Naslov
Photoionization of pyrrole from the B_2 state: a computational study on the effects of Rydberg–valence mixing

Autori
Ponzi, Aurora ; Sapunar, Marin ; Došlić, Nađa ; Decleva, Piero

Izvornik
Theoretical chemistry accounts (1432-881X) 139 (2020), 8; 137, 8

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, ostalo

Ključne riječi
Dyson orbitals ; MFPAD ; Photodynamics ; Photoionization ; Pyrrole ; Valence–Rydberg character

Sažetak
Does the optically bright B2(π→ π∗) transition in pyrrole correspond to an inter-valence or to a mixed valence–Rydberg transition? State-of- the-art electronic structure methods provide inconclusive results and relegate the answer to future time-resolved photoelectron spectroscopy experiments. Here, benchmark calculations of photoionization cross sections, asymmetry parameters and molecular frame photoelectron angular distributions (MFPADs) have been performed with the aim of discerning between the two types of transitions. In particular, we show that MFPADs are very sensitive probes of the electronic wave function and that accurate experimental MFPADs could be used to identify the electronic character of the B2 state.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA