Dipole moment analysis of excited van der Waals vibrational states of ArH35Cl

Title:
Dipole moment analysis of excited van der Waals vibrational states of ArH35Cl
Authors:
Cooksy, A. L.; Elrod, Matthew J.; Saykally, Richard J.; Klemperer, W.
Abstract:
The far-infrared laser electric resonance spectra of the prototypical atom—diatom complex ArH35Cl are analyzed using improved zero-field molecular constants, yielding accurate permanent and transition dipole moments for the three lowest excited van der Waals vibrational states. The constants are obtained from a multistate fit to previous microwave, far-infrared laser electric resonance, and far-infrared tunable laser spectra, as well as new far-infrared measurements of the Sigma -stretch state, which are reported here. The signs of the dipole moments and Coriolis coefficients establish the relative orientations of the HCl subunit in these states. The fit is found to converge only if these signs correspond to the HCl pointing in opposite directions along the a inertial axis in the Sigma -stretch and Sigma -bend states. A weak preference, near the experimental error limit, is found for the Ar—Cl—H average angle in the Pi -bend state to be greater than 90°, contrary to expectation. For the best fit, we obtain the a-axis dipole moment components -0.5413(11) D ( Sigma bend), -0.263 45(29) D ( Pi bend), and 0.6754(36) D ( Sigma -stretch); and the b-axis components 0.365(12) D ( Pi and Sigma -bend) and -0.0465(43) D ( Pi and Sigma stretches), where the signs of the Coriolis coefficients and µa for the Sigma stretch have been arbitrarily fixed positive. For the expected Pi -bend configuration, with the Ar—Cl—H angle less than 90°, the magnitudes along the a axis change only slightly, but the b-axis components become 0.149(12) and -0.1403(64) D for the Pi — Sigma -bend and Pi — Sigma -stretch interactions, respectively.
Citation:
Cooksy, A.L., M.J. Elrod, R.J. Saykally, and W. Klemperer. 1993. "Dipole Moment Analysis of Excited Van der Waals Vibrational States of ArH35Cl." Journal of Chemical Physics 99(3200).
Publisher:
American Institute of Physics
DATE ISSUED:
1993-09-01
Department:
Chemistry
Type:
article
PUBLISHED VERSION:
10.1063/1.465128
PERMANENT LINK:
http://hdl.handle.net/11282/309813

Full metadata record

DC FieldValue Language
dc.contributor.authorCooksy, A. L.en_US
dc.contributor.authorElrod, Matthew J.en_US
dc.contributor.authorSaykally, Richard J.en_US
dc.contributor.authorKlemperer, W.en_US
dc.date.accessioned2013-12-23T16:18:27Z-
dc.date.available2013-12-23T16:18:27Z-
dc.date.issued1993-09-01en
dc.identifier.citationCooksy, A.L., M.J. Elrod, R.J. Saykally, and W. Klemperer. 1993. "Dipole Moment Analysis of Excited Van der Waals Vibrational States of ArH35Cl." Journal of Chemical Physics 99(3200).en_US
dc.identifier.issn0021-9606en_US
dc.identifier.urihttp://hdl.handle.net/11282/309813-
dc.description.abstractThe far-infrared laser electric resonance spectra of the prototypical atom—diatom complex ArH35Cl are analyzed using improved zero-field molecular constants, yielding accurate permanent and transition dipole moments for the three lowest excited van der Waals vibrational states. The constants are obtained from a multistate fit to previous microwave, far-infrared laser electric resonance, and far-infrared tunable laser spectra, as well as new far-infrared measurements of the Sigma -stretch state, which are reported here. The signs of the dipole moments and Coriolis coefficients establish the relative orientations of the HCl subunit in these states. The fit is found to converge only if these signs correspond to the HCl pointing in opposite directions along the a inertial axis in the Sigma -stretch and Sigma -bend states. A weak preference, near the experimental error limit, is found for the Ar—Cl—H average angle in the Pi -bend state to be greater than 90°, contrary to expectation. For the best fit, we obtain the a-axis dipole moment components -0.5413(11) D ( Sigma bend), -0.263 45(29) D ( Pi bend), and 0.6754(36) D ( Sigma -stretch); and the b-axis components 0.365(12) D ( Pi and Sigma -bend) and -0.0465(43) D ( Pi and Sigma stretches), where the signs of the Coriolis coefficients and µa for the Sigma stretch have been arbitrarily fixed positive. For the expected Pi -bend configuration, with the Ar—Cl—H angle less than 90°, the magnitudes along the a axis change only slightly, but the b-axis components become 0.149(12) and -0.1403(64) D for the Pi — Sigma -bend and Pi — Sigma -stretch interactions, respectively.en_US
dc.language.isoen_USen_US
dc.publisherAmerican Institute of Physicsen_US
dc.identifier.doi10.1063/1.465128-
dc.subject.departmentChemistryen_US
dc.titleDipole moment analysis of excited van der Waals vibrational states of ArH35Clen_US
dc.typearticleen_US
dc.identifier.journalJournal of Chemical Physicsen_US
dc.subject.keywordVan der Waals forcesen_US
dc.subject.keywordExcited statesen_US
dc.subject.keywordDipole momentsen_US
dc.subject.keywordVibrational statesen_US
dc.subject.keywordArgon complexesen_US
dc.subject.keywordHydrochloric aciden_US
dc.subject.keywordChlorine 35en_US
dc.subject.keywordFar infrared radiationen_US
dc.subject.keywordLasersen_US
dc.subject.keywordElectric resonanceen_US
dc.subject.keywordZero field splittingen_US
dc.subject.keywordAccuracyen_US
dc.subject.keywordTuningen_US
dc.subject.keywordLaser spectroscopyen_US
dc.subject.keywordCoriolis forceen_US
dc.subject.keywordReorientationen_US
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