title: Franck-Condon simulation of the photoelectron spectrum of AsCl₂ and the photodetachment spectrum of AsCl ₂⁻ employing UCCSD(T)-F12a potential energy functions: IE and EA of AsCl₂.
abstract: The currently most reliable theoretical estimates of the adiabatic ionization energies (AIE(0)) from the X̃(2)B(1) state of AsCl(2) to the X̃(1)A(1) and ã(3)B(1) states of AsCl 2+, and the electron affinity (EA(0)) of AsCl(2) , 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 X̃(2)B(1) state of AsCl(2) , the X̃(1)A(1) , ã(3)B(1) , and Ã(1)B(1) states of AsCl 2+, and the X̃(1)A(1) state of AsCl 2-. 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 AsCl(2) , AsCl (2)(+), and AsCl( 2)(-) were used to calculate Franck-Condon factors, which were then used to simulate the valence photoelectron spectrum of AsCl(2) and the photodetachment spectrum of AsCl (2)(-), both yet to be recorded. Lastly, we have also computed the AIE and EA values for NCl(2) , PCl(2) , and AsCl(2) at the G4 level and for SbCl(2) at the RCCSD(T)/CBS level. The trends in the AIE and EA values of the group V pnictogen dichlorides, PnCl(2) , where Pn = N, P, As, and Sb, were examined. The AIE and EA of PCl(2) were found to be smaller than those of AsCl(2) , contrary to the order expected from the IE values of P and As.
authors.affiliation: Department of Applied Biology and Chemical Technology, Hong Kong Polytechnic University, Hung Hom, Hong Kong. bcdaniel@polyu.edu.hk
authors.forename: Daniel K W
authors.initials: DK
authors.lastname: Mok
authors.forename: Edmond P F
authors.initials: EP
authors.lastname: Lee
authors.forename: Foo-Tim
authors.initials: FT
authors.lastname: Chau
authors.forename: John M
authors.initials: JM
authors.lastname: Dyke