Dissociation Potential Curves of Low-Lying States in Transition Metal Hydrides. 3. Hydrides of Groups 6 and 7

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Koseki, Shiro
Matsushita, Takeshi
Gordon, Mark
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The dissociation curves of low-lying spin-mixed states in monohydrides of groups 6 and 7 were calculated by using an effective core potential (ECP) approach. This approach is based on the multiconfiguration self-consistent field (MCSCF) method, followed by first-order configuration interaction (FOCI) calculations, in which the method employs an ECP basis set proposed by Stevens and co-workers (SBKJC) augmented by a set of polarization functions. Spin−orbit coupling (SOC) effects are estimated within the one-electron approximation by using effective nuclear charges, since SOC splittings obtained with the full Breit−Pauli Hamitonian are underestimated when ECP basis sets are used. The ground states of group 6 hydrides have Ω = 1/2(X6 ), where Ω is the z component of the total angular momentum quantum number. Although the ground states of group 7 hydrides have Ω = 0+, their main adiabatic components are different; the ground state in MnH originates from the lowest 7Σ+, while in TcH and ReH the main component of the ground state is the lowest 5Σ+. The present paper reports a comprehensive set of theoretical results including the dissociation energies, equilibrium distances, electronic transition energies, harmonic frequencies, anharmonicities, and rotational constants for several low-lying spin-mixed states in these hydrides. Transition dipole moments were also computed among the spin-mixed states and large peak positions of electronic transitions are suggested theoretically for these hydrides. The periodic trends of physical properties of metal hydrides are discussed, based on the results reported in this and other recent studies.


Reprinted (adapted) with permission from Journal of Physical Chemistry A 110 (2006): 2560, doi:10.1021/jp056258z. Copyright 2006 American Chemical Society.