From Molecule to Cluster to Bulk - Water OH Vibrations in Different Surroundings
1992 (English)In: International Journal of Quantum Chemistry, ISSN 0020-7608, E-ISSN 1097-461X, Vol. 42, no 5, 1251-1270 p.Article, review/survey (Refereed) Published
Vibrational spectra for the O-H stretching motion of HDO molecules in different surroundings have been calculated by quantum mechanical ab initio methods and compared with experimental spectra. The free water molecule, water chains, and ion-water clusters are discussed. Solvent effects on OH vibrations in liquid water have been calculated as well as "in-crystal" OH frequencies in some ice and ionic crystalline hydrate structures. The importance of nonadditivity effects, electron correlation (at the MP2 level), and long-range interactions for the total frequency downshift is demonstrated. It is shown that the inclusion of these effects, in conjunction with a variational quantum mechanical treatment of the anharmonic vibrational stretching motion (force constants up to the fourth order), yields vibrational frequencies in quantitative agreement with experiment for a wide range of aqueous systems.
Place, publisher, year, edition, pages
1992. Vol. 42, no 5, 1251-1270 p.
IdentifiersURN: urn:nbn:se:liu:diva-115171ISI: A1992HP60500010OAI: oai:DiVA.org:liu-115171DiVA: diva2:794201