Collect. Czech. Chem. Commun. 2008, 73, 771-785

Geometry Relaxations After Inner-Shell Excitations and Ionizations

Masahiro Eharaa,b,* and Hiroshi Nakatsujib,c,*

a Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan
b JST, CREST, Sanbancho-5, Chiyoda-ku, Tokyo 102-0075, Japan
c Quantum Chemistry Research Institute, Kyodai Katsura Venture Plaza 106, Goryo Oohara 1-36, Nishikyo-ku, Kyoto 615-8245, Japan


The geometry relaxations due to the inner-shell excitations and ionizations have been studied by the SAC-CI method. The characteristic molecular geometry changes were predicted for the core-hole states of CH4, NH3, H2O and HF: the calculated CH bond length change agrees well with the result simulated by the observed spectrum. The C1s excitation spectrum of CH4 was also investigated for the Rydberg states of the principal quantum numbers n = 3, 4 and 5. The potential energy curves of the dipole-allowed excited states were calculated for the totally symmetric stretching mode. The vibrational structure and Franck-Condon factors for the C1s excitation spectrum were well reproduced, which shows that the equilibrium geometries of the excited states were accurately evaluated. The geometries of the inner-shell π* excited states of N2O and CO2 were also examined. The calculated geometries of these states qualitatively agreed with the experimental values of the corresponding equivalent-core molecules.

Keywords: Core-electron process; Electronic structure; SAC-CI; Geometry optimization; Vibrational spectrum.

References: 47 live references.