Complete characterization of the water dimer vibrational ground state and testing the VRT(ASP-W)III, SAPT-5st, and VRT(MCY-5f) surfaces

We report the observation of extensive a- and c-type rotation-tunnelling (RT) spectra of (H 2 O) 2 for K a = 0-3, and (D 2 O) 2 for K a = 0-4. These data allow a detailed characterization of the vibrational ground state to energies comparable to those of the low-lying (70-80 cm −1 ) intermolecular v...

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Published inMolecular physics Vol. 101; no. 23-24; pp. 3477 - 3492
Main Authors KEUTSCH, FRANK N., GOLDMAN, NIR, HARKER, HEATHER A., LEFORESTIER, CLAUDE, SAYKALLY, RICHARD J.
Format Journal Article
LanguageEnglish
Published Taylor & Francis Group 10.12.2003
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Summary:We report the observation of extensive a- and c-type rotation-tunnelling (RT) spectra of (H 2 O) 2 for K a = 0-3, and (D 2 O) 2 for K a = 0-4. These data allow a detailed characterization of the vibrational ground state to energies comparable to those of the low-lying (70-80 cm −1 ) intermolecular vibrations. We present a comparison of the experimentally determined molecular constants and tunnelling splittings with those calculated on the VRT(ASP-W)III, SAPT-5st, and VRT(MCY-5f) intermolecular potential energy surfaces. The SAPT-5st potential reproduces the vibrational ground state properties of the water dimer very well. The VRT(MCY-5f) and especially the VRT(ASP-W)III potentials show larger disagreements, in particular for the bifurcation tunnelling splitting.
ISSN:0026-8976
1362-3028
DOI:10.1080/00268970310001636486