Title: High-resolution infrared spectroscopy of HCF in the CH stretch region

Abstract

We present the results from a high-resolution infrared study of jet-cooled singlet monofluorocarbene (HCF) in the CH stretch region near 2600 cm^-1. Absorption signals are recorded using near quantum shot noise limited laser absorption methods. The fully resolved absorption spectra of the CH stretch (ν1) fundamental band and a partial progression of transitions of the HCF bend plus CF stretch (ν₂ + ν₃) combination band are observed and show clear evidence of a strong rovibrational coupling between the ν₁ $$K^{'}_{a}$$ = 2 and ν₂ + ν₃ $$K^{'}_{a}$$ = 3 manifolds, including the observation of “dark state” transitions. A detailed perturbation analysis of a c-type Coriolis interaction is carried out for these two coupled vibrational states, providing experimental determination of precise rovibrational constants. A combined ground state combination difference fit of the transitions to the ν₁ and ν₂ + ν₃ vibrational states in this study with previously reported LIF Ã(0,0,0) ← $$\tilde {X}$$(0,0,0) data has been done to increase the accuracy of the ground state rotational constants [M. Kakimoto et al., J. Mol. Spec. 88, 300–310 (1981)]. Moreover, we report, for the first time, hot band (ν₁ + ν₃ ← ν₃) transitions due to vibrationally excited HCF in the CF stretch mode, ν₃. The high-resolution results for all vibrational frequencies and rotational constants are in good agreement with and significantly extend the analysis of the rovibrational manifold of HCF. Finally, the present ground state and ν₃ spectroscopic parameters now permit improved predictions for pure rotational and ν₃ fundamental transitions to aid spectral searches for HCF in the laboratory and the interstellar medium.

Authors:

Doney, Kirstin D.  ^[1];

• Search DOE PAGES for author "Doney, Kirstin D."
• Search DOE PAGES for ORCID "0000-0002-9829-0346"

Kortyna, Andrew  ^[1];

• Search DOE PAGES for author "Kortyna, Andrew"
• Search DOE PAGES for ORCID "0000-0002-8911-6864"

Nesbitt, David J.  ^[1]

• Search DOE PAGES for author "Nesbitt, David J."
• Search DOE PAGES for ORCID "0000-0001-5365-1120"

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+ Show Author Affiliations

1. Univ. of Colorado, Boulder, CO (United States)

Publication Date:

Tue Jan 07 00:00:00 EST 2020

Research Org.:

Univ. of Colorado, Boulder, CO (United States)

Sponsoring Org.:

USDOE Office of Science (SC); National Science Foundation (NSF)

OSTI Identifier:

1801532

Alternate Identifier(s):

OSTI ID: 1581041; OSTI ID: 1924530

Grant/Contract Number:  

SC0002123; FG02-09ER16021; CHE-1665271; PHY-1734006

Resource Type:

Accepted Manuscript

Journal Name:

Journal of Chemical Physics

Additional Journal Information:

Journal Volume: 152; Journal Issue: 1; 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