Vibrational interference effects in x-ray emission of a model water dimer: implications for the interpretation of the liquid spectrum
2011 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 134, no 4, 044513- p.Article in journal (Refereed) Published
We apply the Kramers-Heisenberg formula to a model water dimer to discuss vibrational interference in the x-ray emission spectrum of the donor molecule for which the core-ionized potential energy surface is dissociative but bounded by the accepting molecule. A long core-hole life time leads to decay from Zundel-like, fully delocalized vibrational states in the intermediate potential without involvement of a specific dissociated component. Comparison is made to a model with an unbound intermediate state allowing dissociation to infinity which gives a sharp, fully dissociated feature and a broad molecular peak at long core-hole life time. The implications of the vibrational interference effect on the liquid water spectrum are discussed and it is proposed that this mainly gives rise to an isotope-dependent asymmetrical broadening of the lone pair peak.
Place, publisher, year, edition, pages
2011. Vol. 134, no 4, 044513- p.
Research subject Quantum Chemistry
IdentifiersURN: urn:nbn:se:su:diva-47126DOI: 10.1063/1.3533956ISI: 000286897600079PubMedID: 21280754OAI: oai:DiVA.org:su-47126DiVA: diva2:373051