Theoretical study of transition-element carbonyls MCO and carbenes MCH2 (M=Ti, Fe, Ni) in the ground and first electronic excited states by DFT methods

摘要

The electronic structure and properties of the carbonyls TiCO, FeCO, and NiCO in the quintuplet, triple;, and singlet ground states and tripler, quintuplet, and triplet first electronic excited states, respectively, were studied using density functional theory (DFT) methods. The ADF program (version 2.1) with the parameterizations BP86, BPW91, and BLYP (for the GGA corrections) and the Slater-type orbital (STO) basis sets TV as well as the GAUSSIAN 94 program with the parameterizations BP86, PW91, BLYP, B3PW91, and B3LYP and the Gaussian basis sets 6-311G(d, p) were used. Similar calculations were done on the carbenes TiCH2, FeCH2, and NiCH2 in the triplet, triplet, and singlet ground electronic states and the quintuplet, quintuplet, and triplet first electronic excited states. Geometry optimization and the calculation of dissociation energies for the M-C bond, vibrational frequencies, electric atomic charges, and dipole moments were performed for these compounds in the above-mentioned states, and comparisons between the results obtained as well as with those reported in the literature were made. (C) 1998 John Wiley & Sons. Inc. [References: 33]