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Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry.
1993 (English)In: International Journal of Quantum Chemistry, ISSN 0020-7608, E-ISSN 1097-461X, Vol. 45, no 6, 747-758 p.Article in journal (Refereed) Published
Abstract [en]

Ab initio calculations of potential energy, dipole moment, equilibrium OH distance, force constants, and anharmonic frequencies, and correlation between these quantities, are presented for a water molecule and an OH- ion in a uniform electric field of varying field strength. It is explained why a bound H2O molecule in nature always experiences a frequency downshift with respect to the free molecule, and a bound OH-1 ion, either a downshift or an upshift. The frequency-field variation is well accounted for by the expression DELTAnu(OH) is-proportional-to -E(parallel-to) . (dmu(parallel-to)free/dr(OH) + 1/2 . partial derivative mu(parallel-to)induced/partial derivative r(OH)). A frequency maximum occurs at the field strength where partial derivative mu(parallel-to)tot/partial derivative r(OH) is similar to 0. Two cases can be discerned: (1) the frequency maximum falls at a positive field strength when dmu(parallel-to)free/dr(OH) is positive (this is the situation for OH-), and (2) the maximum frequency falls at a negative field when dmu(parallel-to)free/dr(OH) is negative (this occurs for water). In general, for an OH bond in a bonding situation where the intermolecular interactions are dominated by electrostatic forces, the nonlinearity of the frequency shift with respect to an applied field is governed by how close to the frequency maximum one is, i.e., by both dmu(parallel-to)free/dr(OH) and partial derivative mu(parallel-to)induced/partial derivative r(OH). Correlation curves between the external linear force constant, k(ext), and r(OH,e) are closely linear over the whole field range studied here, whereas the frequency vs. r(OH,e) and force constants vs. r(OH,e) correlation curves form two approximately linear, parallel branches, corresponding to ''before'' and ''after'' the maximum in the frequency vs. field curves. Each branch of the nu vs. r(OH,e) curves has a slope of approximately -16,000 cm-1/angstrom.

Place, publisher, year, edition, pages
1993. Vol. 45, no 6, 747-758 p.
National Category
Chemical Sciences
URN: urn:nbn:se:uu:diva-228784DOI: 10.1002/qua.560450621ISI: A1993KN55300019OAI: oai:DiVA.org:uu-228784DiVA: diva2:734871
Available from: 2014-07-21 Created: 2014-07-21 Last updated: 2014-07-21

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