Experimental Evidence of Long-Range Intramolecular Vibrational Energy Redistribution through Eight Covalent Bonds: NIR Irradiation Induced Conformational Transformation of E-Glutaconic Acid

Benjámin Kovács, Nihal Kuş, G. Tarczay, Rui Fausto

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5 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)3392-3400
Number of pages9
JournalJournal of Physical Chemistry A
Volume121
Issue number18
DOIs
Publication statusPublished - May 11 2017

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Covalent bonds
covalent bonds
Irradiation
Dicarboxylic Acids
acids
Molecules
irradiation
Stretching
energy
life (durability)
dicarboxylic acids
matrices
molecules
glutaconic acid
harmonics
excitation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "Experimental Evidence of Long-Range Intramolecular Vibrational Energy Redistribution through Eight Covalent Bonds: NIR Irradiation Induced Conformational Transformation of E-Glutaconic Acid",
abstract = "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.",
author = "Benj{\'a}min Kov{\'a}cs and Nihal Kuş and G. Tarczay and Rui Fausto",
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T1 - Experimental Evidence of Long-Range Intramolecular Vibrational Energy Redistribution through Eight Covalent Bonds

T2 - NIR Irradiation Induced Conformational Transformation of E-Glutaconic Acid

AU - Kovács, Benjámin

AU - Kuş, Nihal

AU - Tarczay, G.

AU - Fausto, Rui

PY - 2017/5/11

Y1 - 2017/5/11

N2 - 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.

AB - 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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