Franck–Condon simulation of the photoelectron spectrum of AsCl2 and the photodetachment spectrum of AsCl employing UCCSD(T)-F12a potential energy functions: IE and EA of AsCl2
✍ Scribed by Daniel K. W. Mok; Edmond P. F. Lee; Foo-Tim Chau; John M. Dyke
- Book ID
- 102876988
- Publisher
- John Wiley and Sons
- Year
- 2011
- Tongue
- English
- Weight
- 571 KB
- Volume
- 32
- Category
- Article
- ISSN
- 0192-8651
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✦ Synopsis
The currently most reliable theoretical estimates of the adiabatic ionization energies (AIE 0 ) from the X ˜2B 1 state of AsCl 2 to the X ˜1A 1 and a ˜3B 1 states of AsCl þ 2 , and the electron affinity (EA 0 ) of AsCl 2 , including DZPE 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 5 a or b) calculations with basis sets of up to quintuple-zeta quality, have been carried out on the X ˜2B 1 state of AsCl 2 , the X ˜1A 1 , a ˜3B 1 , and A ˜1B 1 states of AsCl þ 2 , and the X ˜1A 1 state of AsCl À 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 þ 2 , and AsCl À 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 À 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 5 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.