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Title: Infrared spectroscopy of jet-cooled HCCl singlet chlorocarbene diradical: CH stretching and vibrational coupling dynamics

Abstract

Quantum shot noise limited laser absorption methods are used to obtain first high-resolution infrared rovibrational spectra of jet cooled chlorocarbene (HCCl) diradical in a supersonic slit-jet discharge expansion spectrometer. The rotationally resolved absorption spectra of the C–H stretch ν 1 fundamental are analyzed in the framework of a Watson non-rigid asymmetric rotor Hamiltonian model. Further analysis of the mid-infrared data reveals the additional presence of what has nominally been assigned as the $$\tilde x$$(012) combination band with one quantum of the H–C–Cl bend (ν 2) and two quanta of the C–Cl stretch (2ν 3). Rovibrational constants are obtained from least squares fits for each of the four excited vibrational states built on the ν 1 fundamental $$\tilde x$$(100) and the $$\tilde x$$(012) combination mode for each 35Cl and 37Cl atom isotopologue. The four bands occur within a narrow spectral window, requiring detailed comparison of multiple spectral properties (e.g., rotational constant dependence on vibrational excitation, band types/transition dipole moment alignment in the body-fixed frame, etc.) to aid in the vibrational assignment. Indeed, the IR transition intensities arise from strong anharmonic mixing between the “bright” ν 1 C–H stretch and “dark” $$\tilde x$$(012) H–C–Cl bend/C–Cl stretch combination modes, resulting in nearly equal amplitudes for the zeroth order $$\tilde x$$(100) and $$\tilde x$$(012) harmonic states. Lastly, to aid the spectral search for HCCl in the interstellar medium, ground state two-line combination differences are combined with previous laser-induced fluorescence results to predict precision microwave transitions for HC 35Cl and HC 37Cl.

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. National Inst. of Standards and Technology and Univ.of Colorado, Boulder, CO (United States)
Publication Date:
Research Org.:
Univ. of Colorado, Boulder, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1540229
Alternate Identifier(s):
OSTI ID: 1464992
Grant/Contract Number:  
SC0002123; FG02-09ER16021
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 7; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics

Citation Formats

Kortyna, A., and Nesbitt, D. J. Infrared spectroscopy of jet-cooled HCCl singlet chlorocarbene diradical: CH stretching and vibrational coupling dynamics. United States: N. p., 2018. Web. doi:10.1063/1.5039882.
Kortyna, A., & Nesbitt, D. J. Infrared spectroscopy of jet-cooled HCCl singlet chlorocarbene diradical: CH stretching and vibrational coupling dynamics. United States. doi:10.1063/1.5039882.
Kortyna, A., and Nesbitt, D. J. Fri . "Infrared spectroscopy of jet-cooled HCCl singlet chlorocarbene diradical: CH stretching and vibrational coupling dynamics". United States. doi:10.1063/1.5039882. https://www.osti.gov/servlets/purl/1540229.
@article{osti_1540229,
title = {Infrared spectroscopy of jet-cooled HCCl singlet chlorocarbene diradical: CH stretching and vibrational coupling dynamics},
author = {Kortyna, A. and Nesbitt, D. J.},
abstractNote = {Quantum shot noise limited laser absorption methods are used to obtain first high-resolution infrared rovibrational spectra of jet cooled chlorocarbene (HCCl) diradical in a supersonic slit-jet discharge expansion spectrometer. The rotationally resolved absorption spectra of the C–H stretch ν1 fundamental are analyzed in the framework of a Watson non-rigid asymmetric rotor Hamiltonian model. Further analysis of the mid-infrared data reveals the additional presence of what has nominally been assigned as the $\tilde x$(012) combination band with one quantum of the H–C–Cl bend (ν2) and two quanta of the C–Cl stretch (2ν3). Rovibrational constants are obtained from least squares fits for each of the four excited vibrational states built on the ν1 fundamental $\tilde x$(100) and the $\tilde x$(012) combination mode for each 35Cl and 37Cl atom isotopologue. The four bands occur within a narrow spectral window, requiring detailed comparison of multiple spectral properties (e.g., rotational constant dependence on vibrational excitation, band types/transition dipole moment alignment in the body-fixed frame, etc.) to aid in the vibrational assignment. Indeed, the IR transition intensities arise from strong anharmonic mixing between the “bright” ν1 C–H stretch and “dark” $\tilde x$(012) H–C–Cl bend/C–Cl stretch combination modes, resulting in nearly equal amplitudes for the zeroth order $\tilde x$(100) and $\tilde x$(012) harmonic states. Lastly, to aid the spectral search for HCCl in the interstellar medium, ground state two-line combination differences are combined with previous laser-induced fluorescence results to predict precision microwave transitions for HC35Cl and HC37Cl.},
doi = {10.1063/1.5039882},
journal = {Journal of Chemical Physics},
number = 7,
volume = 149,
place = {United States},
year = {2018},
month = {8}
}

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