Rotational Spectroscopy of 2-Furoic Acid and Its Dimer: Conformational Distribution and Double Proton Tunneling.

carboxylic acid conformational landscape double proton transfer non-covalent interaction rotational spectroscopy

Journal

Chemphyschem : a European journal of chemical physics and physical chemistry
ISSN: 1439-7641
Titre abrégé: Chemphyschem
Pays: Germany
ID NLM: 100954211

Informations de publication

Date de publication:
20 06 2022
Historique:
revised: 06 04 2022
received: 17 03 2022
pubmed: 8 4 2022
medline: 23 6 2022
entrez: 7 4 2022
Statut: ppublish

Résumé

Structural and tunneling properties of the 2-furoic acid (FA) monomer and dimer were investigated using rotational spectroscopy and DFT calculations. CREST, a conformational ensemble space exploration tool, was used to identify all possible low-energy conformations of the FA monomer and dimer, followed by the DFT geometry optimization and harmonic frequency calculations. Broadband rotational spectra in the 2-6 and 8-12 GHz regions were recorded in a supersonic jet expansion. The monomeric FA was found to exist dominantly as three different conformers: I, II, and III in a jet, with I and II taking on the cis-COOH configuration while III having the trans-COOH configuration. For the FA dimer, only the I-II conformer was observed experimentally, whereas the symmetric I-I and II-II conformers were not observed because of their zero dipole moments. The analysis of the splittings in the rotational transitions of I-II allowed one to extract the tunneling splitting to be 1056.0(12) MHz. The barrier height was determined to be ∼442 cm

Identifiants

pubmed: 35390214
doi: 10.1002/cphc.202200176
doi:

Substances chimiques

Furans 0
Protons 0
2-furoic acid P577F6494A

Types de publication

Journal Article

Langues

eng

Sous-ensembles de citation

IM

Pagination

e202200176

Subventions

Organisme : University of Alberta
Organisme : Natural Sciences and Engineering Research Council (NSERC) of Canada
Organisme : Compute/Calcul Canada
Organisme : Centro de Supercomputacion de Galicia (CESGA)
Organisme : Basque Government Egonlabur grant
Organisme : H. E. Gunning Research Fellowship
Organisme : Tier I Canada Research Chair in Chirality and Chirality Recognition

Informations de copyright

© 2022 Wiley-VCH GmbH.

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Auteurs

Aran Insausti (A)

Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2, Canada.
Departamento de Química Física, Universidad del País Vasco (UPV/EHU), Barrio Sarriena s/n, 48940, Leioa, Spain.
Instituto Biofisika (UPV/EHU, CSIC), Barrio Sarriena s/n, 48940, Leioa, Spain.

Jiarui Ma (J)

Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2, Canada.

Qian Yang (Q)

Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2, Canada.

Fan Xie (F)

Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2, Canada.
Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, 22607, Hamburg, Germany.

Yunjie Xu (Y)

Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2, Canada.

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