Hyoseok Kim

Spin−Orbit and Electron Correlation Effects on the Structure of EF3 (E = I, At, and Element 117)†

Structures and vibrational frequencies of group 17 fluorides EF3 (E = I, At, and element 117) are calculated at the density functional theory (DFT) level of theory using relativistic effective core potentials (RECPs) with and without spin-orbit terms in order to investigate the effects of spin-orbit interactions and electron correlations on the structures and vibrational frequencies of EF3. Various tests imply that spin-orbit and electron correlation effects estimated presently from Hartree-Fock (HF) and DFT calculations with RECPs with and without spin-orbit terms are quite reasonable. Spin-orbit and electron correlation effects generally increase bond lengths and/or angles in both C2v and D3h structures. For IF3, the C2v structure is a global minimum, and the D3h structure is a second-order saddle point in both HF and DFT calculations with and without spin-orbit interactions. Spin-orbit effects for IF3 are negligible in comparison to electron correlation effects. The D3h global minimum is the only minimum structure for (117)F3 in all RECP calculations, and the C2v structure is neither a local minimum nor a saddle point. In the case of AtF3, the C2v structure is found to be a local minimum in all RECP calculations without spin-orbit terms, and the D3h structure becomes a local minimum at the DFT level of theory with and without spin-orbit interactions. In the HF calculation with spin-orbit terms, the D3h structure of AtF3 is a second-order saddle point. AtF3 is a borderline case between the valence-shell-electron-pair-repulsion (VSEPR) structure of IF3 and the non-VSEPR structure of (117)F3. Relativistic effects, including scalar relativistic and spin-orbit effects, and electron correlation effects together or separately stabilize the D3h structures more than the C2v structures. As a result, one may suggest that the VSEPR predictions agree very well with the structures optimized by the nonrelativistic HF level of theory even for heavy-atom molecules but not so well with those from more elaborate theoretical methods. Vibrational frequencies of AtF3 and (117)F3 are modified substantially and nonadditively by spin-orbit and electron correlation contributions. This is one of those rare cases for which vibrational frequencies of the closed-shell molecules are significantly affected by spin-orbit interactions. Spin-orbit interactions decrease all vibrational frequencies of EF3 molecules considered.

Vibrational assignment and Franck-Condon analysis of the mass-analyzed threshold ionization (MATI) spectrum of CH2ClI: the effect of strong spin-orbit interaction.

Detailed analysis of the one-photon mass-analyzed threshold ionization (MATI) spectrum of CH(2)ClI is presented. This includes the determination of the ionization energy of CH(2)ClI, 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 CH(2)ClI(+) 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 Cl-C-I bond angle show large deviations among different SODFT calculations, but the empirical spectral fitting yields 2.191 +/- 0.003 Angstroms for the C-I bond length and 107.09 +/- 0.09 degrees for the Cl-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.

One-photon mass-analyzed threshold ionization spectroscopy of CH2BrI: extensive bending progression, reduced steric effect, and spin-orbit effect in the cation.

One-photon mass-analyzed threshold ionization (MATI) spectrum of CH2BrI was obtained using coherent vacuum-ultraviolet radiation generated by four-wave difference-frequency mixing in Kr. Unlike CH2ClI investigated previously, a very extensive bending (Br-C-I) progression was observed. Vibrational frequencies of CH2BrI+ were measured from the spectra and the vibrational assignments were made by utilizing frequencies calculated by the density-functional-theory (DFT) method using relativistic effective core potentials with and without the spin-orbit terms. A noticeable spin-orbit effect on the vibrational frequencies was observed from the DFT calculations, even though its influence was not so dramatic as in CH2ClI+. A simple explanation based on the bonding characteristics of the molecular orbitals involved in the ionization is presented to account for the above differences between the MATI spectra of CH2BrI and CH2ClI. The 0-0 band of the CH2BrI spectrum could be identified through the use of combined data from calculations and experiments. The adiabatic ionization energy determined from the position of this band was 9.5944+/-0.0006 eV, which was significantly smaller than the vertical ionization energy reported previously.