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Title: High-resolution infrared spectroscopy of supersonically cooled singlet carbenes: Bromomethylene (HCBr) in the CH stretch region

Abstract

First high-resolution spectra of cold (~35 K) singlet bromomethylene HCBr in the CH stretching (v1) region from 2770 to 2850 cm-1 are reported using near quantum shot-noise limited laser absorption methods in a slit jet supersonic discharge expansion source. Three rovibrational bands are identified at high S/N (20:1 - 40:1) and rotationally assigned to i) the CH stretch fundamental (v1) band $$\tilde{X}$$(1,0,0) ← $$\tilde{X}$$ (0,0,0) and ii) vibrational hot bands ($$\tilde{X}$$(1,1,0) ← $$\tilde{X}$$(0,1,0) and $$\tilde{X}$$(1,0,1) ← $$\tilde{X}$$(0,0,1)) arising from vibrationally excited HCBr populated in the discharge with single quanta in either the H–C–Br bend (v2) or C–Br stretch (v3) modes. Precision rotational constants are reported for a total of six states, with an experimentally determined CH stretch vibrational frequency (2799.38 cm-1) in good agreement with previous low-resolution fluorescence studies. Detailed analysis of the fundamental v1 band highlights the presence of perturbations in the $$\tilde{X}$$(1,0,0) level, which we tentatively attribute to arise from the nearby triplet state $$\tilde{a}$$(0,0,1) through spin-orbit interaction or the multiple quanta $$\tilde{X}$$(0,2,1) singlet state via c-type Coriolis coupling. Reduced-Doppler resolution (60 MHz) in the slit-jet IR spectrometer permits clear observation of nuclear spin hyperfine structure, with experimental line shapes well reproduced by nuclear quadrupole/spin-rotation coupling constants from microwave studies. Lastly, the a-type to b-type transition intensity ratio for the fundamental CH stretch band is notably larger than predicted by a bond-dipole model, which from high level ab initio quantum calculations (CCSD(T)/PVQZ) can be attributed to vibrationally induced “charge-sloshing” of electron density along the polar C–Br bond.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Colorado, Boulder, CO (United States); National Inst. of Standards and Technology (NIST), Boulder, CO (United States)
  2. Cold Quanta, Boulder, CO (United States)
Publication Date:
Research Org.:
Univ. of Colorado, Boulder, CO (United States)
Sponsoring Org.:
USDOE; National Science Foundation (NSF)
Contributing Org.:
NSF(CHE, PHYS)
OSTI Identifier:
1924524
Alternate Identifier(s):
OSTI ID: 1838207
Grant/Contract Number:  
SC0002123; FG02-09ER16021; CHE 1665271/2053117; PHY 1734006
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 156; 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; Triplet state; Free radicals; Infrared spectroscopy; Spin-orbit interactions; Hyperfine structure; Coriolis effects; Quantum molecular calculations; Fluorescence; Rotational spectra

Citation Formats

Chan, Ya-Chu, Kortyna, Andrew, and Nesbitt, David J. High-resolution infrared spectroscopy of supersonically cooled singlet carbenes: Bromomethylene (HCBr) in the CH stretch region. United States: N. p., 2022. Web. doi:10.1063/5.0077341.
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Chan, Ya-Chu, Kortyna, Andrew, & Nesbitt, David J. High-resolution infrared spectroscopy of supersonically cooled singlet carbenes: Bromomethylene (HCBr) in the CH stretch region. United States. https://doi.org/10.1063/5.0077341
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Chan, Ya-Chu, Kortyna, Andrew, and Nesbitt, David J. Tue . "High-resolution infrared spectroscopy of supersonically cooled singlet carbenes: Bromomethylene (HCBr) in the CH stretch region". United States. https://doi.org/10.1063/5.0077341. https://www.osti.gov/servlets/purl/1924524.
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@article{osti_1924524,
title = {High-resolution infrared spectroscopy of supersonically cooled singlet carbenes: Bromomethylene (HCBr) in the CH stretch region},
author = {Chan, Ya-Chu and Kortyna, Andrew and Nesbitt, David J.},
abstractNote = {First high-resolution spectra of cold (~35 K) singlet bromomethylene HCBr in the CH stretching (v1) region from 2770 to 2850 cm-1 are reported using near quantum shot-noise limited laser absorption methods in a slit jet supersonic discharge expansion source. Three rovibrational bands are identified at high S/N (20:1 - 40:1) and rotationally assigned to i) the CH stretch fundamental (v1) band $\tilde{X}$(1,0,0) ← $\tilde{X}$ (0,0,0) and ii) vibrational hot bands ($\tilde{X}$(1,1,0) ← $\tilde{X}$(0,1,0) and $\tilde{X}$(1,0,1) ← $\tilde{X}$(0,0,1)) arising from vibrationally excited HCBr populated in the discharge with single quanta in either the H–C–Br bend (v2) or C–Br stretch (v3) modes. Precision rotational constants are reported for a total of six states, with an experimentally determined CH stretch vibrational frequency (2799.38 cm-1) in good agreement with previous low-resolution fluorescence studies. Detailed analysis of the fundamental v1 band highlights the presence of perturbations in the $\tilde{X}$(1,0,0) level, which we tentatively attribute to arise from the nearby triplet state $\tilde{a}$(0,0,1) through spin-orbit interaction or the multiple quanta $\tilde{X}$(0,2,1) singlet state via c-type Coriolis coupling. Reduced-Doppler resolution (60 MHz) in the slit-jet IR spectrometer permits clear observation of nuclear spin hyperfine structure, with experimental line shapes well reproduced by nuclear quadrupole/spin-rotation coupling constants from microwave studies. Lastly, the a-type to b-type transition intensity ratio for the fundamental CH stretch band is notably larger than predicted by a bond-dipole model, which from high level ab initio quantum calculations (CCSD(T)/PVQZ) can be attributed to vibrationally induced “charge-sloshing” of electron density along the polar C–Br bond.},
doi = {10.1063/5.0077341},
journal = {Journal of Chemical Physics},
number = 1,
volume = 156,
place = {United States},
year = {Tue Jan 04 00:00:00 EST 2022},
month = {Tue Jan 04 00:00:00 EST 2022}
}
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Works referenced in this record:

Laser excitation and dispersed fluorescence spectra of the HCBr ÖX̃ vibronic transition
journal, July 2001

  • Tsai, Tsung-Chuan; Chen, Chun-Wei; Chang, Bor-Chen
  • The Journal of Chemical Physics, Vol. 115, Issue 2
  • DOI: 10.1063/1.1379583

Prying Apart a Water Molecule with Anionic H-Bonding:  A Comparative Spectroscopic Study of the X - ·H 2 O (X = OH, O, F, Cl, and Br) Binary Complexes in the 600−3800 cm -1 Region
journal, April 2006

  • Roscioli, Joseph R.; Diken, Eric G.; Johnson, Mark A.
  • The Journal of Physical Chemistry A, Vol. 110, Issue 15
  • DOI: 10.1021/jp056022v

Lifetime lengthening and the Renner–Teller effect in the HCF (Ã1A″←X̃1A′) system
journal, September 2003

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

  • Matthews, Devin A.; Cheng, Lan; Harding, Michael E.
  • The Journal of Chemical Physics, Vol. 152, Issue 21
  • DOI: 10.1063/5.0004837

Direct IR laser absorption spectroscopy of jet‐cooled CO 2 HF complexes: Analysis of the ν 1 HF stretch and a surprisingly low frequency ν 6 intermolecular CO 2 bend
journal, May 1987

  • Lovejoy, Christopher M.; Schuder, Michael D.; Nesbitt, David J.
  • The Journal of Chemical Physics, Vol. 86, Issue 10
  • DOI: 10.1063/1.452559

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

  • Riedle, E.; Ashworth, S. H.; Farrell, J. T.
  • Review of Scientific Instruments, Vol. 65, Issue 1
  • DOI: 10.1063/1.1144744

Rigid bender analysis of van der Waals complexes: The intermolecular bending potential of a hydrogen bond
journal, April 1992

  • Nesbitt, David J.; Lovejoy, Christopher M.
  • The Journal of Chemical Physics, Vol. 96, Issue 8
  • DOI: 10.1063/1.462670

A Molecular Beam Microwave Fourier Transform (MB-MWFT) Spectrometer with an Electric Discharge Nozzle
journal, October 1991

  • Grabow, J. -U.; Heineking, N.; Stahl, W.
  • Zeitschrift für Naturforschung A, Vol. 46, Issue 10
  • DOI: 10.1515/zna-1991-1012

Methylene: A study of the X ̃  3 B 1 and a ̃  1 A 1 states by photoelectron spectroscopy of CH − 2 and CD − 2
journal, November 1985

  • Leopold, Doreen G.; Murray, Kermit K.; Miller, Amy E. Stevens
  • The Journal of Chemical Physics, Vol. 83, Issue 10
  • DOI: 10.1063/1.449746

High-resolution determination of the electron affinity of fluorine and bromine using crossed ion and laser beams
journal, October 1989

New electronic spectra of the HCCl and DCCl Ã-X̃ vibronic bands
journal, September 2004

  • Lin, Chia-Shih; Chen, Ying-En; Chang, Bor-Chen
  • The Journal of Chemical Physics, Vol. 121, Issue 9
  • DOI: 10.1063/1.1779572

Catalytic Asymmetric C−H Activation of Alkanes and Tetrahydrofuran
journal, March 2000

  • Davies, Huw M. L.; Hansen, Tore; Churchill, Melvyn Rowen
  • Journal of the American Chemical Society, Vol. 122, Issue 13
  • DOI: 10.1021/ja994136c

High-resolution infrared spectra of vibrationally excited HC4H in a supersonic hydrocarbon plasma jet
journal, February 2014

  • Zhao, Dongfeng; Doney, Kirstin D.; Linnartz, Harold
  • Journal of Molecular Spectroscopy, Vol. 296
  • DOI: 10.1016/j.jms.2013.11.008

High resolution near‐infrared electronic spectroscopy of HCBr
journal, August 1996

  • Chang, Bor‐Chen; Sears, Trevor J.
  • The Journal of Chemical Physics, Vol. 105, Issue 6
  • DOI: 10.1063/1.472086

Towards a global model of spin-orbit coupling in the halocarbenes
journal, June 2015

  • Nyambo, Silver; Karshenas, Cyrus; Reid, Scott A.
  • The Journal of Chemical Physics, Vol. 142, Issue 21
  • DOI: 10.1063/1.4921466

Quantum Variational Calculations for a Range of C H 2 Configurations
journal, April 1960

The halocarbenes: model systems for understanding the spectroscopy, dynamics and chemistry of carbenes
journal, July 2009

  • Kable, Scott H.; Reid, Scott A.; Sears, Trevor J.
  • International Reviews in Physical Chemistry, Vol. 28, Issue 3
  • DOI: 10.1080/01442350903087792

Indiscriminate Reaction of Methylene with the Carbon-Hydrogen bond
journal, July 1956

  • von E. Doering, W.; Buttery, R. G.; Laughlin, R. G.
  • Journal of the American Chemical Society, Vol. 78, Issue 13
  • DOI: 10.1021/ja01594a071

Fluorescence excitation and single vibronic level emission spectroscopy of the ÃA″1←X̃A′1 system of CHCl
journal, June 2006

  • Tao, Chong; Mukarakate, Calvin; Reid, Scott A.
  • The Journal of Chemical Physics, Vol. 124, Issue 22
  • DOI: 10.1063/1.2204916

Collision-induced vibrational energy transfer in small polyatomic molecules
journal, November 1987

  • Orr, Brian J.; Smith, Ian W. M.
  • The Journal of Physical Chemistry, Vol. 91, Issue 24
  • DOI: 10.1021/j100308a013

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

First observation of the elusive iodocarbene: ground state multiplicity and singlet–triplet gap of CHI
journal, January 2008

  • Tao, Chong; Ebben, Carlena; Ko, Hsiang-Ting
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 40
  • DOI: 10.1039/b812734d

Total Synthesis of Iejimalide A−D and Assessment of the Remarkable Actin-Depolymerizing Capacity of These Polyene Macrolides
journal, June 2007

  • Fürstner, Alois; Nevado, Cristina; Waser, Mario
  • Journal of the American Chemical Society, Vol. 129, Issue 29
  • DOI: 10.1021/ja072334v

Collision-induced energy flow between vibrational modes of small polyatomic molecules
journal, November 1981

Photodissociation of Bromoform at 248 nm:  Single and Multiphoton Processes
journal, March 2004

  • Zou, Peng; Shu, Jinian; Sears, Trevor J.
  • The Journal of Physical Chemistry A, Vol. 108, Issue 9
  • DOI: 10.1021/jp0310394

Bismacrocyclic Inhibitors of Hepatitis C NS3/4a Protease
journal, November 2008

  • McCauley, John A.; Rudd, Michael T.; Nguyen, Kevin T.
  • Angewandte Chemie International Edition, Vol. 47, Issue 47
  • DOI: 10.1002/anie.200803298

High-resolution infrared spectroscopy of HCF in the CH stretch region
journal, January 2020

  • Doney, Kirstin D.; Kortyna, Andrew; Nesbitt, David J.
  • The Journal of Chemical Physics, Vol. 152, Issue 1
  • DOI: 10.1063/1.5133397

Role of Spin−Orbit Coupling and Symmetry in Triplet Carbenic Addition Chemistry
journal, January 1996

  • Su, Ming-Der
  • The Journal of Physical Chemistry, Vol. 100, Issue 11
  • DOI: 10.1021/jp950290j

Experimental and theoretical studies of the near-infrared spectrum of bromomethylene
journal, September 2001

  • Yu, Hua-Gen; Gonzalez-Lezana, Tomas; Marr, Andrew J.
  • The Journal of Chemical Physics, Vol. 115, Issue 12
  • DOI: 10.1063/1.1386812

Methylene: A Paradigm for Computational Quantum Chemistry
journal, March 1986

Fluorescence excitation and emission spectroscopy of the ÃA″1←X̃A′1 system of CHBr
journal, April 2006

  • Deselnicu, Mihaela; Tao, Chong; Mukarakate, Calvin
  • The Journal of Chemical Physics, Vol. 124, Issue 13
  • DOI: 10.1063/1.2183302

Anharmonicities and Isotopic Effects in the Vibrational Spectra of X − ·H 2 O, ·HDO, and ·D 2 O [X = Cl, Br, and I] Binary Complexes †
journal, January 2010

  • Horvath, Samantha; McCoy, Anne B.; Elliott, Ben M.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 3
  • DOI: 10.1021/jp9088782

Hot bands in the spectrum of HCBr
journal, May 2003

The Reactivity of Methylene from Photolysis of Diazomethane
journal, September 1960

  • Richardson, Davis B.; Simmons, M. C.; Dvoretzky, Isaac
  • Journal of the American Chemical Society, Vol. 82, Issue 18
  • DOI: 10.1021/ja01503a062

The Role of Electrical Anharmonicity in the Association Band in the Water Spectrum
journal, April 2014

  • McCoy, Anne B.
  • The Journal of Physical Chemistry B, Vol. 118, Issue 28
  • DOI: 10.1021/jp501647e

Vibrational excitation and relaxation of five polyatomic molecules in an electrical discharge
journal, May 2005

  • Sanz, M. Eugenia; McCarthy, Michael C.; Thaddeus, Patrick
  • The Journal of Chemical Physics, Vol. 122, Issue 19
  • DOI: 10.1063/1.1869988

Ab initio potential energy surface and vibrational frequencies of Ã(1A″) HCF
journal, July 1998

New dispersed fluorescence spectra of HCBr and DCBr
journal, September 2005

Angular momentum dependence of first‐ and second‐order singlet‐triplet interactions in polyatomic molecules
journal, April 1973

  • Stevens, Charles G.; Brand, John C. D.
  • The Journal of Chemical Physics, Vol. 58, Issue 8
  • DOI: 10.1063/1.1679659

Enhancement of infrared activity by moving electrons through bonds – The case of CO2 anion and carboxylate
journal, September 2017

High resolution study of spin-orbit mixing and the singlet-triplet gap in chlorocarbene: Stimulated emission pumping spectroscopy of CH35Cl and CD35Cl
journal, September 2008

  • Tao, Chong; Mukarakate, Calvin; Terranova, Zack
  • The Journal of Chemical Physics, Vol. 129, Issue 10
  • DOI: 10.1063/1.2977686

Visible absorption and magnetic‐rotation spectroscopy of 1 CH 2 : Analysis of the 1 A 1 state and the 1 A 1 – 3 B 1 coupling
journal, February 1987

  • Petek, Hrvoje; Nesbitt, David J.; Moore, C. Bradley
  • The Journal of Chemical Physics, Vol. 86, Issue 3
  • DOI: 10.1063/1.452264

Rotational spectrum of HCBr produced by 193-nm laser photolysis of bromoform
journal, July 2003

High-resolution infrared studies in slit supersonic discharges: CH2 stretch excitation of jet-cooled CH2Cl radical
journal, August 2006

  • Whitney, Erin S.; Haeber, Thomas; Schuder, Michael D.
  • The Journal of Chemical Physics, Vol. 125, Issue 5
  • DOI: 10.1063/1.2208612

An experimental and theoretical study on rotational constants of vibrationally excited CH2OO
journal, February 2015

Magnetic properties of the A ̃  1 A ″ state of HCF
journal, May 1984

  • Butcher, R. J.; Saito, Shuji; Hirota, Eizi
  • The Journal of Chemical Physics, Vol. 80, Issue 9
  • DOI: 10.1063/1.447271

Divalent Carbon Intermediates: Laser Photolysis and Spectroscopy
journal, September 1984

Rotationally Resolved Near-Infrared Spectrum of the HCCI Ã1A″ ← X̃1A′ Transition
journal, October 1995

Methylene: ab initio vibronic analysis and reinterpretation of the spectroscopic and negative ion photoelectron experiments
journal, April 1978

Near-Infrared Spectroscopy of Bromomethylene in a Slit-Jet Expansion
journal, July 2000

  • Chang, Bor-Chen; Costen, Matthew L.; Marr, Andrew J.
  • Journal of Molecular Spectroscopy, Vol. 202, Issue 1
  • DOI: 10.1006/jmsp.2000.8116
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