Dyson orbitals of N2O: electron momentum spectroscopy and symmetry adapted cluster-configuration interaction calculations.

ABSTRACT

Electron momentum spectroscopy and symmetry adapted cluster-configuration interaction (SAC-CI) theory were combined to study electron correlation effects in nitrous oxide molecule (N(2)O). The SAC-CI General-R method accurately reproduced the experimental ionization spectrum. This bench-marked method was also introduced for calculating the momentum distributions of N(2)O Dyson orbitals. Several calculated momentum distributions with different theoretical methods were compared with the high resolution experimental results. In the outer-valence region, Hartree-Fock (HF), density functional theory (DFT), and SAC-CI theory can well describe the experimental momentum distributions. SAC-CI presented a best performance among them. In the inner-valence region, HF and DFT cannot work well due to the severe breaking of the molecular orbital picture, while SAC-CI still produced an excellent description of experimental momentum profiles because it can accurately take into account electron correlations. Moreover, the thermally averaged calculation showed that the geometrical changes induced by the vibration at room temperature have no noticeable effects on momentum distribution of valence orbitals of N(2)O.