{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,28]],"date-time":"2026-04-28T02:05:40Z","timestamp":1777341940492,"version":"3.51.4"},"reference-count":47,"publisher":"AIP Publishing","issue":"12","funder":[{"name":"Anadolu University Eskisehir - Turkey","award":["1605F423"],"award-info":[{"award-number":["1605F423"]}]},{"name":"FEDER\/COMPETE 2020 - UE","award":["POCI-01-0145-FEDER-016617"],"award-info":[{"award-number":["POCI-01-0145-FEDER-016617"]}]},{"name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia - Portugal","award":["PTDC\/QEQ-QFI\/3284\/2014"],"award-info":[{"award-number":["PTDC\/QEQ-QFI\/3284\/2014"]}]},{"name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia - Portugal","award":["SFRH\/BPD\/88372\/2012"],"award-info":[{"award-number":["SFRH\/BPD\/88372\/2012"]}]},{"name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia - Portugal","award":["UI0313\/QUI\/2013"],"award-info":[{"award-number":["UI0313\/QUI\/2013"]}]}],"content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2017,3,28]]},"abstract":"<jats:p>DFT(B3LYP)\/6-311++G(d,p) calculations on 2-fluorobenzoic acid (2FBA) show that the molecule has four conformers: two low energy conformers (forms I and II) with the carboxylic acid group assuming the cis configuration (O=C\u2014O\u2014H dihedral equal to 0\u00b0) and two higher-energy conformers (III, IV) with a trans carboxylic group configuration. Isolation of 2FBA monomers in argon or nitrogen matrices allows for the efficient trapping of both low-energy conformers. Narrowband selective near-IR (NIR) excitation of the 2\u03bdOH mode of I in both argon and N2 matrices leads to its efficient conversion into conformer III, which is stabilized by an intramolecular O\u2014H\u00b7\u00b7\u00b7F interaction. On the other hand, upon identical selective vibrational excitation of II no changes could be noticed in the argon matrix spectra, while experiments carried out on N2 matrices showed conversion of II into III. In conformer IV (the expected direct product resulting from NIR excitation of II), the stabilizing O\u2014H\u00b7\u00b7\u00b7F interaction existing in III is replaced by an O\u2014H\u00b7\u00b7\u00b7H repulsive interaction, which leads to a barrier separating this form from II that is about one third of that separating III from I. Under these circumstances, once formed by vibrational excitation of II, conformer IV can easily convert to the reactant species by fast tunneling, justifying the apparent inefficiency of the II\u2008\u2192\u2008IV conversion upon vibrational excitation of II in an argon matrix. On the other hand, the stabilization of the initially formed conformer IV by the N2 matrix (due to OH\u00b7\u00b7\u00b7N2 interactions) allows this species to survive long enough to allow the IV\u2008\u2192\u2008III over-the-barrier conversion to be competitive with the IV\u2008\u2192\u2008II tunneling, justifying the observed net conversion of the NIR excited conformer II into form III in N2 matrix. These results demonstrate as the intramolecular local topology may decisively influence the intrinsic kinetic stability of different conformers of the same molecule. They are also a clear additional evidence of the stabilization of higher-energy trans conformers of carboxylic acids by the N2 matrix medium that has been found before for other molecules of the same family.<\/jats:p>","DOI":"10.1063\/1.4978794","type":"journal-article","created":{"date-parts":[[2017,3,22]],"date-time":"2017-03-22T15:23:56Z","timestamp":1490196236000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":16,"title":["Effects of the matrix and intramolecular interactions on the stability of the higher-energy conformers of 2-fluorobenzoic acid"],"prefix":"10.1063","volume":"146","author":[{"given":"Nihal","family":"Ku\u015f","sequence":"first","affiliation":[{"name":"University of Coimbra 1 CQC, Department of Chemistry, , P-3004-535 Coimbra, Portugal"},{"name":"Anadolu University 2 Department of Physics, , TR-26470 Eski\u015fehir, Turkey"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8264-6854","authenticated-orcid":false,"given":"Rui","family":"Fausto","sequence":"additional","affiliation":[{"name":"University of Coimbra 1 CQC, Department of Chemistry, , P-3004-535 Coimbra, Portugal"}]}],"member":"317","published-online":{"date-parts":[[2017,3,22]]},"reference":[{"key":"2023071803475946100_c1","doi-asserted-by":"publisher","first-page":"2445","DOI":"10.1021\/es961007c","volume":"31","year":"1997","journal-title":"Environ. 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