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Time domain fingerprints of a ‘perpendicular’ rotational Raman band: formic acid studied by femtosecond degenerate four‐wave mixing
Author(s) -
Riehn Christoph,
Matylitsky Victor V.,
Gelin Maxim F.
Publication year - 2003
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.1089
Subject(s) - polarizability , anisotropy , chemistry , femtosecond , molecular physics , raman spectroscopy , tensor (intrinsic definition) , degenerate energy levels , rotational diffusion , distortion (music) , principal axis theorem , formic acid , rotational transition , moment of inertia , mixing (physics) , atomic physics , nuclear magnetic resonance , optics , physics , angular momentum , classical mechanics , amplifier , laser , geometry , mathematics , optoelectronics , organic chemistry , cmos , chromatography , quantum mechanics , molecule , pure mathematics
Formic acid (HCOOH) vapor was studied by femtosecond degenerate four‐wave mixing (fs DFWM) and rotational recurrences of J‐, C‐ and K‐type were observed with this time‐resolved rotational spectroscopy. The occurrence of Δ K ≠0 transitions can be rationalized with the different anisotropy (oblate vs prolate) of the polarizability and moments‐of‐inertia tensor. Based on comprehensive computer simulations with a general non‐rigid asymmetric rotor model, the experimental spectrum was reproduced very well. From the fitting to the data, rotational and centrifugal distortion constants and also information on the anisotropy of the polarizability tensor were obtained in good agreement with reference values. Copyright © 2003 John Wiley & Sons, Ltd.