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Extensive theoretical study on the low‐lying electronic states of silicon monofluoride cation including spin‐orbit coupling
Author(s) -
Liu Kun,
Bian Wensheng
Publication year - 2007
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20785
Subject(s) - atomic physics , chemistry , multireference configuration interaction , configuration interaction , spin–orbit interaction , ab initio , dipole , hamiltonian (control theory) , avoided crossing , basis set , ionization energy , potential energy , radiative transfer , ground state , coupled cluster , ionization , ion , physics , computational chemistry , excited state , molecule , quantum mechanics , density functional theory , mathematical optimization , mathematics , organic chemistry
Ab initio calculations on the low‐lying electronic states of SiF + are performed using the internally contracted multireference configuration interaction method with the Davidson correction and entirely uncontracted aug‐cc‐pV5Z basis set. The effects of spin‐orbit coupling are accounted for by the state interaction approach with the full Breit–Pauli Hamiltonian. The entire 23 Ω states generated from the 12 valence Λ–S states, which correlate with the first dissociation channel are studied for the first time. Good agreement is found between the calculated results and the available experimental data. The spin‐orbit coupling effects on the potential energy curves and spectroscopic properties are studied. Various curve crossings are revealed, which could lead to the predissociation of the a 3 Π, A 1 Π, and (2) 3 Σ + states and the predissociation pathways are analyzed based upon the calculated spin‐orbit matrix elements. The calculated ionization potentials of the ground‐state SiF to a few states of SiF + are in good agreement with the available experimental measurements. Moreover, the transition dipole moments of the dipole‐allowed transitions and the transition properties for the A 3 Π 0+ –X 1 Σ + 0+and B 3 Π 1 –X 1 Σ + 0+transitions are predicted, including the Franck–Condon factors and the radiative lifetimes. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2008