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PHYSICAL REVIEW A, VOLUME 61, 042705

Calculation of properties of two-center systems


M. J. Jamieson* and A. Dalgarno
Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, Massachusetts 02138

L. Wolniewicz
Institute of Physics, Nicholas Copernicus University, 87-100 Torun, Poland
Received 5 August 1999; published 6 March 2000
A procedure is described by which the response of a two-center system to a perturbation can be expressed
in terms of single-center wave functions. We use the formulation to evaluate the asymptotic long-range part of
the Pauli-Dirac relativistic interaction between two ground-state hydrogen atoms and compare with the results
of ab initio calculations.
PACS numbers: 34.20.Cf

I. INTRODUCTION H 0 E 0 0 ra1 ,rb2 0 1

The study of atomic collisions in ultracold regimes has where H 0 and E 0 are the unperturbed Hamiltonian and en-
become important in interpreting observations made possible ergy, respectively, given by the sum of the separate Hamil-
by the current experimental techniques for cooling and trap- tonians or energies for the centers A and B. The Hamiltonian
ping gaseous atomic samples; topics attracting interest in- for center A is
clude the construction of gaseous Bose-Einstein condensates,
accurate measurement of time, and the production of mol- 2 2
H a0 V a r a1 2
ecules in specified vibrational states by cold atom photoas- 2m 1 1a
sociation. Reviews of ultracold atomic physics are given in
1. where m 1 is the mass of particle 1, and the Hamiltonian H b0
This current interest in cold atomic collisions brings a for center B is defined similarly. We may write the wave
need for precise interaction potentials because the effects on function as the product
scattering induced by small corrections to the potentials are
enhanced at the very low energies of the ultracold ensembles. 0 ra1 ,rb2 u ara1 u b ra2 3
Relativistic corrections influence the scattering at ultralow
where u a(ra1 ), assumed to be normalized, satisfies the equa-
temperatures. They have been calculated for the X 1 g state
tion
of H2 by ab initio variational methods for internuclear dis-
tances R between 0 bohr and 12 bohr 2 but their asymptotic H a0 E a0 u a ra1 0 4
form has not been determined. We introduce here a proce-
dure with which a precise determination can be achieved. We and u b(rb2 ) satisfies a similar equation. We introduce the two-
extend the calculations of Wolniewicz 2 to larger values of center perturbation
R for both the X 1 3
g and b u states and compare the
N
results with the calculated long-range form.
The procedure, in which the effects of certain two-center V ra1 ,rb2
i1
f (i) a (i) b
a r1 f b r2 . 5
interactions are factored into products of one-center func-
tions, is general and we describe it in Secs. II and III. We Let
apply it to the relativistic interaction calculation in Sec. IV
and present the ab initio calculations in Sec. V. PI 0 0 6

II. TWO-CENTER PERTURBATION be the operator that projects off the unperturbed state 0 ,
assumed normalized, where I denotes the identity operator.
We consider an unperturbed two-center dynamical system The first-order wave function 1 (ra1 ,rb2 ), chosen to be or-
consisting of a particle labeled 1 centered on point A and thogonal to the unperturbed wave function, satisfies the
moving in the potential V a(ra1 )V a(r a1 ) where ra1 is its dis- equation
placement from A and a particle labeled 2 centered on point
B and moving in the potential V b(rb2 )V b(r b2 ) where rb2 is 1 P H 0 E 0 1 PV 0 H 0 E 0 1 PV 0 .
its displacement from B. The wave function 0 (ra1 ,rb2 ) of the 7
system satisfies the equation
The second-order wave function satisfies the equation

2 P H 0 E 0 1 P V 0 V 0
*Permanent address: Department of Computing Science, Univer-
sity of Glasgow, Glasgow G12 8QQ, UK. P H 0 E 0 1 PV 0 8

1050-2947/2000/614/0427056/$15.00 61 042705-1 2000 The American Physical Society


M. J. JAMIESON, A. DALGARNO, AND L. WOLNIEWICZ PHYSICAL REVIEW A 61 042705

which, if 0 V 0 vanishes through, for example, symme- H a0 E a0 2 2 (i)


a ;r1 H 0 E 0 Pa f a r1 u a r1
a a a (i) a a
try considerations, may be written
2 u a (i)
a u a r1
a
16
1 1
2 H 0 E 0 PV H 0 E 0 PV 0 . 9
and (i)
b ( ;r2 ) satisfies a similar equation. Equation 16
b

Let Pa and Pb project out the ground states, assumed nor- may be solved by direct numerical methods 3 or by varia-
malized, of the single-center Hamiltonians H a0 and H b0 , re- tional methods such as that used by Chan and Dalgarno 4,
spectively. Then who calculated the dynamical polarizability of atomic hydro-
gen by finding the stationary values of the functional

PPa u b u b Pb u a u a PaPb . 10
a a H 0 E 0 a
J (i) (i) a a 2 2 (i)

We need 2 (i)
a H 0 E 0 u a a u a
a a 2 (i) 2
17

a ( ;r1 ). We adopt their


with respect to a trial function (i) a
H 0 E 0 1 H a0 E a0 H b0 E b0 1 11
method.
which we may rewrite using the integral, for a and b posi-
tive, III. PERTURBED EXPECTATION VALUE

Suppose we wish to determine the expectation value of

ab 1
2

0
d
ab
a b 2 2
2 2
. 12
the operator LL aL b , effective on each center separately,
in the presence of the two-center perturbation 5. The
zeroth-order contribution is straightforward to evaluate.
The first-order contribution is with 0 1 vanishing
Equation 12 enables us to obtain a product form for the
first-order wave function, albeit with the need to evaluate an
integral. We use Eqs. 3, 5, 7, 10, 11, and 12 to L 1 0 L 1 1 L 0 18
express the first-order wave function as the following sum of
single-center products:
which may be expressed with the aid of Eqs. 13 and 15 as

0 d u a L a (i)a u b (i)b
N N
2
1
1 ra1 ,rb2 P f (i) ra1 u a ra1 u b f (i)
a a a
i1 H 0 E 0
a b u b u b r2
b L 1
i1

N
1 u b L b (i)
b u a a a L a u a b u b
(i) (i) (i)

H b E b Pb f (i)b rb2 u b rb2 u a f (i)a u a u a ra1


i1 (i)
b L b u b a u a .
(i)
19
0 0


2
N
H a0 E a0 The second-order contribution is with 0 2 vanish-


i1 0
d
H a0 E a0 2
P f (i) ra1
2 a a
ing

L 2 1 L 1 0 L 2 2 L 0
H b0 E b0
u a ra1 Pb f (i) b b
b r2 u b r2 . 13 0 L 0 1 1 . 20
H b0 E b0 2 2
It is not necessary to find the second-order wave function to
The first term in Eq. 13 may be obtained from the solution evaluate L 2 ; we can use the first-order wave function and
(i) a another first-order wave function corresponding to the per-
a (r1 ) of the equation
turbation L to evaluate the matrix elements 0 L 2 and
2 L 0 5. From Eqs. 7 and 9 we may write with
H a0 E a0 (i)
a r1 Pa f a r1 u a r1
a (i) a a
14 0 V 0 vanishing
and the second term may be found similarly. In studies of 0 L 2 0 L H 0 E 0 1 PV 1 1 V 1
interacting atoms that have no permanent dipole or higher 21
moments these induction terms vanish identically. The last
term in Eq. 13 is where 1 is the first-order wave function induced by the
perturbation L alone, chosen orthogonal to 0 , that satis-

0 d (i)a ;ra1 (i)b ;rb2


N fies the equation
2
1 ra1 ,rb2 15
i1 H 0 E 0 1 L 0 L 0 0 0. 22

where (i)
a ( ;r1 ) satisfies the equation
a
Similarly we find

042705-2
CALCULATION OF PROPERTIES OF TWO-CENTER SYSTEMS PHYSICAL REVIEW A 61 042705

2 L 0 1 V 1 . 23 H a0 E a0 g a ra1 u a ra1 L a u a L a u a u a ra1 0


25
We may express 1 as

1 ra1 ,rb2 g a ra1 g b rb2 0 ra1 ,rb2 24


6 and g b(rb2 ) satisfies a similar equation. From Eqs. 15,
where g a(ra1 ) satisfies the equation 20, 21, 23, and 24 we obtain

d d (i)a L a (aj) (i)b (bj) (i)b L b (bj) (i)a (aj)


N N
4
L 2
2 i1 j1 0

0 d g au a f (aj) (i)a u b (i)b g bu b f (bj) (i)b u a (i)a (i)a f (aj) g au a


N N
2

i1 j1

0 d (i)a (i)a
N
4
(i)
b u b b f b g bu b a u a
(i) ( j) (i)
u a L a u a u b L b u b
2 i1

0 d (i)b (i)b .
N

26
i1

IV. APPLICATION TO LONG-RANGE PROPERTIES where C m n


denotes the binomial coefficient and Y1, (r)
The method described in Secs. II and III is generally ap- rY 1, (r).
plicable to two-center problems. We need to be able to solve The Hamiltonians H a0 and H b0 , the perturbations f a and
equations of the form 25; the method is much more conve- f b , and the operators L a and L b do not depend essentially on
nient when this equation has an analytic solution. The Dirac the centers; henceforth where possible we dispense with no-
contribution is an important part of the relativistic energy of tation that distinguishes the centers.
two interacting ground-state hydrogen atoms and influences The normalized ground-state orbital is
cold collisions and it happens that its calculation provides an
example where Eq. 25 can be solved analytically, as we u r u 1s r Y 0,0 r 2 exp r Y 0,0 r . 29
demonstrate below.
In the Pauli approximation the Dirac energy of the hydro- The expectation value of the function summed over both
gen molecule is 2,7 centers to zeroth order is 2a 30
1
, or 2 1 in atomic
units.
From 2 r 1 4 (3) (r) Dalgarno and Stewart 9
4 2 e 2 a 20 (3) ra1 (3) rb2 (3) ra1 rb2 R
found a closed form expression for g(r); with our require-
27
ment that (r) and u(r) are orthogonal it is in atomic units
where is the fine structure constant, e is the electronic 1
charge, a 0 denotes one bohr, and (3) is the three- g r g r r 1 2 ln r2r 12 2 3 2 ln 2
2
dimensional delta function. The function has dimension 30
L 3 . The third term vanishes for the triplet state and de-
creases exponentially for the singlet state. The leading two where (k) is the digamma function see the Appendix.
terms decrease as inverse powers of R. To evaluate the long- We note that (3)0.922 784 335 1 and ln 2
range perturbation of the expectation value of the function 0.693 147 180 6. The overlined terms ensure orthogonality.
we identify the operator L with (3) (ra1 ) (3) (rb2 ) and the The dimensions of g(r) are E 1 L 1 .
perturbation V(ra1 ,rb2 ) with the long-range electrostatic inter- For any given value of Eq. 16 can be solved varia-
action between the atoms. The dipole-dipole component of tionally by adopting the trial function
this interaction can be expressed as a sum of one-center n
products such as Eq. 5 by 8
()
;r F ;r Y 1, r u r
p1
a p r p Y 1, r u r

4e2
1 31
V ra1 ,rb2
3R 3

1
2
C 1 Y1, r1 Y1, r2
a b
and finding the stationary values of the functional 17 with
28 respect to variations in the coefficients a p ( ). The dimen-

042705-3
M. J. JAMIESON, A. DALGARNO, AND L. WOLNIEWICZ PHYSICAL REVIEW A 61 042705

sions of F( ;r) are E 1/2 L 3/2 . The coefficients satisfy TABLE I. Born-Oppenheimer potentials hartree.
a matrix equation whose elements, being combinations of
expectation values of powers of r for the ground-state hydro- R bohr X 1
g b 3
u
gen wave function, can be found following considerable 1.0 1.124539713 0.622264306
algebraic manipulation; Chan 10 has presented the matrix
1.5 1.172855073 0.809666437
equations. The first-order contribution to the expectation
2.0 1.138132950 0.897076283
value of the function vanishes on account of angular sym-
2.5 1.093938123 0.945453719
metry. The trial function determined as described above can
3.0 1.057326262 0.972015035
be substituted into Eq. 26 and the necessary quadratures
over performed to yield the second-order contribution, 3.5 1.031858079 0.986130885
whose R dependence is R 6 . The perturbed wave functions 4.0 1.016390249 0.993380059
are each linear in r near each center and hence the func- 4.5 1.007993726 0.996972880
tions in the first term of L 2 in Eq. 26 cause that term to 5.0 1.003785656 0.998687253
vanish. 5.5 1.001774578 0.999471748
The second and third parts of L 2 involve the sum of inte- 6.0 1.000835707 0.999813447
grals 6.5 1.000400548 0.999952833
7.0 1.000197914 1.000003987
1.000102106 1.000018912

1 1 7.5
I
1 1
2
C 1 2
C 1 * r1 Y 0,0
dr1 dr2 Y 1, * r1 8.0
8.5
1.000055605
1.000032172
1.000020214
1.000017232
9.0 1.000019782 1.000013517
Y 1, r1 Y 0,0 r1 Y 1,
* r2 Y 0,0
* r2 Y 1, r2 Y 0,0 r2 . 9.5 1.000012856 1.000010246
32 10.0 1.000008755 1.000007674
10.5 1.000006190 1.000005744
The integration over r1 yields a factor 11.0 1.000004506 1.000004323


11.5 1.000003356 1.000003281
3 1 1 0 1 1 0 1 12.0 1.000002546 1.000002515
I 1
4 0 0 0 0 4 , 12.5 1.000001961 1.000001948
33 13.0 1.000001529 1.000001524
13.5 1.000001206 1.000001204
and hence 14.0 1.000000961 1.000000960
1 14.5 1.000000772 1.000000772
1 1 3
I
16

2 1
2
C 1 C 1
2
16
C 4 2 .
2 2
8
34 15.0
15.5
1.000000625
1.000000510
1.000000625
1.000000510
16.0 1.000000420 1.000000420
The second part of L 2 in Eq. 26 becomes 16.5 1.000000347 1.000000347
17.0 1.000000289 1.000000289

3R
16a 30
6 0

d

0
r 2 drF ;r g r ru 1s r
17.5
18.0
1.000000242
1.000000203
1.000000242
1.000000203
18.5 1.000000172 1.000000172
0

r 2 drF ;r ru 1s r . 35
19.0
19.5
1.000000146
1.000000125
1.000000146
1.000000125
20.0 1.000000107 1.000000107
The third part of L 2 in Eq. 26 is 1.000000000 1.000000000


16a 30
3 R 3 6
0

0
d d r 2 drF ;r F ;r u 1s r .
proved sufficient in the trial function to achieve convergence.
36 The intermediate numerical data that Chan and Dalgarno in-
cluded because of their possible future utility were used in a
The total second-order contribution is obtained by adding check of our presently adopted numerical procedures.
the expressions 35 and 36. Once the coefficients a p ( ) We found that the expectation value of the function is
are known for a value of the quadratures over r in expres- perturbed, to O(R 6 ), by 28.29a 30 R 6 . Thus asymptoti-
sions 35 and 36 can be done analytically. We performed cally, in atomic units,
the quadratures over over the range 0,100 by Simpsons
rule and added the contributions from the range 100,
which was evaluated analytically using the asymptotic form
for the perturbed wave functions; Eq. 16 shows that the
dependence is as 2 for large values of . Six terms
(3) r1 (3) r2
2
28.29

1 6 .
R
37

042705-4
CALCULATION OF PROPERTIES OF TWO-CENTER SYSTEMS PHYSICAL REVIEW A 61 042705

TABLE II. function expectation values (bohr3 ). TABLE III. R 6 L 2 (bohr3 ).

R bohr X 1
g b 3
u R bohr X 1
g b 3
u Average

1.0 2.023490 1.386921 8.5 52 17 34


1.5 1.353334 1.098815 9.0 43 20 31
2.0 1.069361 1.073996 9.5 42 24 33
2.5 0.948122 1.067863 10.0 33 25 29
3.0 0.911053 1.052201 10.5 30 26 28
3.5 0.918475 1.035008 11.0 28 28 28
4.0 0.942387 1.021268 11.5 29 29 29
4.5 0.965166 1.011918 12.0 30 27 29
5.0 0.980793 1.006203 12.5 29 24 27
5.5 0.989925 1.002990 13.0 28 25 26
6.0 0.994839 1.001321 13.5 27 27 27
6.5 0.997371 1.000502 14.0 29 24 26
7.0 0.998649 1.000101 14.5 24 18 21
7.5 0.999293 0.999969 15.0 29 22 25
8.0 0.999617 0.999925 15.5 26 26 26
8.5 0.999784 0.999930 16.0 22 22 22
9.0 0.999871 0.999940 16.5 13 26 20
9.5 0.999910 0.999948 17.0 16 31 23
10.0 0.999948 0.999960 17.5 37 19 28
10.5 0.999965 0.999969 18.0 44 22 33
11.0 0.999975 0.999975 18.5 76 26 51
11.5 0.999980 0.999980 19.0 89 30 60
12.0 0.999984 0.999986 19.5 104 35 70
12.5 0.999988 0.999990 20.0 83 41 62
13.0 0.999991 0.999992
13.5 0.999993 0.999993
14.0 0.999994 0.999995 and the expectation values of (3) (r1 ) (3) (r2 ) in Table II.
14.5 0.999996 0.999997 Asymptotically the expectation values of an operator L for
15.0 0.999996 0.999997 the X 1 3
g and b u states vary as the sum and difference
15.5 0.999997 0.999997 of a direct term L dir that decreases as a series in inverse
16.0 0.999998 0.999998 powers of R and an exchange term L exc which decreases
16.5 0.999999 0.999998 exponentially; at large R
17.0 0.999999 0.999998
17.5 0.999998 0.999999
18.0 0.999998 0.999999
LL dirL exc . 38
18.5 0.999997 0.999999
19.0 0.999997 0.999999 We have calculated the leading term of L dir for the func-
19.5 0.999997 0.999999 tion.
20.0 0.999998 0.999999 In Table III we show the results of adding the expectation
1.000000 1.000000 values of the function of the X 1 3
g and b u states for
R8.5 bohr. The procedure eliminates asymptotically the
V. AB INITIO CALCULATIONS exchange contribution. Dividing by two and subtracting the
zero-order contribution 2/ yields estimates of the direct
High precision variational methods to calculate Born- term, which tends to 28.29R 6 for large R. The values
Oppenheimer potential energies and eigenfunctions for mo- obtained after multiplying by R 6 are given in Table III. The
lecular hydrogen using carefully chosen basis sets have been ab initio results are less reliable for large R where the chosen
developed by Kolos and Wolniewicz 11. Wolniewicz 2 basis functions are less appropriate. This is in contrast to the
calculated the potential energies of the X 1
g state over the calculated asymptotic results of Sec. IV where the depen-
range 0,12 bohr and used the electronic eigenfunctions to dence on R is included explicitly. Also the variational calcu-
calculate the adiabatic and relativistic corrections to the po- lations are dominated by the zero-order contribution. After it
tential energies. We have extended further the calculations of is subtracted we are left with few significant figures. The
the potential energies and the expectation values of the resulting cancellation error is occasionally large by chance
function to a larger range of R and to the b 3 u state. The as, for example, at nuclear separations 9.5 bohr, 16.5 bohr,
resulting Born-Oppenheimer energies are given in Table I and 1820 bohr. However, the remaining figures in Table III

042705-5
M. J. JAMIESON, A. DALGARNO, AND L. WOLNIEWICZ PHYSICAL REVIEW A 61 042705

do serve to show that our evaluation of the asymptotic form, tion to the Smithsonian Institution and Harvard University.
which is numerically exact, is consistent with the ab initio M.J.J. acknowledges support in part for this research from
results. the Engineering and Physical Sciences Research Council.
The research of A.D. is supported by the U.S. Department of
VI. CONCLUSION Energy, Division of Chemical Sciences, Office of Basic En-
ergy Sciences, Office of Energy Research.
We have demonstrated how the first-order wave function
of a two-center system can be expressed by an integral for- APPENDIX
mula and how it can be used in evaluating the second-order
contribution to the expectation values of other operators. We To derive the term in Eq. 30 that ensures orthogonality
showed that the leading term in the expectation value of the and in performing the quadratures in Eq. 35 we need
function, part of the relativistic interaction between atoms, to evaluate definite integrals of the form
is proportional to R 6 where R is the nuclear separation, and 0 dt exp(st)tk1 ln t. We use the equation
found the calculated coefficient to be consistent with ab ini-
tio variational calculations for hydrogen atoms at large dis-
tances. 0

dt exp st
t k1
k
k ln t s k ln s, A1

ACKNOWLEDGMENTS from the theory of Laplace transforms 12, where (k) is


the digamma function, which can be calculated from
This work was done while M.J.J. was visiting the Institute
for Theoretical Atomic and Molecular Physics at the 1 1 1
Harvard-Smithsonian Center for Astrophysics; he is very k 1 A2
2 3 k1
pleased to thank the Institute for its hospitality. The Institute
is supported by a grant from the National Science Founda- where 0.577 215 664 9 is Eulers constant.

1 P. S. Julienne, A. M. Smith, and K. Burnett, Adv. At., Mol., 7 H. A. Bethe and E. E. Salpeter, Quantum Mechanics of One-
Opt. Phys. 30, 141 1993; T. Walker and P. Feng, ibid. 34, and Two-electron Atoms Springer-Verlag, Berlin, 1957.
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A 49, 982 1994. 1965 unpublished.
4 Y. M. Chan and A. Dalgarno, Mol. Phys. 9, 349 1965. 11 W. Kolos and L. Wolniewicz, J. Chem. Phys. 41, 3663 1964.
5 A. Dalgarno, in Quantum Theory, edited by D. R. Bates Aca- 12 Handbook of Mathematical Functions, Natl. Bur. Stand. Appl.
demic Press, New York, 1961, Vol. 1.
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