Experimental Evidence of Long-Range Intramolecular
Vibrational Energy Redistribution through Eight Covalent Bonds: NIR
Irradiation Induced Conformational Transformation of E‑Glutaconic Acid
Version 3 2018-04-19, 08:16
Version 2 2017-05-02, 19:05
Version 1 2017-05-02, 19:03
Posted on 2018-04-19 - 08:16
Long-range
intramolecular vibrational energy redistribution (IVR)
driven conformational changes were investigated in a matrix-isolated
open-chain, asymmetrical dicarboxylic acid, E-glutaconic
acid. Although the analysis was challenging due to the presence of
multiple backbone conformers and short lifetimes of the prepared higher
energy cis conformers, it was shown that the selective
excitation of the O–H stretching overtone of one of the carboxylic
groups can induce the conformational change (trans to cis) of the other carboxylic group, located
at the other end of the E-glutaconic acid molecule.
This is a direct proof that the IVR process can act through eight
covalent bonds in a flexible molecule before the excess energy completely
dissipates into the matrix. The lifetime of the prepared higher energy
conformers (averaged over the different backbones) was measured to
be 12 s.
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Kovács, Benjámin; Kuş, Nihal; Tarczay, György; Fausto, Rui (2017). Experimental Evidence of Long-Range Intramolecular
Vibrational Energy Redistribution through Eight Covalent Bonds: NIR
Irradiation Induced Conformational Transformation of E‑Glutaconic Acid. ACS Publications. Collection. https://doi.org/10.1021/acs.jpca.7b00615
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AUTHORS (4)
BK
Benjámin Kovács
NK
Nihal Kuş
GT
György Tarczay
RF
Rui Fausto
KEYWORDS
carboxylic groupsExperimental EvidenceIVR processglutaconic acid moleculeglutaconic acidbackbone conformerslifetimecovalent bondsmatrix-isolated open-chainenergy conformersLong-Range Intramolecular Vibrational Energy RedistributionCovalent Bondsasymmetrical dicarboxylic acidLong-range intramolecular vibrational energy redistributionenergy cis conformersNIR Irradiation Induced Conformational Transformationcarboxylic group