Proton transfer mediated by the vibronic coupling in oxygen core ionized states of glyoxalmonoxime studied by infrared-X-ray pump-probe spectroscopy.
2006 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 110, no 47, 12805-12813 p.Article in journal (Refereed) Published
The theory of IR-X-ray pump-probe spectroscopy beyond the Born-Oppenheimer approximation is developed and applied to the study of the dynamics of intramolecular proton transfer in glyoxalmonoxime leading to the formation of the tautomer 2-nitrosoethenol. Due to the IR pump pulses the molecule gains sufficient energy to promote a proton to a weakly bound well. A femtosecond X-ray pulse snapshots the wave packet route and, hence, the dynamics of the proton transfer. The glyoxalmonoxime molecule contains two chemically nonequivalent oxygen atoms that possess distinct roles in the hydrogen bond, a hydrogen donor and an acceptor. Core ionizations of these form two intersecting core-ionized states, the vibronic coupling between which along the OH stretching mode partially delocalizes the core hole, resulting in a hopping of the core hole from one site to another. This, in turn, affects the dynamics of the proton transfer in the core-ionized state. The quantum dynamical simulations of X-ray photoelectron spectra of glyoxalmonoxime driven by strong IR pulses demonstrate the general applicability of the technique for studies of intramolecular proton transfer in systems with vibronic coupling.
Place, publisher, year, edition, pages
2006. Vol. 110, no 47, 12805-12813 p.
Approximation theory; Ionization; Isomers; Molecular vibrations; Protons; Quantum theory; X ray analysis
IdentifiersURN: urn:nbn:se:kth:diva-5654DOI: 10.1021/jp065036dISI: 000242298800012ScopusID: 2-s2.0-33846115235OAI: oai:DiVA.org:kth-5654DiVA: diva2:10092
Uppdaterad från manuskript till artikel: 20100825 QC 201008252006-05-052006-05-052016-09-02Bibliographically approved