n c e l l a t i o n of errors. T h e r e are a few levels, b o t h states n u m b e r 17 for e x a m p l e , for w h i c h the S D L f r e q u e n c i e s are u p to 3 0 c m -1 lower t h a n the B V D H ones. T h e s e levels can be associated w i t h states with 2 q u a n t a in the v2 a n d v3 m o d e s , p r o b a b l y 2v2, for w h i c h d i s c r e p a n c i e s of this m a g n i t u d e b e t w e e n the p o t e n t i a l s are to be expected [3]. N o t all the states fall exactly into the three categories g i v e n above, w h i c h can be e x p l a i n e d b y the m i x e d v i b r a t i o n a l p a r e n t a g e of some states a n d the s i m p l i s t i c t r e a t m e n t of the rotational c o n s t a n t s in the above discussion. H o w e v e r , it is clear that the c o m p a r a t i v e b e h a v i o u r of the two p o t e n t i a l s can be u n d e r s t o o d f r o m their p r o p e r t i e s at low J. It is w o r t h n o t i n g that, a l t h o u g h the a b s o l u t e shifts for J = 16

1082

J. T e n n y s o n a n d B. T . Sutcliffe

levels are as m u c h as 3 0 c m -1, t r a n s i t i o n s in s i m u l a t e d s p e c t r a , w h i c h o f c o u r s e o n l y i n v o l v e A J = 0 , ~ 1 , will g e n e r a l l y agree to a b o u t 1 c m - 1 p r o v i d e d the t r a n sitions i n v o l v e no v i b r a t i o n a l e x c i t a t i o n . F i g u r e s 1 a n d 2 i l l u s t r a t e t h e q u a l i t a t i v e b e h a v i o u r o f t h e r e s u l t s o f t a b l e s 8 to 11. F i g u r e 1 s h o w s t h e b r o a d e n i n g o f the r o t a t i o n a l m a n i f o l d s for one s y m m e t r y b l o c k (the total s y m m e t r i c ee b l o c k ) as J increases 9 F o r c o m p a r i s o n , t h e p o s i t i o n of the l o w e s t 10 b a n d o r i g i n s are g i v e n for J = 0. W h a t figure | s h o w s is the p r o g r e s s i v e o v e r l a p o f t h e r o t a t i o n a l m a n i f o l d s b e l o n g i n g to d i f f e r e n t v i b r a t i o n a l states. T h u s for J = 4 a n d above, the v 2 a n d v a states b e c o m e s i g n i f i c a n t l y m i x e d , s o m e t h i n g t h a t is k n o w n f r o m b o t h t h e o r y [2] a n d e x p e r i m e n t [10, 12]. A b o v e J = 11 t h e r o t a t i o n a l levels of t h e g r o u n d state o v e r l a p t h o s e o f t h e v i b r a t i o n a l l y e x c i t e d states. By J = 20 the l o w e s t v 2 level is t h e t h i r d e x c i t e d state 9 I t is t h u s p o s s i b l e to e x t r a p o l a t e to J ~ 25 w h e r e o n e will find t h a t t h e l o w e s t v i b r a t i o n a l e x c i t a t i o n is less t h a n t h e lowest r o t a t i o n a l e x c i t a t i o n ! I n m o s t of t h e p r e v i o u s w o r k on h i g h l y - e x c i t e d r o t a t i o n a l states t h e m o l e c u l e has b e e n t r e a t e d as a r i g i d a s y m m e t r i c top. I t is w e l l - k n o w n [7, 25] t h a t this m o d e l p r e d i c t s a large n u m b e r of a c c i d e n t a l d e g e n e r a c i e s , w i t h s p l i t t i n g s as s m a l l as 1 0 - 1 3 c m -1 w h e n ~: = 0 a n d J = 20 [7]. I t is i n t e r e s t i n g to see h o w far this s t r u c t u r e is p r e s e r v e d w h e n t h e c o n s t r a i n t s o f r i g i d i t y a n d no r o - v i b r a t i o n a l i n t e r action are lifted. F i g u r e 2 gives t h e levels o f J - - 15 p l o t t e d to e m p h a s i z e the
10
H2D+ n_,i. e ~ar.tv j even
---" : = -

" = ._
___- __-- -

=-=
.
-

-_- _
-

_-

8
i

E
U

_-

_-

6
_ .,0

_-.. _

--

__

E
r >

=-

4
= __

=
I

(}

10

15

2LO

Figure 1. Rotational levels associated with the lowest three vibrational states of H2 D+ as a function of J. Results are for the symmetry block with j even (para H2) and e (p = 0) total parity.

Rotationally excited states of HzD +

.

1083

-Z =
_ --

1.1 -" _

= 0.002 = Ok _"
_ = -

=
.

= 0.8 -

(1031.7

1.8 0.1 - 0 . 0 6 0.5

-~5
-

0.1 25 0.6

0115

- 0 2

-0.02

= _

~o
.0 E
D r

7,

= -

-0117 -

2.2

- 0 . 6 -

1.1

>
0

6.
0.08--0,01 --

-0.007-

0.1

1.6

oe

ee

ef

of

oe

Figure 2. Comparison between symmetry species for rotational levels with J = 15. The figures give the splittings, in cm-1, of near degenerate levels between neighbouring symmetries. The symmetries are labelled by parity of j (e for even, 0 for odd) and total parity (e for p = 0 and f for p = 1), see table 12. degeneracies. T h e separation of all levels closer than 5 c m - 1 are given explicitly. Splittings of less than 0"01 cm -1 can have no significance because of the convergence criteria of the diagonalization and it should be remembered that the absolute convergence of the J = 15 calculation is only about 1 c m - 1, although the splittings between systematically degenerate levels are probably better converged. Inspection of figure 2 shows that the structure of the nearly degenerate levels corresponds, for the lowest levels, with that found by Harter and Patterson for a rigid asymmetric top with ~: = 0 [7]. T h e lowest states are three nearly degenerate pairs for each total parity : each pair is composed of one state with j even and one with j odd, the so-called Cz(x)-Type Clusters [7]. At higher energy there are another 3 interleaved pairs, this time with the members of each pair having a c o m m o n j parity and differing in the total parity, the so-called C2(z)-Type Clusters [7]. Overlapping the higher degeneracies are a large n u m b e r of near degeneracies with c o m m o n j parity and differing in total parity. These come from rotational states associated with vibrationally excited states. However, because of the overlap between the levels associated with vibrational states v2 and v3, and no doubt higher vibrational states, there is no easily discernible structure in this energy region. One would expect that for J ~ 15 the structure of the rotational manifold of the vibrational ground state would also be destroyed.

1084

J. T e n n y s o n and B. T. Sutcliffe

6. CONCLUSION
In this paper we propose a m e t h o d of performing calculations on the highly rotationally excited state of triatomic molecules. T h e method is in principle exact within the constraints of the variation theorem, which we apply twice. We use the method to calculate the rotational levels with J ~< 20 of the lowest three vibrational state of H 2 D +, a molecule chosen because of the likely strength of Coriolis and centrifugal distortion effects. Qualitatively, we see the progressive overlap of rotational manifolds belonging to different vibrational states. We thus probe both low and intermediate J regions and expect the high J region, where the width of a rotational manifold is m u c h greater than the vibrational spacing, to be reached at J ~ 25 for HED+. We hope that our results might aid the observation of high J states of H2D +. T h e r e are two main sources of error in our calculations caused by inaccuracies in the underlying electronic potential and truncation of the vibrational basis sets. By comparing results for different potentials we see that the absolute energy of the lowest states vary by about 5 cm -1 for J = 16, where the variational calculations are converged to about l c m -1. Transition frequencies, which do not involve vibrational excitation, will allow for a cancellation of m u c h of this absolute error and should be accurate to about I c m - 1 for J ~ 15 and 5 c m - 1 for J ~ 20, where the convergence of the basis set is poorer. We are grateful to Professor J.-L. Destombes for bringing this problem to our attention and for helpful correspondence.

REFERENCES TENNYSON,J., and SUTCLIFFE,B. T., 1984, Molec. Phys., 51,887. TENNYSON,J., and SUTCLIFEE,B. T., 1985, Molec. Phys., 54, 141. TENNYSON,J., and S~TCLIFFE,B. T., 1985, Molec. Phys., 56, 1175. TENNYSON,J., and SUTCLIFFE,B. T., 1986, J. chem. Soc. Faraday II (in the press) SPIRKO,V., JENSEN, P., BUNKER, P. R., and CEJCHAN,A., 1985, J. molec. Spectrosc., 112, 183. JENSON, P., SPIRKO,V., and BUNKER,P. R., 1986, J. molec. Spectrosc., 115, 269. [6] LEMOINE,B., BOG/~Y,M., and DESTOMBES,J. L., 1985, Chem. Phys. Lett., 117, 532. [7] HARTER,W. G., and PATTERSON,C. W., 1984, J. chem. Phys., 80, 4241. [8] BOHR, A., and MOTTELSON, B. R., 1975, Nuclear Structure, Vol. II (Benjamin), Chap. 4. [9] CHEN, C.-L., MAESSEN,B., and WOLFSBERG,M., 1985, J. chem. Phys., 83, 175. [10] SHY,J.-Z., FARLEY,J. W., and WING, W. H., 1981, Phys. Rev. A, 24, 1146. [11] AMANO,T., and WATSON,J. K. G., 1984, J. chem. Phys., 81, 2869. [12] FOSTER,S. C., McKELLAR,A. R. W., PETERKIN,I. R., WATSON,J. K. G., PAN, F. S., CROFTON, M. W., ALTMAN,R. S., and OKA, T., 1986, ff. chem. Phys., 84, 91. [13] BOGEY, M., DEMUYNCK,C., DENIS, M., DESTOMBES,J. L., and LEMOINE, B., 1984, Astron. Astrophys., 137, L15. WARNER,H. E., CONNER, W. T., PETRMICHL, R. H., and WooDs, R. C., 1984, ]. chem. Phys., 81, 2514. SAITO, S., KAWAGUCHI,K., and HIROTA, E., 1985,J. chem. Phys., 82, 45. [14] DESTOMBES,J. L. (private communication). 1-15] SUTCLIFFE,B. T., and TENNYSON,J., 1986, Motec. Phys., 58, 1053. [16] TENNYSON,J., 1986, Comput. Phys. Rep. (in the press). [17] Subroutine EIGSFM, GARBOW,B. S., BOYLE, J. M., DONCARRA,J. J., and MOLER, C. B., 1977, Matrix Eigensystem Routines--EISPACK Guide Extension (Lecture Notes in Computer Science, Vol. 51) (Springer). [18] Subroutines BANDR and BISECT [17]. [1] [2] [3] [4] [5]

Rotationally excited states of H 2 D +

1085

[19] FO2FJF, 1983, NAG Fortran Library Manual, Mark 11, Vol. 4. NIKOLAI, P. J., 1979, A C M Trans. Math. Software, S, 118. [20] TENNYSON,J., 1983, Comput. phys. Commun., 29, 307. [21] SCHINKE,R., DUPUIS, M., and LESTER,W. A., JR., 1980, J. chem. Phys., 72, 3909. [22] WATSON, J. K. G., FOSTER, S. C., McKELLAR, A. R. W., BERNATH,P., AMANO, T., PAN, F. S., CROFTON, M. W., ALTMAN, R. S., and OICA,T., 1984, Can. J. Phys., 62, 1875. [23] MARTIRE,B., and BURTON,P. G., 1985, Chem. Phys. Lett., 121,479. [24] BURTON, P. G., VON NAGY-FELSOBUKI,E., DOHERTY, G., and HAMILTON, M., 1985, Molec. Phys., 55,527. [25] GORDY, W., and CooK, R. L., 1970, Microwave Molecular Spectra, 2nd edition, (Interscience-Wiley), Appendix 1. TOWNES, C. H., and SCHAWLOW, A. L., 1955, Microwave Spectroscopy (McGraw-Hill), Appendix IV.