Formation and detection of metastable formic acid in a supersonic expansion: High resolution infrared spectroscopy of the jet-cooled cis-HCOOH conformer

Doney, Kirstin D.; Kortyna, Andrew; Chan, Ya-Chu; Nesbitt, David J.

doi:10.1063/5.0093401

Title: Formation and detection of metastable formic acid in a supersonic expansion: High resolution infrared spectroscopy of the jet-cooled cis-HCOOH conformer

Abstract

High-resolution direct absorption infrared spectra of metastable cis-formic acid (HCOOH) trapped in a cis-well resonance behind a 15 kcal/mol barrier are reported for the first time, with the energetically unstable conformer produced in a supersonic slit plasma expansion of trans-formic acid/H₂ mixtures. We present a detailed high-resolution rovibrational analysis for cis-formic acid species in the OH stretch (ν₁) fundamental, providing first precision vibrational band origin, rotational constants, and term values, which in conjunction with ab initio calculations at the couple-cluster with single, double, and perturbative triple [CCSD(T)]/ANOn (n = 0, 1, 2) level support the experimental assignments and establish critical points on the potential energy surface for internal rotor trans-to-cis isomerization. Relative intensities for a- and b-type transitions observed in the spectra permit the transition dipole moment components to be determined in the body fixed frame and prove to be in good agreement with ab initio CCSD(T) theoretical estimates but in poor agreement with simple bond-dipole predictions. As a result, the observed signal dependence on H₂ in the discharge suggests the presence of a novel H atom radical chemical mechanism for strongly endothermic “up-hill” internal rotor isomerization between trans- and cis-formic acid conformers.

Authors:

^[1];

^[2];

^[1];

^[1]

Univ. of Colorado, Boulder, CO (United States); National Inst. of Standards and Technology (NIST), Boulder, CO (United States)
Univ. of Colorado, Boulder, CO (United States); National Inst. of Standards and Technology (NIST), Boulder, CO (United States); ColdQuanta, Boulder, CO (United States)

Publication Date:: Wed May 25 00:00:00 EDT 2022

Research Org.:: Univ. of Colorado, Boulder, CO (United States)

Sponsoring Org.:: USDOE; National Science Foundation (NSF)

Contributing Org.:: NSF (PHYS), NIST NRC

OSTI Identifier:: 1924522

Alternate Identifier(s):: OSTI ID: 1869737

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: 156; Journal Issue: 20; 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; Ab-initio methods; Infrared spectroscopy; Plasma expansion; Transition moment; Rotational dynamics; Potential energy surfaces; Isomerization; Acids; Vibrational states; Rotational spectra

Citation Formats


                    Doney, Kirstin D., Kortyna, Andrew, Chan, Ya-Chu, and Nesbitt, David J. Formation and detection of metastable formic acid in a supersonic expansion: High resolution infrared spectroscopy of the jet-cooled cis-HCOOH conformer.  United States: N. p., 2022. 
Web.  doi:10.1063/5.0093401.

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                    Doney, Kirstin D., Kortyna, Andrew, Chan, Ya-Chu, & Nesbitt, David J. Formation and detection of metastable formic acid in a supersonic expansion: High resolution infrared spectroscopy of the jet-cooled cis-HCOOH conformer.  United States.  https://doi.org/10.1063/5.0093401

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                    Doney, Kirstin D., Kortyna, Andrew, Chan, Ya-Chu, and Nesbitt, David J. Wed .  
"Formation and detection of metastable formic acid in a supersonic expansion: High resolution infrared spectroscopy of the jet-cooled cis-HCOOH conformer".  United States.  https://doi.org/10.1063/5.0093401.  https://www.osti.gov/servlets/purl/1924522.

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@article{osti_1924522,

  title        = {Formation and detection of metastable formic acid in a supersonic expansion: High resolution infrared spectroscopy of the jet-cooled cis-HCOOH conformer},

  author       = {Doney, Kirstin D. and Kortyna, Andrew and Chan, Ya-Chu and Nesbitt, David J.},

  abstractNote = {High-resolution direct absorption infrared spectra of metastable cis-formic acid (HCOOH) trapped in a cis-well resonance behind a 15 kcal/mol barrier are reported for the first time, with the energetically unstable conformer produced in a supersonic slit plasma expansion of trans-formic acid/H2 mixtures. We present a detailed high-resolution rovibrational analysis for cis-formic acid species in the OH stretch (ν1) fundamental, providing first precision vibrational band origin, rotational constants, and term values, which in conjunction with ab initio calculations at the couple-cluster with single, double, and perturbative triple [CCSD(T)]/ANOn (n = 0, 1, 2) level support the experimental assignments and establish critical points on the potential energy surface for internal rotor trans-to-cis isomerization. Relative intensities for a- and b-type transitions observed in the spectra permit the transition dipole moment components to be determined in the body fixed frame and prove to be in good agreement with ab initio CCSD(T) theoretical estimates but in poor agreement with simple bond-dipole predictions. As a result, the observed signal dependence on H2 in the discharge suggests the presence of a novel H atom radical chemical mechanism for strongly endothermic “up-hill” internal rotor isomerization between trans- and cis-formic acid conformers.},

  doi          = {10.1063/5.0093401},

  journal      = {Journal of Chemical Physics},

  number       = 20,

  volume       = 156,

  place        = {United States},

  year         = {Wed May 25 00:00:00 EDT 2022},

  month        = {Wed May 25 00:00:00 EDT 2022}

}

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Title: Formation and detection of metastable formic acid in a supersonic expansion: High resolution infrared spectroscopy of the jet-cooled cis-HCOOH conformer

Abstract

Citation Formats

Trans-cis molecular photoswitching in interstellar space journal, November 2016

The Hot Core around the Low-Mass Protostar IRAS 16293-2422: Scoundrels Rule! journal, July 2003

New High-Resolution Analysis of the ν7 and ν9 Fundamental Bands of trans-Formic Acid by Fourier Transform Infrared and Millimeter-Wave Spectroscopy journal, December 2002

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Treatment of Fermi resonance effects on transition moments in vibrational perturbation theory journal, January 2007

The Other Rotamer of Formic Acid, cis-HCOOH1 journal, September 1976

Sub-Doppler laser-Stark and high-resolution Fourier transform spectroscopy of the ν3 band of formic acid journal, February 1987

General contraction of Gaussian basis sets. I. Atomic natural orbitals for first‐ and second‐row atoms journal, April 1987

IR Spectrum of the Other Rotamer of Formic Acid, cis -HCOOH journal, December 1997

High‐resolution laser spectroscopy of the ν 3 vibration‐rotation band of HCOOH journal, July 1982

Rotational Spectra of cis-HCOOH, trans-HCOOH, and trans-H13COOH journal, December 2002

Sub-Doppler Spectroscopy of the trans -HOCO Radical in the OH Stretching Mode journal, June 2013

Basis Set Exchange: A Community Database for Computational Sciences journal, March 2007

High resolution FTIR spectra of the ν9 vibrational band of cis-rotamers HCOOH and H13COOH journal, August 2006

Observations of Formic Acid in Hot Molecular Cores journal, May 2001

Ice absorption features in the 5-8 μ m region toward embedded protostars journal, September 2001

ν7 and ν9 bands of formic acid near 16 μm journal, December 1979

Kinetic and mechanistic study of the hydroxyl + formic acid reaction journal, June 1985

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PGOPHER: A program for simulating rotational, vibrational and electronic spectra journal, January 2017

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Slit pulsed valve for generation of long‐path‐length supersonic expansions journal, May 1987

High-resolution infrared spectroscopy of jet cooled trans -deuteroxycarbonyl ( trans -DOCO) radical journal, May 2019

The high-resolution infrared spectrum of the ν 3 + ν 5 combination band of jet-cooled propyne journal, September 2017

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Trans-cis molecular photoswitching in interstellar space
journal, November 2016

The Hot Core around the Low-Mass Protostar IRAS 16293-2422: Scoundrels Rule!
journal, July 2003

New High-Resolution Analysis of the ν7 and ν9 Fundamental Bands of trans-Formic Acid by Fourier Transform Infrared and Millimeter-Wave Spectroscopy
journal, December 2002

Coupled-cluster techniques for computational chemistry: The CFOUR program package
journal, June 2020

Stabilization and precise calibration of a continuous‐wave difference frequency spectrometer by use of a simple transfer cavity
journal, January 1994

Treatment of Fermi resonance effects on transition moments in vibrational perturbation theory
journal, January 2007

The Other Rotamer of Formic Acid, cis-HCOOH1
journal, September 1976

Sub-Doppler laser-Stark and high-resolution Fourier transform spectroscopy of the ν3 band of formic acid
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General contraction of Gaussian basis sets. I. Atomic natural orbitals for first‐ and second‐row atoms
journal, April 1987

IR Spectrum of the Other Rotamer of Formic Acid, cis -HCOOH
journal, December 1997

High‐resolution laser spectroscopy of the ν ₃ vibration‐rotation band of HCOOH
journal, July 1982

Rotational Spectra of cis-HCOOH, trans-HCOOH, and trans-H13COOH
journal, December 2002

Sub-Doppler Spectroscopy of the trans -HOCO Radical in the OH Stretching Mode
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Basis Set Exchange: A Community Database for Computational Sciences
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High resolution FTIR spectra of the ν9 vibrational band of cis-rotamers HCOOH and H13COOH
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Ice absorption features in the 5-8 μ m region toward embedded protostars
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