Vibrationally averaged dipole moments of methane and benzene isotopologues
- Laboratório de Átomos e Moléculas Especiais, Departamento de Física, ICEx, Universidade Federal de Minas Gerais, P. O. Box 702, 30123-970 Belo Horizonte, MG (Brazil)
DFT-B3LYP post-Born-Oppenheimer (finite-nuclear-mass-correction (FNMC)) calculations of vibrationally averaged isotopic dipole moments of methane and benzene, which compare well with experimental values, are reported. For methane, in addition to the principal vibrational contribution to the molecular asymmetry, FNMC accounts for the surprisingly large Born-Oppenheimer error of about 34% to the dipole moments. This unexpected result is explained in terms of concurrent electronic and vibrational contributions. The calculated dipole moment of C{sub 6}H{sub 3}D{sub 3} is about twice as large as the measured dipole moment of C{sub 6}H{sub 5}D. Computational progress is advanced concerning applications to larger systems and the choice of appropriate basis sets. The simpler procedure of performing vibrational averaging on the Born-Oppenheimer level and then adding the FNMC contribution evaluated at the equilibrium distance is shown to be appropriate. Also, the basis set choice is made by heuristic analysis of the physical behavior of the systems, instead of by comparison with experiments.
- OSTI ID:
- 22657905
- Journal Information:
- Journal of Chemical Physics, Vol. 144, Issue 14; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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