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

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

doi:10.1063/5.0077341

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

Journal Article · 03 January 2022 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/5.0077341 · OSTI ID:1924524

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Univ. of Colorado, Boulder, CO (United States); National Inst. of Standards and Technology (NIST), Boulder, CO (United States); JILA/Department of Chemistry
Cold Quanta, Boulder, CO (United States)
Univ. of Colorado, Boulder, CO (United States); National Inst. of Standards and Technology (NIST), Boulder, CO (United States)

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.

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Research Organization:: University of Colorado, Boulder, CO (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE

Contributing Organization:: NSF(CHE, PHYS)

Grant/Contract Number:: SC0002123

OSTI ID:: 1924524

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 1 Vol. 156; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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

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