Intracavity laser absorption spectroscopy of HOCl overtones .1. The 3v(1)+2v(2) band and numbers of vibrational states

被引:51
作者
Abel, B
Hamann, HH
Kachanov, AA
Troe, J
机构
[1] UNIV GOTTINGEN,INST PHYS CHEM,D-37077 GOTTINGEN,GERMANY
[2] RUSSIAN ACAD SCI,INST SPECTROSCOPY,TROITSK 142092,RUSSIA
[3] UNIV GRENOBLE 1,SPECTROMETRIE PHYS LAB,F-38402 ST MARTIN DHERES,FRANCE
关键词
D O I
10.1063/1.471016
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The near infrared high-resolution spectra of the a-type transitions of the weak 3v(1)+2v(2) combination band of transient HO35(37)Cl at 12600 cm(-1) has been recorded in an ultrasensitive titanium:sapphire intracavity laser absorption spectrometer (ICLAS). We report line assignments, new and refined anharmonicity parameters, and the spectroscopic constants for the excited rovibrational states of 3v(1)+2v(2). The Fermi resonance perturbations in this five quanta region, where the internal energy of the molecule is already more than 2/3 of the dissociation energy E(0), remain localized and they are the exception, while the extent of intermode mixing and thus intramolecular vibrational energy distribution (IVR) seems to be still small. A Dunham expansion is used for band origin predictions and representations of vibrational states N(E) of (HOCl)-Cl-35 up to the dissociation threshold. The results are compared with harmonic and anharmonic numbers of states from a recently proposed stretch-bend coupling model. (C) 1996 American Institute of Physics.
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页码:3189 / 3197
页数:9
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