Vibrational assignment and Franck-Condon analysis of the mass-analyzed threshold ionization (MATI) spectrum of CH2CII: The effect of strong spin-orbit interaction

Abstract

Detailed analysis of the one-photon mass-analyzed threshold ionization (MATI) spectrum of CH2ClI is presented. This includes the determination of the ionization energy of CH2ClI, complete vibrational assignments, and quantum-chemical calculations at the spin-orbit density-functional-theory (SODFT) level with various basis sets. Relativistic effective core potentials with effective spin-orbit operators can be used in SODFT calculations to treat the spin-orbit term on an equal footing with other relativistic effects and electron correlations. The comparison of calculated and experimental vibrational frequencies indicate that the spin-orbit effects are essential for the reasonable description of the CH2ClI+ cation. Geometrical parameters and thus the molecular shape of the cation are greatly influenced by the spin-orbit effects even for the ground state. Calculated geometrical parameters deviate substantially for different basis sets or effective core potentials. In an effort to derive the exact geometrical parameters for this cation, SODFT geometries were further improved utilizing Franck-Condon fit of the MATI spectral pattern. This empirical fitting produced the well-converged set of geometrical parameters that are quite insensitive to the choice of SODFT calculations. The C-I bond length and the CI-C-I bond angle show large deviations among different SODFT calculations, but the empirical spectral fitting yields 2.191 +/- 0.003 A for the C-I bond length and 107.09 +/- 0.09 degrees for the CI-C-I angle. Those fitted geometrical parameters along with the experimental vibrational frequencies could serve as a useful reference in calibrating relativistic quantum-chemical methods for radicals. (c) 2005 American Institute of Physics.