Abstract
A recently developed partitioning of the vibrational-electronic Hamiltonian is coupled with analytical gradient techniques to calculate the energies of the first vibronic transitions for some simple molecular systems. The formulae for the first vibronic transition are presented. The corrections to harmonic frequencies due to electron correlation, anharmonicity and the non-adiabatic effects are derived using many-body perturbation theory (MBPT). For non-adiabatic effects, we present results for H2, HD and D2 and compare to reference values. About 70% of the non-adiabatic correction is recovered. Additional non-adiabatic corrections in H2O, NH3, and H2CO are reported for the first time. The comparison of the current method with that based upon gradient techniques is discussed.
This work has been supported by the U.S. ONR.
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© 1989 Springer-Verlag Berlin Heidelberg
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Hubac, I., Svrcek, M., Salter, E.A., Sosa, C., Bartlett, R.J. (1989). Partitioning of the Vibrational-Electronic Hamiltonian. Ab Initio Correlated Calculations of the First Vibronic Transitions for Some Simple Molecules. In: Kaldor, U. (eds) Many-Body Methods in Quantum Chemistry. Lecture Notes in Chemistry, vol 52. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-93424-7_5
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DOI: https://doi.org/10.1007/978-3-642-93424-7_5
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