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Near-infrared in situ generation of the higher-energy trans conformer of tribromoacetic acid: Observation of a large-scale matrix-site changing mediated by conformational conversion

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Author
Apostolo, Rui F. G.
Bazso, Gabor
Öğrüç Ildız, Gülce
Tarczay, Gyorgy
Fausto, Rui
Type
Article
Date
2018-01-28
Language
en_US
Metadata
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Abstract
The first observation of the higher-energy conformer of tribromoacetic acid (trans-TBAA) is reported. The conformer was produced in cryogenic matrices (Ar, Kr, and N-2) by in situ selective narrowband near-infrared excitation of the lower-energy cis-TBAA conformer and characterized both structurally and vibrationally. The novel trans-TBAA conformer is shown to spontaneously decay to the most stable cis-TBAA form in all studied matrix media, by tunneling, and the measured decay rates in the different matrices were compared with those of the trans conformers of other carboxylic acids in similar experimental conditions. In the N-2 matrix, where trans-TBAA establishes a specific stabilizing intermolecular interaction with the host N-2 molecules via its OH group and is about 11 times more stable than in rare gas matrices, the effect of changing the irradiation wavenumber within the 2 nu OH absorption profile was investigated in detail. An interesting phenomenon of matrix-site changing mediated by conformational conversion was observed in the N-2 matrix: vibrational excitation of cis-TBAA in the 2 nu OH wavenumber range predominantly converts the molecules located in a specific "matrix site" into trans-TBAA; then, relaxation (by tunneling) of the produced higher-energy conformer back to the cis form populates almost exclusively another "matrix site." The experimental studies received support from quantum chemistry calculations, which allowed a detailed characterization of the relevant regions of the potential energy surface of the molecule and the detailed assignment of the infrared spectra of the two conformers in the various matrices. Published by AIP Publishing.
Subject
Correlated Molecular Calculations
1St Experimental-Observation
Disinfection By-Products
Gaussian-Basis Sets
Trifluoroacetic-Acid
Drinking-Water
Formic-Acid
Acetic-Acid
Vibrational Spectroscopy
Rotational-Isomerism
URI
https://doi.org/10.1063/1.5010288
https://hdl.handle.net/11413/2308
Collections
  • Makaleler / Articles [293]
  • Scopus Publications [724]
  • WoS Publications [1016]

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İstanbul Kültür University

Hakkında |Politika | Kütüphane | İletişim | Send Feedback | Admin

Istanbul Kültür University, Ataköy Campus E5 Karayolu Üzeri Bakırköy 34158, İstanbul / TURKEY
Copyright © İstanbul Kültür University

Creative Commons Lisansı
IKU Institutional Repository, Creative Commons Alıntı-GayriTicari-Türetilemez 4.0 Uluslararası Lisansı ile lisanslanmıştır.

Designed by  UNIREPOS