The vibrating hydroxide ion in water
2011 (English)In: Chemical Physics Letters, ISSN 0009-2614, E-ISSN 1873-4448, Vol. 514, no 1-3, 1-15 p.Article in journal (Refereed) Published
The OH− ion in water is studied using a CPMD/BLYP + QMelectronic + QMvibrational approach. The ion resides in a cage of water molecules, which are H-bonded among each other, and pinned by H-bonding to the ion’s O atom. The water network keeps the ‘on-top’ water in place, despite the fact that this particular ion-water pair interaction is non-binding. The calculated OH− vibrational peak maximum is at ∼3645 cm−1 (experiment ∼3625 cm−1) and the shift with respect to the gas-phase is ∼ +90 cm−1 (experiment +70 cm−1). The waters molecules on each side of the ion (O and H) induce a substantial OH− vibrational blueshift, but the net effect is much smaller than the sum. A parabolic ‘frequency-field’ relation qualitatively explains this non-additivity. The calculated ‘in-liquid’ ν(OH−) anharmonicity is 85 cm−1.
Place, publisher, year, edition, pages
2011. Vol. 514, no 1-3, 1-15 p.
Materials Chemistry Inorganic Chemistry
Research subject Chemistry with specialization in Inorganic Chemistry
IdentifiersURN: urn:nbn:se:uu:diva-159932DOI: 10.1016/j.cplett.2011.07.042ISI: 000295537500001OAI: oai:DiVA.org:uu-159932DiVA: diva2:447454