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

VL - 122

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 16

M1 - 164101

ER -