Symmetry and vibrationally resolved absorption spectra near theN Kedges ofN2O: Experiment and theory

Abstract

This is the published version of a paper published in Physical Review A. Atomic, Molecular, and Optical Physics. Citation for the original published paper (version of record):Ehara, M., Horikawa, T., Fukuda, R., Nakatsuji, H., Tanaka, T. et al. (2011) Symmetry and vibrationally resolved absorption spectra near the N K edges of N2O: experiment and theory.Physical Review A. Atomic, Molecular, and Optical Physics, 83(6) In this study, angle-resolved energetic-ion yield spectra were measured in the N 1s excitation region of N 2 O. A Franck-Condon analysis based on ab initio two-dimensional potential energy surfaces of the coreexcited Rydberg states, which were calculated by the symmetry-adapted cluster-configuration interaction method, reproduced observed vibrational excitations specific to the individual Rydberg states well and enabled quantitative assignments. Geometric changes in the terminal nitrogen N t 1s and the central nitrogen N c 1s excited states with respect to the 3pπ , 3pσ , and 4sσ transitions were analyzed. The coupling of these valence and Rydbergs states was examined based on the second moment analysis. Irregular Rydberg-state behavior in the N c 1s −1 4sσ state was observed.

Physical Properties, Exciton Analysis, and Visualization of Core-Excited States: An Intermediate State Representation Approach

“…Using the Full-CI (FCI) approach is computationally not possible; thus, the SAC-CI method has been chosen. This method is well known to provide accurate results for core-excited states as well as their excited state properties. ,− However, SAC-CI cannot be used as real benchmark method for our CVS-ADC calculations because both methods are at similar level of theory with similar expected accuracy. The SAC-CI results, however, help to demonstrate the correct behavior of the CVS-ADC/ISR approach.…”