GEOMETRY RELAXATIONS AFTER INNER-SHELL EXCITATIONS AND IONIZATIONS

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 CH(4), NH(3), H(2)O and HF: the calculated CH bond length change agrees well with the result simulated by the observed spectrum. The C1s excitation spectrum of CH(4) 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 pi* excited states of N(2)O and CO(2) were also examined. The calculated geometries of these states qualitatively agreed with the experimental values of the corresponding equivalentcore molecules.