Theoretical study of electronic structures and spectroscopic properties of Ga3Sn, GaSn3, and their ions

Ground and excited states of mixed gallium stannide tetramers (Ga3Sn, Ga3Sn+, Ga3Sn-, GaSn3, GaSn3+, and GaSn3-) are investigated employing the complete active space self-consistent-field (CASSCF), density function theory (DFT), and the coupled-cluster single and double substitution (including triple excitations) (CCSD(T)) methods. The ground states of Ga3Sn, Ga3Sn+, and Ga3Sn- are found to be the 2A1, 3B1, and 1A1 states in C2v symmetry with a planar quadrilateral geometry, respectively. The ground states of GaSn3 and GaSn3- is predicted to be the 2A1 and 1A1 states in C2v point group with a planar quadrilateral structure, respectively, while the ground state of GaSn3+ is the 1A1 state with ideal triangular pyramid C3v geometry. Equilibrium geometries, vibrational frequencies, binding energies, electron affinities, ionization energies, and other properties of Ga3Sn and GaSn3 are computed and discussed. The anion photoelectron spectra of Ga3Sn- and GaSn3- are also predicted. It is interesting to find that the amount of charge transfer between Ga and Sn2 atoms in the 1A1 state of GaSn3+ greatly increases upon electron ionization from the 2A1 state of GaSn3, which may be caused by large geometry change. On the other hand, the results of the low-lying states of Ga3Sn and GaSn3 are compared with those of Ga3Si and GaSi3.