Ab initio calculations on low-lying electronic states of SnCl(2)- and Franck-Condon simulation of its photodetachment spectrum.
Geometry optimization and harmonic vibrational frequency calculations have been carried out on low-lying doublet and quartet electronic states of stannous (tin(II)) dichloride anion (SnCl(2)(-)) employing the CASSCF and RCCSD(T) methods. The small-core fully-relativistic effective core potential, ECP28MDF, was used for Sn in these calculations, together with valence basis sets of up to augmented correlation-consistent polarized-valence quintuple-zeta (aug-cc-pV5Z) quality. The ground electronic state of SnCl(2)(-) is determined to be the X(2)B(1) state, with the A(2)B(2) and ã(4)Sigma state, calculated to be ca. 1.50 and 2.72 eV higher in energy respectively. The electron affinities of the X(1)A(1) and ã(3)B(1) states of SnCl(2) have been computed to be 1.568+/-0.007 and 4.458+/-0.002 eV respectively, including contributions of core correlation and extrapolation to the complete basis set limit. The SnCl(2) (X(1)A(1)) + e <-- SnCl(2)(-) (X(2)B(1)) and SnCl(2) (ã(3)B(1)) + e <-- SnCl(2)(-) (X(2)B(1)) photodetachment bands have been simulated with computed Franck-Condon factors, which include an allowance for anharmonicity and Duschinsky rotation.
Lee
Edmond P F
EP
Department of Building Services Engineering, Hong Kong Polytechnic University, Hung Hom, Hong Kong. epl@soton.ac.uk
Dyke
John M
JM
Mok
Daniel K W
DK
Chow
Wan-ki
WK
Chau
Foo-tim
FT
D003198:Computer Simulation; D004583:Electrons; D008956:Models, Chemical; D010777:Photochemistry; D011789:Quantum Theory; D012680:Sensitivity and Specificity; D017971:Tin Compounds / Q000737:chemistry*
D017971:Tin Compounds; C023599:stannous chloride