CEPA calculations on openhyphen;shell molecules. IV. Electron correlation effects inB1Rydberg states of H2O

摘要

We have calculated the vertical electronic excitation energies of ten 1b1rarr;a1excited states of H2O belonging to different Rydberg series. The calculations have been carried out with the FRC, SCF, PNOndash;CI, and CEPA approximations in order to investigate the electron correlation of Rydberg states. We report on correlation contributions to the electron binding energies, to the quantum defect of Rydberg series, and to the singletndash;triplet splitting energies. In addition we make predictions for the dipole moments of the Rydberg states based on SCF calculations. Comparison of our results with experiment allows the assignment of transitions belonging to anpseries and twondseries and it suggests an analysis for the 1b1rarr;ns1B1Rydberg series.