APPLICATION OF THE FINITE ELEMENT METHOD TO MOLECULAR QUANTUM

MECHANICS
V. V. Gusev, S. G. Potapov,
and L. P. Sukhanov
UDC 539,194
We present a general formalism of the finite element method and its computational
aspects that influence the solution accuracy of spectral quantum mechanical prob-
lems. The possibilities of the method are demonstrated using as an example in-
version vibrational spectra of structurally non-rigid complexes.
Despite its relatively old applications in engineering problems, the finite element
method (FEM) [i] makes just its first steps in molecular quantum mechanics. In the theory of
chemical reactions, studies using the FEM began approximately 15 years ago but it has
only been in recent years that the method has been more widely used to describe the dynamics
of the "atom + diatomic molecule" [2, 3] interaction processes. This recent interest has
been mainly due to the introduction of vector supercomputers in theoretical chemistry studies.
Their special features of the method. In the present paper, the FEM possibilities are
evaluated by analyzing results of FEM calculations of the inversion vibrational spectra of
systems with double minima and large-scale motion, i.e., motion whose amplitude is compar-
able to the characteristic dimensions of the system itself. As examples of such quantum
mechanical systems one can take complexes with hydrogen bonds, structurally non-rigid molec-
ules, impurities in crystals transferable at an elementary-cell distance, etc.
General Formalism and Basic Ideas of the FEM. The FEM proposes a numerical solution
of the standard Schrodinger equation
/~ () 'v (x) = ~ (x) ( 1 )
in space of one two, or three variables contained in a vector x, in the region ~ (x ~;
= {x, y, z} with the Dirichlet boundary conditions ~F = 0). The search for eigenvalues
and eigenfunctions of the Schrodinger equation is equivalent to the fulfillment of a varia-
tional principle
6 L = [ d Q 6 ~ ( x ) [ h J - - -2--~- v ~ + V ( x ) - - E ( x ) = 0 , ( 2 )
which can be represented, after taking into account the Ostrogradskii--Gauss theorem and the
Dirichlet boundary conditions, in the form
d ~ [ h2 V 6 ~ t V ~ + 6 ~ ( V ( ) - - E ) ~ t ] = O .
6 L
The basic ideas of the FEM are the following.
I. Discretization of the region in which a solution is being sought into finite ele-
ments ~
M
l=l
This means that a one-, two-, or three-dimensional grid is constructed in the region ~.
2. Approximation of the unknown wave function by a local function ~()(x) within each
element ~
( 4 )
High Energy Physics Institute, Protvino. I. V. Kurchatov, Atomic Energy Institute,
Moscow. Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 27, No. 4, pp.
442-446. July-August, 1991. Original article submitted April 4, 1991.
0040-5760/91/2704-0381512.50 1992 Plenum Publishing Corporation 381
~ . . a u
-5,7z
He 0 x He
-e/2 e,~
-~,78
15 - A a o
~f J~
~z
Fig. i. C h a r g e p a t t e r n , c a l c u l a t e d u s i n g the H a r t r e e - F o c k
m e t h o d , d e s c r i b i n g the a x i a l l y - s y m m e t r i c m o t i o n of p o s i t i v e
c h a r g e s M + (M + = H +, p+) in i n t e r s t i c e s of t h e h e l i u m c r y s t a l
for t h e i n t e r n o d e d i s t a n c e R = 5 au (the d o t t e d line r e p r e -
s e n t s t h e p r o j e c t i o n of the m i n i m a l - e n e r g y p a t h on t h e (x, P)
p l a n e ).
PEQI
~ ( X E ~ L ) - - ~ ] ; U ) ( X ) _ : c, ~' i ( X ) , ( 5 )
f =l
where t he c o e f f i c i e n t s c i ( ) need t o be d e t e r mi n e d . The f or m- ( or b a s i s ) f u n c t i o n s F i ( ) ( x )
are u s u a l l y c h o s e n as p o l y n o m i a l s of d e g r e e m w i t h r e s p e c t to the c o m p o n e n t s of the v e c t o r
= {x, y, z}, or as the L a g r a n g e i n t e r p o l a t i o n p o l y n o m i a l s = {x, y, z). In the l a t e r case,
the c o e f f i c i e n t s ci (~) are e q u a l to the v a l u e of the w a v e f u n c t i o n at the i-th n o d e on the
b o u n d a r y F I of the e l e m e n t ~i, i.e., ~lh----~FIo(,)=~Irl . W e n o t e t h a t t h e local f u n c t i o n
~(~), as w e l l as the g l o b a l f u n c t i o n P r e m a i n c o n t i n u o u s l y d i f f e r e n t i a b l e .
3. R e p l a c e m e n t of t h e i n t e g r a l o v e r the r e g i o n fl in Eq. 2 by a s u m of a p p r o p r i a t e in-
t e g r a l s over all e l e m e n t s ~i
M
6 L = \ " 6 L t =: O.
l='--i (6)
As a result, the p r o b l e m (i) is f o r m u l a t e d as a g e n e r a l i z e d a l g e b r a i c p r o b l e m of f i n d i n g n
lowest e i g e n p a i r s {Ek, ~k} (k = 0 . . . . . n--l):
A ~
X' ( Hj i - - E S i i ) c i = O,
i =l
( 7 )
w h e r e N is the t o t a l n u m b e r of g r i d n o d e s in the r e g i o n ~,
n ( . ~ ' [ F I " E l " t r - ( [ V F } , ~ ( x ) ] I V F / ' ( x ) l d~ = ~, = ~-~ (x) v ( x ) (x) d ~ + ~ ~t
h2
= ( F ~ I V l F , ) " ~ + - 2 ~ - < V F ~ I V F ~ > " ~ '
382
TABLE 1. Calculated and Experimentally Measured Energy Levels
(in cm-') of Inversion Vibrations in the NH, Molecule
Energy Our Calculation Calculation
level I calculation* I [S)*fc I [ 6 ] * . Experiment (5, 61
trFEM calculation with the potential V(x) = 112 ax2+v(exp'
(-yx2)-1) taken from [ 5, 61;
**Calculation using the generalized Wentzel-Kramers-Brillouin
(WKB) method;
***Variational calculation using a basis of harmonic oscillator
functions.
TABLE 2. Tunneling Splitting (in cm-') of the Energy Levels of
Quantum Mechanical Systems with a Double Well Symmetric Potential
for Various Degrees of Its Relative Perturbation
System
I
?=I 0 ",.
I
E= 1 ",,
I
F=O ",, Experiment
A(!! 7 - 1 1 - )
NH, *
A@--o-) 0.58 (30) 031 ( 4) 0.84 0.79
A(lT-I-) 27.1 ( 21) 34.7 ( 3) 35.6 35.6
A(? !--2-) 255.6 ( 9) 7 8 , 8 (1 ) 2PI.? 280
tic-HW-Hc"'
A(o+-0-) 0. 025(40) - 0.042 , -
A( ] +- I - ) 2. 78(33) - 4.54 -
A(?+-2-) 10 1.02 ( 29) - 142.27 -
*The percentage difference of the tunneling splitting from their
unperturbed values are given in brackets.
;k*The potential V(x) from Table 1 has been used with parameters
a, v, and y taken from [ S, 61.
**'kThe Hartree-Fock potential has been approximated by the
function V(X) = bx4-kx2 with parameters k = 2b = 0.053315 au [ 7 ] .
All matrix elements of the algebraic problem ( 7 ) , excluding perhaps the matrix elements of
the potential energy V(x), can be evaluated analytically. Hence, in contrast to quantum
chemical calculations of the molecular electronic structure, in the FEM a large fraction of
computer time is spent not evaluating matrix elements but searching for the n lowest eigen-
values of a sparse (thanks to the local character of the form-functions Fi(')(d) matrix of
large dimension N x N, where usually N - lo3-lo5. .. .
AS in all numerical methods, there are some intrinsic errors in the FEM. Their source
lies in basic approximations of the method: the discretization ( 4 ) , the numerical integra-
tion in the evaluation of <Ff (V l ~ ~ > , and the interpolation of the form-functions Fi(')(d
For example, in the case of an interpolation polynomial of degree m, the error in the cal-
culation of the k-th energy level is I Ek-E'ial -a(h2"' ) [4] (h=max diam Qr). However, as we
I ~ l S r n
- -
shall demonstrate below, it is not the intrinsic but rather the external errors (introduced
by the p o t e n t i a l V(x)) t h a t l i m i t the a b i l i t y of the m e t h o d to d e s c r i b e t h e l o w e s t p a r t of
the s p e c t r u m of the p r o b l e m (i).
Q u a n t u m M e c h a n i c a l A p p l i c a t i o n s of the FEM. In o r d e r to d e m o n s t r a t e the p o s s i b i l i t i e s
of t h e m e t h o d in s o l v i n g o n e - d i m e n s i o n a l e i g e n v a l u e p r o b l e m s , w e h a v e c a r r i e d out t h e cal-
c u l a t i o n of the i n v e r s i o n v i b r a t i o n a l s p e c t r u m of the N-H 3 m o l e c u l e . It is c l e a r f r o m T a b l e 1
that the i n t r i n s i c e r r o r s of F E M can be e s s e n t i a l l y e l i m i n a t e d t h a n k s to an o p t i m a l c h o i c e
of the g r i d d i m e n s i o n s a n d of the i n t e r p o l a t i o n p o l y n o m i a l d e g r e e . W e h a v e u s e d s q u a r e
f i n i t e e l e m e n t s ( w i t h t w o n o d e s per e l e m e n t ) and the L a g r a n g e i n t e r p o l a t i o n p o l y n o m i a l s as
F i. W e h a v e f o u n d that in o r d e r to d e t e r m i n e the a b s o l u t e e n e r g i e s of the l e v e l s w i t h 0.01
cm -l a c c u r a c y , it has b e e n s u f f i c i e n t to t a k e N ~ 103 on a u n i f o r m grid. O t h e r d e t a i l s of
the n u m e r i c a l p r o c e d u r e a r e d i s c u s s e d in [7].
W e h a v e u s e d the F E M to s o l v e a p r o b l e m of p o s i t i v e c h a r g e ( p r o t o n s , m u o n s ~+) local-
i z a t i o n in i n t e r s t i c e s of a q u a n t u m h e l i u m c r y s t a l [7, 8]. T h e p o t e n t i a l c u r v e d e s c r i b i n g
the m o t i o n of p o s i t i v e p a r t i c l e s b e t w e e n the h e l i u m a t o m s (see Fig. i, p = 0) c a l c u l a t e d
u s i n g the H a r t r e e - - F o c k m e t h o d at 37 points, is s i m i l a r to an i n v e r s i o n c u r v e of a m m o n i a ,
w i t h the o n l y d i f f e r e n c e b e i n g the b o u n d a r y c o n d i t i o n s : in the c a s e of c h a r g e l o c a l i z a t i o n
one takes ~(x = R/2) = 0 (x is the c o o r d i n a t e d e s c r i b i n g t h e l a r g e s c a l e m o t i o n a n d R is
the d i s t a n c e b e t w e e n He a t o m s ) i n s t e a d of ~(x = ~) = 0.
It f o l l o w s f r o m T a b l e 1 t h a t in the case of a s u c c e s s f u l c h o i c e of the p o t e n t i a l func-
tion V(x), the i n v e r s i o n v i b r a t i o n a l s p e c t r u m can be d e s c r i b e d w i t h the same a c c u r a c y as
o b t a i n e d e x p e r i m e n t a l l y . U n f o r t u n a t e l y , s u c h a s u c c e s s f u l c h o i c e is o f t e n n o t p o s s i b l e .
It is thus j u s t i f i e d to a s k h o w the a c c u r a c y of the p o t e n t i a l V ( x ) c o n t r o l s the a c c u r a c y
of the m a g n i t u d e of t u n n e l i n g s p l i t t i n g A of the e n e r g y levels. T h e a n s w e r is c o n t a i n e d
in the d a t a in T a b l e 2 c o n c e r n i n g the FEM s t u d i e s of t h e i n f l u e n c e of p o t e n t i a l p e r t u r b a -
tions (the p e r t u r b a t i o n d e g r e e is d e f i n e d as e = [ V ( x ) - - V ( x ) ] / V ( x ) (V(x) and V(x) are, re-
s p e c t i v e l y , the p e r t u r b e d a n d u n p e r t u r b e d v a l u e s of t h e p o t e n t i a l at t h e p o i n t x) on the
m a g n i t u d e of the t u n n e l i n g s p l i t t i n g for s y s t e m s w i t h two e q u i v a l e n t m i n i m a on the p o t e n -
tial curve. F o r the p e r t u r b a t i o n d e g r e e g, the t u n n e l i n g s p l i t t i n g m a g n i t u d e s are d e t e r -
m i n e d w i t h r e l a t i v e e r r o r s of s e v e r a l e and this e r r o r d e c r e a s e s as t h e level n u m b e r n
increases. In this way, w i t h e < 10%, the t u n n e l i n g s p l i t t i n g s A can be, in t h e limit,
c a l c u l a t e d w i t h i n t h e l i m i t s of the q u a n t i t y ~ itself. In t h e r e m a i n i n g cases, t h e a c c u r a c y
of the t u n n e l i n g s p l i t t i n g c a l c u l a t i o n is a l r e a d y n o t c o n t r o l l e d . A l l this i n d i c a t e s h i g h
level of r e q u i r e m e n t s for a c c u r a c y of the p o t e n t i a l V(x).
A m o n g o t h e r m e r i t s of t h e F E M in c o m p a r i s o n with, for e x a m p l e , the f i n i t e d i f f e r e n c e
method, w e n o t e that it can be q u i t e e a s i l y g e n e r a l i z e d to t h e c a s e of h i g h e r d i m e n s i o n D
~r, the S c h r o d i n g e r e q u a t i o n (I) [4]. To i l l u s t r a t e t h i s w e h a v e s t u d i e d h o w a d d i n g a s e c o n d
d i m e n s i o n i n f l u e n c e s the s p e c t r u m of l a r g e - s c a l e m o t i o n of p o s i t i v e c h a r g e s in i n t e r s t i c e s
of the H e c r y o c r y s t a l . T h e c h a r g e p a t t e r n V(x, p) d e s c r i b i n g s u c h a x i a l l y - s y m m e t r i c m o t i o n
of c h a r g e s (see Fig. i) r e p r e s e n t s a H a r t r e e - F o c k p o t e n t i a l at 375 p o i n t s of the r e g i o n ~ =
(x, p). A m o n g the p h y s i c a l e f f e c t s a r i s i n g f r o m the a d d i t i o n of a s e c o n d d i m e n s i o n , w e n o t e
the a p p e a r a n c e of d o u b l e t l e v e l s (not only in x but a l s o in p) d u e to t h e i n t e r a c t i o n b e t w e e n
the x a n d p v a r i a b l e s (a k n o w n a n a l o g is e x p e r i m e n t a l l y o b s e r v e d in a m m o n i a s p e c t r a [9]), and
also an a n h a r m o n i c level s p l i t t i n g r e l a t i v e to the p c o o r d i n a t e (in t h e case of t w o - d i m e n -
s i o n a l i s o t r o p i c h a r m o n i c p o t e n t i a l the levels w o u l d be (np + I) d e g e n e r a t e in p). F i n a l l y ,
for the p r o t o n in one d i m e n s i o n (D = i), the t u n n e l i n g s p l i t t i n g s of the f i r s t t h r e e l e v e l s
are 0.03, 6.17, and 2 2 6 . 2 3 cm -I, r e s p e c t i v e l y [7]; w h i l e in t h e t w o - d i m e n s i o n a l v e r s i o n (D =
2) t h e y i n c r e a s e to 0.14, 35.65, and 9 1 4 . 4 9 cm -I , r e s p e c t i v e l y . F o r t h e m u o n p+ a n d D = i,
the t u n n e l i n g s p l i t t i n g of the g r o u n d level is 4 0 5 . 7 8 c m -I [7], a n d for D = 2 , it d e c r e a s e s
to 130.67 cm -I W e thus see t h a t w h e n the s e c o n d d i m e n s i o n is i n t r o d u c e d , the m a g n i t u d e s
of the t u n n e l i n g s p l i t t i n g can b o t h i n c r e a s e as w e l l as d e c r e a s e . T h i s a g r e e s w i t h t h e cal-
c u l a t i o n s of the a m m o n i a i n v e r s i o n [I0].
B a s e d on the F E M a p p l i c a t i o n s c o n s i d e r e d above, w e t h i n k t h a t t h e m e t h o d c a n be r e c o m -
m e n d e d as an e f f i c i e n t a p p r o a c h to t h e o r e t i c a l s t u d i e s of q u a n t u m m e c h a n i c a l s y s t e m s w i t h
an a r b i t r a r y l o w - d i m e n s i o n a l H a m i l t o n i a n .
L I T E R A T U R E C I T E D
i. G. S t r a n g a n d J. Fix, A n A n a l y s i s of the F i n i t e E l e m e n t M e t h o d , P r e n t i c e - H a l l , E n g l e w o o d
C l i f f s (1973).
2. R. J a q u e t , Th. Chim. Acta. 71, No. 2, 4 2 5 - 4 4 8 (1987).
384
3. R. Jaquet, Chem. Phys., 118, No. i, 17-23 (1987).
4. D. J. Malik, J. E c c l e s , a n d D. S e c r e s t , J. Comp. Phys., 38, No. 2, 1 5 7 - 1 8 4 (1980).
5. A. V. T u r ' e v a n d N. I. Z h i r n o v , Opt. S p e k t r o s k . , 46, No. 4, 6 6 9 - 6 7 2 (1979).
6. J. B. Coon, N. W. N a u g l e , a n d R. D. M c K e n z i e , J. Mol. S p e c t r o s c . , 20, No. I, 1 0 7 - 1 2 9
(1966).
7. V. V. Gusev, S. G. P o t a p o v , a n d L. P. S u k h a n o v , M e t h o d i c a l A s p e c t s of S o l v i n g O n e -
D i m e n s i o n a l N u c l e a r S c h r o d i n g e r E q u a t i o n w i t h D o u b l e W e l l N u m e r i c a l P o t e n t i a l , P r e p r i n t
I A E - 4 7 6 0 / I , I. V. K u r c h a t o v I n s t i t u t e of A t o m i c Energy, M o s c o w (1989).
8. S. G. P o t a p o v , L. P. S u k h a n o v , a n d G. V. S h l y a p n i k o v , Phys. Lett. A, 137, No. 7 / 8 ,
4 1 7 - 4 1 9 (1989).
9. V. Spirko, J. Mol. S p e c t r o s c . , I01, No. i, 30-47 (1983).
10. A. I. B o l d y r e v , N o n - e m p i r i c a l M o d e l s of S t r u c t u r a l l y N o n - r i g i d M o l e c u l e s , A u t h o r ' s
A b s t r a c t , M a t h e m a t i c a l a n d P h y s i c a l S c i e n c e s D o c t o r ' s D i s s e r t a t i o n , C h e r n o g o l o v k a
(1986).
385