Franck-Condon simulation of the photoelectron spectrum of AsF2 and the photodetachment spectrum of the AsF2 anion using ab initio calculations: Ionization energy and electron affinity of AsF2

Mok, Daniel K.W., Lee, Edmond P.F., Chau, Foo-Tim and Dyke, John M. (2010) Franck-Condon simulation of the photoelectron spectrum of AsF2 and the photodetachment spectrum of the AsF2 anion using ab initio calculations: Ionization energy and electron affinity of AsF2. Physical Chemistry Chemical Physics, 12, 9075-9089. (doi:10.1039/C003688A).

Abstract

RCCSD(T) and/or CASSCF/MRCI calculations were carried out on the 2B1 state of AsF2, the 1A1, ã3B1 and Ã1B1 states of AsF2+, and the 1A1 state of AsF2? employing the fully-relativistic small-core effective core potential (ECP10MDF) for As and basis sets of up to augmented correlation-consistent polarized valence quintuple-zeta (aug-cc-pV5Z) quality. Minimum-energy geometrical parameters and relative electronic energies were evaluated, including contributions from extrapolation to the complete basis set limit and from outer core correlation of the As 3d10 electrons. In addition, simplified, explicitly correlated RHF/UCCSD(T)-F12x calculations were also performed employing different atomic orbital basis sets, and associated complementary auxiliary and density-fitting basis sets. The best theoretical estimates of the adiabatic ionization energies (AIE0) of AsF2(2B1) to the 1A1 and ã3B1 states of AsF2+, including corrections for zero-point vibrational energy (?ZPE), are 9.099(8) and 13.290(22) eV respectively. The best estimated electron affinity (EA0) of AsF2 is 1.182(16) eV, also including ?(ZPE). These are currently the most reliable AIE0 and EA0 values for AsF2. Potential energy functions (PEFs) of the 2B1 state of AsF2, the 1A1 and ã3B1 states of AsF2+ and 1A1 state of AsF2? were computed at RCCSD(T)/aug-cc-pV5Z, RCCSD(T)/aug-cc-pCV5Z and RHF/UCCSD(T)-F12a/aug-cc-pCVTZ levels. These PEFs were employed in variational calculations of anharmonic vibrational wavefunctions, which were then utilised to calculate Franck–Condon factors (FCFs), using a method which includes allowance for anharmonicity and Duschinsky rotation. The computed FCFs were used to simulate the first two bands in the photoelectron spectrum of AsF2 and the first band in the photodetachment spectrum of AsF2?, both yet to be recorded. The simulated spectra obtained using different sets of PEFs were found to be almost identical, suggesting that the simplified explicitly correlated UCCSD(T)-F12x method with a relatively small basis set can be a reliable alternative to the conventional RCCSD(T) correlation methods with a relatively large basis set, but at a significantly lower cost., both yet to be recorded. The simulated spectra obtained using different sets of PEFs were found to be almost identical, suggesting that the simplified explicitly correlated UCCSD(T)-F12x method with a relatively small basis set can be a reliable alternative to the conventional RCCSD(T) correlation methods with a relatively large basis set, but at a significantly lower cost.

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Contributors

Author: John M. Dyke

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