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Rotationally resolved infrared absorption spectrum of N<sup> + </sup><sub>4</sub>
The rotationally resolved infrared band of the antisymmetric stretching vibration (3) of N + 4" align="middle"/> has been recorded by tunable diode laser spectroscopy. A continuous supersonic expansio...
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Fluorescence-dip infrared spectroscopy of the tropolone-H2O complex
Fluorescence dip infrared spectroscopy (FDIRS) is used to probe the effect of a solvent water molecule on intramolecular H-atom tunneling in tropolone. As with the bare molecule discussed in paper I, ...

Fluorescence-dip infrared spectroscopy of tropolone and tropolone-OD

J. Chem. Phys. 105, 2595 (1996); doi:10.1063/1.472119

Issue Date: 15 August 1996

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Rex K. Frost, Fredrick C. Hagemeister, Caleb A. Arrington, and Timothy S. Zwier
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-1393

Kenneth D. Jordan
Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260
Fluorescence-dip infrared spectroscopy (FDIRS) is employed to record the infrared spectra of the isolated, jet-cooled tropolone molecule (TrOH) and its singly deuterated isotopomer TrOD in the O–H and C–H stretch regions. The ability of the method to monitor a single ground-state level enables the acquisition of spectra out of the lower and upper levels of the zero-point tunneling doublet free from interference from one another. The high power of the optical parametric oscillator used for infrared generation produces FDIR spectra with good signal-to-noise despite the weak intensity of the C–H and O–H stretch transitions in tropolone. The expectation that both spectra will exhibit two OH stretch transitions separated by the OH(v=1) tunneling splitting is only partially verified in the present study. The spectra of TrOH are compared with those from deuterated tropolone (TrOD) to assign transitions due to C–H and O–H, which are in close proximity in TrOH. The appearance of the spectra out of lower (a1 symmetry) and upper (b2 symmetry) tunneling levels are surprisingly similar. Two sharp transitions at 3134.9 cm–1 (out of the a1 tunneling level) and 3133.9 cm–1 (out of the b2 tunneling level) are separated by the ground-state tunneling splitting (0.99 cm–1), and thereby terminate in the same upper state tunneling level. Their similar intensities relative to the C–H stretch transitions indicate that the y- and z-polarized transitions are of comparable intensity, as predicted by ab initio calculations. The corresponding transitions to the other member of the upper state tunneling doublet are not clearly assigned by the present study, but the broad absorptions centered about 12 cm–1 below the assigned transitions are suggested as the most likely possibility for the missing transitions. ©1996 American Institute of Physics.
History: Received 13 March 1996; accepted 7 May 1996
Permalink: http://link.aip.org/link/?JCPSA6/105/2595/1
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KEYWORDS and PACS

Keywords
PACS
  • 33.20.Ea
    Molecular properties and interactions with photons Molecular spectra Infrared spectra
  • 33.50.Dq
    Molecular properties and interactions with photons Fluorescence and phosphorescence; radiationless transitions, quenching (intersystem crossing, internal conversion) Fluorescence and phosphorescence spectra
  • YEAR: 1996

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

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