Naslov
Quantum chemical calculations of electronically excited states: formamide, its protonated form and alkali cation complexes as case studies

Autori
Antol, Ivana ; Barbatti, Mario ; Eckert-Maksić, Mirjana ; Lischka, Hans

Izvornik
Monatshefte für Chemie (0026-9247) 139 (2008), 4; 319-328

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

Ključne riječi
photochemistry; basicity; absorption; metal ion affinities; multireference configuration interaction

Sažetak
The properties of formamide, its protonated form and interaction complexes with lithium and sodium cations were studied in electronically excited singlet states by means of high-level multireference ab initio methods. The vertical excitation energies show a marked influence on protonation with particular large effects found for the O-protonated form as compared to neutral formamide. Complexation with Li+ and Na+ leads to a pronounced shift of the nO-π * state to higher energies while the the π -π * state moves in opposite direction. Geometry optimizations in the lowest excited singlet show strong geometrical effects leading to pyramidalization at the N and C atoms. The photodynamical simulations performed for formamide in the first excited singlet state show that the main primary deactivation path is CN dissociation with a lifetime of about 420 fs.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA