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Coupling of torsion and OH-stretching in tert-butyl hydroperoxide. II. The OH-stretching fundamental and overtone spectra

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0048022· OSTI ID:1853713
 [1];  [2];  [3];  [2];  [3];  [4];  [3];  [4];  [2];  [3]
  1. University of Copenhagen (Denmark); Univ. of Washington, Seattle, WA (United States)
  2. University of Washington, Seattle, WA (United States)
  3. University of Copenhagen (Denmark)
  4. University of Pennsylvania, Philadelphia, PA (United States)
+ Show Author Affiliations
We report the vibrational spectra of gas phase tert-butyl hydroperoxide have been recorded in the OH-stretching fundamental and overtone regions (ΔvOH = 1–5) at room temperature using conventional Fourier transform infrared (ΔvOH = 1–3) and cavity ring-down (ΔvOH = 4–5) spectroscopy. In hydroperoxides, the OH-stretching and COOH torsion vibrations are strongly coupled. The double-well nature of the COOH torsion potential leads to tunneling splitting of the energy levels and, combined with the low frequency of the torsional vibration, results in spectra in the OH-stretching regions with multiple vibrational transitions. In each of the OH-stretching regions, both an OH-stretching and a stretch–torsion combination feature are observed, and we show direct evidence for the tunneling splitting in the OH-stretching fundamental region. We have developed two complementary vibrational models to describe the spectra of the OH-stretching regions, a reaction path model and a reduced dimensional local mode model, both of which describe the features of the vibrational spectra well. We also explore the torsional dependence of the OH-stretching transition dipole moment and show that a Franck–Condon treatment fails to capture the intensity in the region of the stretch–torsion combination features. The accuracy of the Franck–Condon treatment of these features improves with increasing ΔvOH.
Research Organization:
Univ. of Washington, Seattle, WA (United States)
Sponsoring Organization:
Carlsberg Foundation; Independent Research Fund Denmark; National Science Foundation; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0021081
OSTI ID:
1853713
Alternate ID(s):
OSTI ID: 1780495
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 16 Vol. 154; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
Fourier transform spectroscopy
Franck Condon factors
gas phase
potential energy surfaces
quantum mechanical calculations
torsional dynamics
transition moment
vibrational spectra