Characterization of Large-Amplitude Motions and Hydrogen Bonding Interactions in the Thiophene–Water Complex by Rotational Spectroscopy

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dc.contributor.authorSilva, Weslley G. D. P.
dc.contributor.authorvan Wijngaarden, Jennifer
dc.date.accessioned2021-10-13T20:48:52Z
dc.date.available2021-10-13T20:48:52Z
dc.date.issued2021-04-21
dc.date.submitted2021-10-12T22:03:21Zen_US
dc.description.abstractThe rotational fingerprint of the thiophene–water complex was investigated for the first time using Fourier transform microwave spectroscopy (7–20 GHz) aided by quantum mechanical calculations. Transitions for a single species were observed and the rotational constants for the parent and 18O isotopomers are consistent with a geometry that is highly averaged over a barrierless large amplitude motion of water that interconverts two equivalent forms corresponding to the global minimum (B2PLYP-D3(BJ)/def2-TZVP). In this effective geometry, the water lies above the thiophene ring close to its σv plane of symmetry. The observed transitions are split by a second water-centered tunneling motion that exchanges its two protons by internal rotation about its C2 axis with a calculated barrier of ~2.7 kJ mol-1 (B2PLYP-D3(BJ)/def2-TZVP). Based on quantum theory of atoms in molecules, non covalent interaction and symmetry-adapted perturbation theory analyses, the observed geometry enables two intermolecular interactions (O–H…π and O–H…S) whose electrostatic and dispersive contributions favour formation of the thiophene-water complex.en_US
dc.description.sponsorshipNSERC RGPIN/0653-2016en_US
dc.identifier.citationSilva, W. G. D. P.; van Wijngaarden, J. Characterization of Large-Amplitude Motions and Hydrogen Bonding Interactions in the Thiophene–Water Complex by Rotational Spectroscopy. J. Phys. Chem. A 2021, 125, 16, 3425–3431en_US
dc.identifier.doi10.1021/acs.jpca.1c02086
dc.identifier.urihttp://hdl.handle.net/1993/36042
dc.language.isoengen_US
dc.publisherThe Journal of Physical Chemistry Aen_US
dc.rightsopen accessen_US
dc.subjectmicrowave spectroscopyen_US
dc.subjectnon-covalent interactionsen_US
dc.subjectquantum chemistry calculationsen_US
dc.subjectmicrosolvationen_US
dc.subjectquantum tunnelingen_US
dc.subjectlarge amplitude motionsen_US
dc.titleCharacterization of Large-Amplitude Motions and Hydrogen Bonding Interactions in the Thiophene–Water Complex by Rotational Spectroscopyen_US
dc.typeArticleen_US
local.author.affiliationFaculty of Scienceen_US
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