Reactive intermediates in 4He nanodroplets: Infrared laser Stark spectroscopy of dihydroxycarbene

Broderick, Bernadette M.; McCaslin, Laura; Moradi, Christopher P.; Stanton, John F.; Douberly, Gary E.

doi:10.1063/1.4917421

Reactive intermediates in ⁴He nanodroplets: Infrared laser Stark spectroscopy of dihydroxycarbene

Journal Article · Tue Apr 14 00:00:00 EDT 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4917421· OSTI ID:1409052

Broderick, Bernadette M. ^[1]; ^[2]; Moradi, Christopher P. ^[3]; Stanton, John F. ^[2]; ^[3]

Univ. of Georgia, Athens, GA (United States); University of Georgia, Athens, GA
Univ. of Texas at Austin, Austin, TX (United States)
Univ. of Georgia, Athens, GA (United States)

Singlet dihydroxycarbene (HO$$\ddot C$$OH) is produced via pyrolytic decomposition of oxalic acid, captured by helium nanodroplets, and probed with infrared laser Stark spectroscopy. Rovibrational bands in the OH stretch region are assigned to either trans, trans-or trans, cis-rotamers on the basis of symmetry type, nuclear spin statistical weights, and comparisons to electronic structure theory calculations. Stark spectroscopy provides the inertial components of the permanent electric dipole moments for these rotamers. The dipole components for trans, trans-and trans, cis-rotamers are (μ_a, μ_b) = (0.00,0.68(6)) and (1.63(3), 1.50(5)), respectively. The infrared spectra lack evidence for the higher energy cis,cis-rotamer, which is consistent with a previously proposed pyrolytic decomposition mechanism of oxalic acid and computations of HO$$\ddot C$$OH torsional interconversion and tautomerization barriers.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Georgia Research Foundation, Athens, GA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0008086

OSTI ID:: 1409052

Alternate ID(s):: OSTI ID: 1228594
OSTI ID: 22415640

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 14 Vol. 142; ISSN 0021-9606

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

Country of Publication:: United States

Language:: English

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