We investigate theoretically the electronic structure of I·CO2 and I·OCS van der Waals complexes including spin-orbit interaction. For the T-shaped geometry of I·CO2, we calculate the potentials using a fully polyatomic treatment and compare the results to the widely used pseudo-diatomic approximation. The latter becomes increasingly invalid at I-CO2 distances shorter than 4 Å. We calculate the potentials of linear I·SCO and I·OCS, and analyze the zero-order electronic structure of nonlinear I·OCS. We also discuss the validity of treating the spin-orbit interaction in I·CO2 and I·OCS as an atomic property of iodine and find this approximation justified at characteristic van der Waals distances.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry