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Elucidating Solvent Effects on Strong Intramolecular Hydrogen Bond: DFT-MD Study of Dibenzoylmethane in Methanol Solution

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2019
Authors
Milovanović, Branislav
Stanković, Ivana
Petković, Milena
Etinski, Mihajlo
Article (Published version)
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Abstract
The dynamic aspect of solvation plays a crucial role in determining properties of strong intramolecular hydrogen bonds since solvent fluctuations modify instantaneous hydrogen‐bonded proton transfer barriers. Previous studies pointed out that solvent‐solute interactions in the first solvation shell govern the position of the proton but the ability of the electric field due to other solvent molecules to localize the proton remains an important issue. In this work, we examine the structure of the O−H⋅⋅⋅O intramolecular hydrogen bond of dibenzoylmethane in methanol solution by employing density functional theory‐based molecular dynamics and quantum chemical calculations. Our computations showed that homogeneous electric fields with intensities corresponding to those found in polar solvents are able to considerably alter the proton transfer barrier height in the gas phase. In methanol solution, the proton position is correlated with the difference in electrostatic potentials on the oxygen ...atoms of dibenzoylmethane even when dibenzoylmethane‐methanol hydrogen bonding is lacking. On a timescale of our simulation, the hydrogen bonding and solvent electrostatics tend to localize the proton on different oxygen atoms. These findings provide an insight into the importance of the solvent electric field on the structure of a strong intramolecular hydrogen bond

Keywords:
density functional theory / hydrogen bond / molecular dynamics / proton transfer / solvation / molecular-dynamics simulation / liquid-methanol / fluctuations / ab-initio mb / proton-transfer / low-barrier / noncovalent interactions / crystal-structure / electric-fields / symmetry / crystal-structure
Source:
ChemPhysChem, 2019, 20, 21, 2852-2859
Publisher:
  • Wienheim : Wiley-VCH Verlag GMBH
Projects:
  • The structure and dynamics of molecular systems in ground and excited electronic states (RS-172040)

DOI: 10.1002/cphc.201900704

ISSN: 1439-7641; 1439-4235

PubMed: 31544323

WoS: 000491179000001

Scopus: 2-s2.0-85074412934
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URI
http://cer.ihtm.bg.ac.rs/handle/123456789/3318
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