A new nonsymmetric As(OH)(3) species. Comparison with the known C-3 species and themochemistry at the HF, DFT(B3LYP), MP2, MP4, and CCSD(T) levels of theory

Abstract

A new nonsymmetric As(OH)(3) species that is more stable than the C-3 structure is found at HF, Density Functional Theory (B3LYP), MP2, MP4 and CCSD(T) levels with the Stuttgart RECP-basis for As and the aug-cc-pvdz/pvtz extended basis sets. Transition state (TS) geometries are close to the C-3 one. Energy differences and interconversion barriers become smaller with increasing inclusion of electronic correlation. However, for MP4 and CCSD(T) descriptions, these differences increase by more than 100% when basis set goes from the AVDZ to AVTZ quality. Zero point energy (ZPE) corrections are essential and have been taken into account at all levels of theory

although this leads to barrier collapse at the B3LYP, MP2, MP4 and CCSD(T) levels, the C-1 isomer remains more stable than the C-3 one. MP2/AVTZ infrared spectra are also given for the C-1 and C-3 isomers as guiding data for future IR studies in the gas phase.