Electronic structure of germanium monohydrides Ge(n)H, n = 1-3.
Quantum chemical calculations were applied to investigate the electronic structure of germanium hydrides, Ge(n)H (n = 1, 2, 3), their cations, and anions. Computations using a multiconfigurational quasi-degenerate perturbation approach (MCQDPT2) based on complete active space wave functions (CASSCF), multireference perturbation theory (MRMP2), and density functional theory reveal that Ge(2)H has a (2)B(1) ground state with a doublet-quartet gap of approximately 39 kcal/mol. A quasidegenerate (2)A(1) state has been derived to be 2 kcal/mol above the ground state (MCQDPT2/aug-cc-pVTZ). In the case of the cation Ge(3)H(+) and anion Ge(3)H(-), singlet low-lying electronic states are derived, that is, (1)A' and (1)A(1), respectively. The singlet-triplet energy gap is estimated to 6 kcal/mol for the cation. An "Atoms in Molecules" (AIM) analysis shows a certain positive charge on the Ge(n) (n = 1, 2, 3) unit in its hydrides, in accordance with the NBO analysis. The topologies of the electron density of the germanium hydrides are different from that of the lithium-doped counterparts. On the basis of our electron localization function (ELF) analysis, the Ge-H bond in Ge(2)H is characterized as a three-center-two-electron bond. Some key thermochemical parameters of Ge(n)H have also been derived.
Gopakumar
G
G
Department of Chemistry, and Institute for Nanoscale Physics and Chemistry, University of Leuven, B-3001 Leuven, Belgium.
Ngan
Vu Thi
VT
Lievens
Peter
P
Nguyen
Minh Tho
MT