New ab initio potential energy surfaces for both the ground (X̃¹A′) and excited (ùA″) electronic states of HSiCl and the absorption and emission spectra of HSiCl/DSiCl

Abstract

New ab initio potential energy surfaces for the ground (X̃1A') and excited (Ã1A″) electronic states of HSiCl were obtained by using the single and double excitation coupled-cluster theory with a noniterative perturbation treatment of triple excitations and the multi-reference configuration interaction with Davidson correction, respectively, employing an augmented correlation-consistent polarized valence quadruple zeta basis set. For the excited state Ã1A″, an extended active space (18 electrons in 12 orbitals) was used. The calculated vibrational energy levels of HSiCl and DSiCl of the ground and excited electronic states are in better agreement with the available experimental values than the previous theoretical results. In addition, with the calculated transition dipole moment, the absorption and emission spectra of HSiCl and DSiCl were calculated using an efficient single Lanczos propagation method and are in reasonable agreement with the available observed spectra.

Ab Initio Potential Energy Surfaces for Both the Ground (X̃1A′) and Excited (ALi1, Lin2, Xie3 2012Advances in Physical ChemistrySelf Cite33040View full textAdd to dashboardCite

“…These emission spectra show that the spectral pattern is quite sensitive to the vibrational state from which the emission originates. These observations are very similar to those in our previous work about HSiCl [20].…”

“…In the present work, we extend our previous studies on the HGeCl [18], HGeBr [19], and HSiCl [20] systems by reporting accurate ab initio PESs for both the ground ( X 1 A ) and excited ( A 1 A ) electronic states of HSiBr using the coupled cluster singles and doubles with perturbative triples method [CCSD(T)] and the internally contracted multireference configuration interaction method with the (0, 0, 9) (0, 0, 10) (0, 0, 11) (1, 0, 6) (2, 0, 4) (3, 0, 0)…”

“…• ,which is very similar to that of HSiCl [20], except that the Si-Br bond is longer than the Si-Cl bond. Our results are compared in Table 1 with the previous experimental and theoretical results.…”

“…After primary test calculations, the state-averaged complete active space self-consistent field (SA-CASSCF) [27,28] for equally weighted 1 1 A and 2 1 A states were employed with a large active space (18 active electrons in 12 active orbitals) to further consider the core-valence correlation effect [15,[18][19][20]. The remnant sixteen core orbitals were kept doubly occupied but fully optimized.…”

Which triatomic monohalosilylenes, monohalogermylenes, and monohalostannylenes (HMX) fluoresce or phosphoresce and why? An ab initio investigation

“…Contemporaneously, Lin et al published similar studies of the ground and first excited singlet states of HGeCl/DGeCl, 18 HGeBr/DGeBr 19 and HSiCl/DSiCl. 20 They emphasized the importance of 3d orbitals in the Ge containing species and found very good agreement between theory and experiment for the molecular geometries, vibrational frequencies and simulations of spectra.…”