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