TY - JOUR
T1 - Elimination of translational and rotational motions in nuclear orbital plus molecular orbital theory
AU - Nakai, Hiromi
AU - Hoshino, Minoru
AU - Miyamoto, Kaito
AU - Hyodo, Shiaki
N1 - Funding Information:
Some of the calculations were performed at the Research Center for Computational Science (RCCS) of the Okazaki National Research Institutes. This study was partially supported by a Grant-in-Aid for Exploratory Research “KAKENHI 16655010” from the Japanese Ministry of Education, Culture, Sports, Science and Technology (MEXT), by a NAREGI Nano-Science Project of MEXT, and by the 21st-Century Center Of Excellence (21COE) “Practical Nano-Chemistry” from MEXT.
PY - 2005/4/22
Y1 - 2005/4/22
N2 - The nuclear orbital plus molecular orbital (NOMO) theory was developed in order to determine the nonadiabatic nuclear and electronic wave functions. This study presents a formulation to remove the contamination of rotational motion as well as translational motion in the NOMO theory. We have formulated the translation- and rotation-free (TRF)-NOMO theory by introducing the TRF Hamiltonian. The principal moment of inertia, which is the denominator in the rotational Hamiltonian, is expanded in a Taylor series. The zeroth-order of the Taylor expansion corresponds to a rigid-body rotator. The first-order terms contribute the coupling between the vibration and the rotation. Hartree-Fock equations have been derived in the framework of the TRF-NOMO theory. Numerical assessments, which were preformed for H2, D2, T2, μ2 (muon dimmer), and H2 O, confirmed the importance of the TRF treatment.
AB - The nuclear orbital plus molecular orbital (NOMO) theory was developed in order to determine the nonadiabatic nuclear and electronic wave functions. This study presents a formulation to remove the contamination of rotational motion as well as translational motion in the NOMO theory. We have formulated the translation- and rotation-free (TRF)-NOMO theory by introducing the TRF Hamiltonian. The principal moment of inertia, which is the denominator in the rotational Hamiltonian, is expanded in a Taylor series. The zeroth-order of the Taylor expansion corresponds to a rigid-body rotator. The first-order terms contribute the coupling between the vibration and the rotation. Hartree-Fock equations have been derived in the framework of the TRF-NOMO theory. Numerical assessments, which were preformed for H2, D2, T2, μ2 (muon dimmer), and H2 O, confirmed the importance of the TRF treatment.
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U2 - 10.1063/1.1871914
DO - 10.1063/1.1871914
M3 - Article
AN - SCOPUS:21244432372
SN - 0021-9606
VL - 122
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 16
M1 - 164101
ER -