A combined ab initio and Franck‐Condon factor simulation study on the photodetachment spectrum of ScO2−

Abstract

AbstractRestricted‐spin coupled‐cluster single‐double plus perturbative triple excitation {RCCSD(T)} potential energy functions (PEFs) of the $ \tilde X $2B2 state of ScO2 and the $ \tilde X $1A1 state of ScO2− were computed, employing the augmented correlation‐consistent polarized‐weighted core‐valence quadruple‐zeta (aug‐cc‐pwCVQZ) basis set for Sc and augmented correlation‐consistent polarized valence quadruple‐zeta (aug‐cc‐pVQZ) basis set for O, and with the outer core Sc 3s23p6 electrons being explicitly correlated. Franck‐Condon factors, which include allowance for Duschinsky rotation and anharmonicity, were calculated using the computed RCCSD(T) PEFs, and were used to simulate the first photodetachment band of ScO2−. The simulated spectrum matches well with the corresponding experimental 355 nm photodetachment spectrum of Wu and Wang, J Phys Chem A 1998, 102, 9129, confirming the assignment of the photodetachment spectrum and the reliability of the RCCSD(T) PEFs used. Further calculations on low‐lying electronic states of ScO2 gave adiabatic relative electronic energies (Te's) of, and vertical excitation energies (Tv's) to, the $ \tilde A $2A1, $ \tilde B $2B1, and $ \tilde C $2A2 states of ScO2 (from the $ \tilde X $2B2 state of ScO2), as well as electron affinities (EAs) and vertical detachment energies (VDEs) to these neutral states from the $ \tilde X $1A1 state of ScO2−. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2009