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Franck–Condon simulation of the photoelectron spectrum of AsCl2 and the photodetachment spectrum of AsClmath image employing UCCSD(T)-F12a potential energy functions: IE and EA of AsCl2

Authors

  • Daniel K. W. Mok,

    Corresponding author
    1. Department of Applied Biology and Chemical Technology, Hong Kong Polytechnic University, Hung Hom, Hong Kong
    • Department of Applied Biology and Chemical Technology, Hong Kong Polytechnic University, Hung Hom, Hong Kong
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  • Edmond P. F. Lee,

    1. Department of Applied Biology and Chemical Technology, Hong Kong Polytechnic University, Hung Hom, Hong Kong
    2. School of Chemistry, Faculty of Natural and Environmental Sciences, University of Southampton, Highfield, Southampton SO17 1BJ, United Kingdom
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  • Foo-Tim Chau,

    1. Department of Applied Biology and Chemical Technology, Hong Kong Polytechnic University, Hung Hom, Hong Kong
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  • John M. Dyke

    1. School of Chemistry, Faculty of Natural and Environmental Sciences, University of Southampton, Highfield, Southampton SO17 1BJ, United Kingdom
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Abstract

The currently most reliable theoretical estimates of the adiabatic ionization energies (AIE0) from the X̃2B1 state of AsCl2 to the X̃1A1 and ã3B1 states of AsClmath image, and the electron affinity (EA0) of AsCl2, including ΔZPE corrections, are calculated as 8.687(11), 11.320(23), and 1.845(12) eV, respectively (estimated uncertainties based on basis-set effects at the RCCSD(T) level). State-of-the-art ab initio calculations, which include RCCSD(T), CASSCF/MRCI, and explicitly correlated RHF/UCCSD(T)-F12x (x = a or b) calculations with basis sets of up to quintuple-zeta quality, have been carried out on the X̃2B1 state of AsCl2, the X̃1A1, ã3B1, and Ã1B1 states of AsClmath image, and the X̃1A1 state of AsClmath image. Relativistic, core correlation and complete basis-set (CBS) effects have been considered. In addition, computed UCCSD(T)-F12a potential energy functions of relevant electronic states of AsCl2, AsClmath image, and AsClmath image were used to calculate Franck–Condon factors, which were then used to simulate the valence photoelectron spectrum of AsCl2 and the photodetachment spectrum of AsClmath image, both yet to be recorded. Lastly, we have also computed the AIE and EA values for NCl2, PCl2, and AsCl2 at the G4 level and for SbCl2 at the RCCSD(T)/CBS level. The trends in the AIE and EA values of the group V pnictogen dichlorides, PnCl2, where Pn = N, P, As, and Sb, were examined. The AIE and EA of PCl2 were found to be smaller than those of AsCl2, contrary to the order expected from the IE values of P and As. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011

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