Scaled Quantum Mechanical (SQM) Force Field Calculations of the Hexathiometadiphosphate Anion P2S2-6

Abstract

AbstractBy ab initio quantum mechanical calculations on P2S2-6 its equilibrium energy, geometry and vibrational frequencies along with their PED values have been obtained. The basis sets STO-5G, 6-31G, STO-5G* and 6-31G* were employed, and force field calculations were carried out at the STO-5G and the STO-5G* levels. The calculations show that the assignment for some bands between 180 and 260 cm -1 should be corrected. Two scaling factors were needed to fit the calculated frequencies with the observed frequencies within a deviation of less then 20 cm -1 for all vibrations, with the exception of v6(B1g). The calculated frequency of this vibration is very dependent on the polarization functions, and use of STO-2G for the 3d-orbitals corrects most of the deviation. STO-5G* and 6-31G* both give a good description of the geometry of the title ion, although STO-5G* yields a 0.04 Å too short terminal P - S distance.