Accessibility navigation


Vibrational energy levels of water

Császár, A. G. and Mills, I. (1997) Vibrational energy levels of water. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 53 (8). pp. 1101-1122. ISSN 1386-1425

Full text not archived in this repository.

It is advisable to refer to the publisher's version if you intend to cite from this work. See Guidance on citing.

To link to this item DOI: 10.1016/S1386-1425(97)00020-6

Abstract/Summary

Several quartic force fields and a full sextic anharmonic force field for H,O have been determined from high-quality ab initio calculations, the highest at the aug-cc-pVQZ CCSD(T) level of theory. These force fields have been used to determine vibrational excited state band origins up to 15 000 cm - ’ above the zero-point level, using both a perturbation-resonancea pproach and a variational approach. An optimisedq uartic force field hasb eeno btained by least squares refinement of our best ab initio results to fit the observed overtone levels of 5 symmetrically substituted isotopomers of water (Hi60, Hi70, HisO, D,O, and T,O) with an rms error of less than 10 cm-‘, using the perturbation-resonancem odel for the vibrational calculation. Predicatel east squaresr efinement was usedt o provide a loose constraint of the refined force field to the ab initio results. The results obtained prove the viability of the perturbation-resonancem odel for usei n larger molecular systemsa nd also highlight someo f its weaknesse

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy
ID Code:7304
Uncontrolled Keywords:Anharmonic force field; Perturbation-resonance model; Vibrational energy
Publisher:Elsevier

University Staff: Request a correction | Centaur Editors: Update this record

Page navigation