We have extended the multicomponent molecular orbital (MC̱MO) method to the full-configuration interaction (full-CI) fully variational molecular orbital method by elimination of translational and rotational motion components from total Hamiltonian. In the MC̱MO scheme, the quantum effects of protons and deuterons as well as electrons can be directly taken into account. All variational parameters in the full-CI scheme, i.e., exponents and centers (α and R) in the Gaussian-type function (GTF) basis set as well as the CI coefficients, are simultaneously optimized by using their analytical gradients. The total energy of the H2 molecule calculated using the electronic [6s3p2d1f] and nuclear [1s1p1d1f] GTFs is 1.161726hartree, which can be compared to the energy of 1.164025hartree reported using a 512 term-explicitly correlated GTF calculation. Although the d- and f-type nuclear GTFs contribute to the improvement of energy convergence, the convergence of electron-nucleus correlation energy is slower than that of electron-electron one. The nuclear wave functions are delocalized due to the electron-nucleus correlation effect compared to the result of Hartree–Fock level of MC̱MO method. In addition, the average internuclear distances of all diatomic molecules are within 0.001Å of the previously reported experimental results. The dipole moment of the HD molecule estimated by our method is 8.4×104D, which is in excellent agreement with the experimental result of (810)×104D.

1.
Atom Tunneling Phenomena in Physics, Chemistry, and Biology
, edited by
T.
Miyazaki
(
Springer-Verlag
,
Berlin
,
2003
).
2.
N. D.
Sokolov
,
M. V.
Vener
, and
V. A.
Savel’ev
,
J. Mol. Struct.
222
,
365
(
1990
).
3.
Reaction Rate of Isotopic Molecules
, edited by
L.
Melander
and
W. H.
Saunders
(
Wiley
,
New York
,
1980
).
4.
A. R.
Ubbelohde
and
K. J.
Gallagher
,
Acta. Cryst.
8
,
71
(
1995
).
5.
N.
Dalal
,
A.
Klymachyov
, and
A.
Bussmann-Holder
,
Phys. Rev. Lett.
81
,
5924
(
1998
).
6.
M.
Tachikawa
,
Chem. Phys. Lett.
360
,
495
(
2002
).
7.
M.
Tachikawa
,
K.
Mori
,
K.
Suzuki
, and
K.
Iguchi
,
Int. J. Quantum Chem.
70
,
491
(
1998
).
8.
M.
Tachikawa
,
K.
Mori
,
H.
Nakai
, and
K.
Iguchi
,
Chem. Phys. Lett.
290
,
437
(
1998
).
9.
H.
Nakai
and
K.
Sodeyama
,
J. Chem. Phys.
118
,
1119
(
2003
).
10.
H.
Nakai
,
K.
Sodeyama
, and
M.
Hoshino
,
Chem. Phys. Lett.
345
,
118
(
2001
).
11.
Y.
Shigeta
,
H.
Nagao
,
K.
Nishikawa
, and
K.
Yamaguchi
,
J. Chem. Phys.
111
,
6171
(
1999
).
12.
Y.
Shigeta
,
Y.
Ozaki
,
K.
Kodama
,
H.
Nagao
,
H.
Kawade
, and
K.
Nishikawa
,
Int. J. Quantum Chem.
69
,
629
(
1998
).
13.
Y.
Shigeta
,
H.
Takahashi
,
S.
Yamanaka
,
M.
Mitani
,
H.
Nagao
, and
K.
Yamaguchi
,
Int. J. Quantum Chem.
70
,
659
(
1998
).
14.
S. P.
Webb
,
T.
Iordanov
, and
S.
Hammes-Schiffer
,
J. Chem. Phys.
117
,
4106
(
2002
).
15.
T.
Iordanov
and
S.
Hammes-Schiffer
,
J. Chem. Phys.
118
,
9489
(
2003
).
16.
E.
Deumens
,
A.
Diz
,
H.
Taylor
, and
Y.
Öhrn
,
J. Chem. Phys.
96
,
6820
(
1992
).
17.
A. D.
Bochevarov
,
E. F.
Valeev
, and
C. D.
SheRrill
,
Mol. Phys.
102
,
111
(
2004
).
18.
T.
Udagawa
,
T.
Ishimoto
,
H.
Tokiwa
,
M.
Tachikawa
, and
U.
Nagashima
,
Chem. Phys. Lett.
389
,
236
(
2004
).
19.
T.
Udagawa
,
T.
Ishimoto
,
H.
Tokiwa
,
M.
Tachikawa
, and
U.
Nagashima
,
J. Phys. Chem. A
110
,
7279
(
2006
).
20.
T.
Ishimoto
,
M.
Tachikawa
,
M.
Yamauchi
,
H.
Kitagawa
,
H.
Tokiwa
, and
U.
Nagashima
,
Chem. Phys. Lett.
372
,
503
(
2003
).
21.
T.
Ishimoto
,
M.
Tachikawa
,
M.
Yamauchi
,
H.
Kitagawa
,
H.
Tokiwa
, and
U.
Nagashima
,
J. Phys. Soc. Jpn.
73
,
1775
(
2004
).
22.
T.
Ishimoto
,
M.
Tachikawa
,
H.
Tokiwa
, and
U.
Nagashima
,
J. Phys. Soc. Jpn.
74
,
3112
(
2005
).
23.
T.
Ishimoto
,
M.
Tachikawa
,
H.
Tokiwa
, and
U.
Nagashima
,
Chem. Phys.
314
,
231
(
2005
).
24.
Y.
Itou
,
S.
Mori
,
T.
Udagawa
,
M.
Tachikawa
,
T.
Ishimoto
, and
U.
Nagashima
,
J. Phys. Chem. A
111
,
261
(
2007
).
25.
T.
Ishimoto
,
M.
Tachikawa
, and
U.
Nagashima
,
J. Chem. Phys.
124
,
014112
(
2006
).
26.
D. B.
Kinghorm
and
L.
Adamowicz
,
J. Chem. Phys.
113
,
4203
(
2000
).
27.
S.
Bubin
and
L.
Adamowicz
,
J. Chem. Phys.
118
,
3079
(
2003
).
28.
M.
Cafiero
,
S.
Bubin
, and
L.
Adamowicz
,
Phys. Chem. Chem. Phys.
5
,
1491
(
2003
).
29.
S.
Bubin
and
L.
Adamowicz
,
J. Chem. Phys.
121
,
6249
(
2004
).
30.
M.
Cafiero
and
L.
Adamowicz
,
J. Chem. Phys.
122
,
184305
(
2005
).
31.
B. T.
Sutcliffe
,
J. Mol. Struct.: THEOCHEM
341
,
217
(
1995
).
32.
H.
Nakai
,
Int. J. Quantum Chem.
86
,
511
(
2002
).
33.
H.
Nakai
,
M.
Hoshino
,
K.
Miyamoto
, and
S.
Hyodo
,
J. Chem. Phys.
122
,
164101
(
2005
).
34.
K.
Miyamoto
,
M.
Hoshino
, and
H.
Nakai
,
J. Chem. Theory Comput.
2
,
1544
(
2006
).
35.
M.
Hoshino
and
H.
Nakai
,
J. Chem. Phys.
124
,
194110
(
2006
).
36.
M.
Tachikawa
,
K.
Taneda
, and
K.
Mori
,
Int. J. Quantum Chem.
75
,
497
(
1999
).
37.
T.
Ishimoto
,
M.
Tachikawa
, and
U.
Nagashima
,
Int. J. Quantum Chem.
108
,
472
(
2008
).
38.
M.
Tachikawa
and
Y.
Osamura
,
J. Chem. Phys.
113
,
4942
(
2000
).
39.
L.
Wolniewicz
and
K.
Dressler
,
J. Chem. Phys.
88
,
3861
(
1988
).
40.
W.
Kolos
,
K.
Szalewicz
, and
H.
Monkhorst
,
J. Chem. Phys.
84
,
3278
(
1986
).
41.
T.
Ishimoto
,
M.
Tachikawa
, and
U.
Nagashima
,
J. Chem. Phys.
125
,
144103
(
2006
).
42.
The Unitary Group for the Evaluation of Electronic Energy Matrix Elements
, edited by
I.
Shavitt
(
Springer
,
Berlin
,
1981
).
43.
T.
Ishimoto
,
M.
Tachikawa
, and
U.
Nagashima
,
Int. J. Quantum Chem.
106
,
1465
(
2006
).
44.
J. S.
Binkley
,
J. A.
Pople
, and
W. J.
Hehre
,
J. Am. Chem. Soc.
102
,
939
(
1980
).
45.
W. J.
Hehre
,
R.
Ditchfield
, and
J. A.
Pople
,
J. Chem. Phys.
56
,
2257
(
1972
).
46.
P. C.
Hariharan
and
J. A.
Pople
,
Theor. Chim. Acta
28
,
213
(
1973
).
47.
R.
Krishnan
,
J. S.
Binkley
,
R.
Seeger
, and
J. A.
Pople
,
J. Chem. Phys.
72
,
650
(
1980
).
48.
T. H.
Dunning
, Jr.
,
J. Chem. Phys.
90
,
1007
(
1989
).
49.
Molecular Spectra Molecular Structure, Constants of Diatomic Molecules
, edited by
K. P.
Huber
and
G.
Herzberg
(
Van Nostrand Reinhold
,
New York
,
1979
).
50.
J. B.
Nelson
and
G. C.
Tabisz
,
Phys. Rev. A
28
,
2157
(
1985
).
51.
M.
Tachikawa
and
Y.
Osamura
,
Theor. Chem. Acc.
104
,
29
(
2000
).
You do not currently have access to this content.