Elucidating Solvent Effects on Strong Intramolecular Hydrogen Bond: DFT-MD Study of Dibenzoylmethane in Methanol Solution
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-structureSource:
ChemPhysChem, 2019, 20, 21, 2852-2859Publisher:
- Wienheim : Wiley-VCH Verlag GMBH
Funding / projects:
- The structure and dynamics of molecular systems in ground and excited electronic states (RS-MESTD-Basic Research (BR or ON)-172040)
DOI: 10.1002/cphc.201900704
ISSN: 1439-7641; 1439-4235
PubMed: 31544323
WoS: 000491179000001
Scopus: 2-s2.0-85074412934
Collections
Institution/Community
IHTMTY - JOUR AU - Milovanović, Branislav AU - Stanković, Ivana AU - Petković, Milena AU - Etinski, Mihajlo PY - 2019 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/3318 AB - 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 PB - Wienheim : Wiley-VCH Verlag GMBH T2 - ChemPhysChem T1 - Elucidating Solvent Effects on Strong Intramolecular Hydrogen Bond: DFT-MD Study of Dibenzoylmethane in Methanol Solution VL - 20 IS - 21 SP - 2852 EP - 2859 DO - 10.1002/cphc.201900704 ER -
@article{ author = "Milovanović, Branislav and Stanković, Ivana and Petković, Milena and Etinski, Mihajlo", year = "2019", 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", publisher = "Wienheim : Wiley-VCH Verlag GMBH", journal = "ChemPhysChem", title = "Elucidating Solvent Effects on Strong Intramolecular Hydrogen Bond: DFT-MD Study of Dibenzoylmethane in Methanol Solution", volume = "20", number = "21", pages = "2852-2859", doi = "10.1002/cphc.201900704" }
Milovanović, B., Stanković, I., Petković, M.,& Etinski, M.. (2019). Elucidating Solvent Effects on Strong Intramolecular Hydrogen Bond: DFT-MD Study of Dibenzoylmethane in Methanol Solution. in ChemPhysChem Wienheim : Wiley-VCH Verlag GMBH., 20(21), 2852-2859. https://doi.org/10.1002/cphc.201900704
Milovanović B, Stanković I, Petković M, Etinski M. Elucidating Solvent Effects on Strong Intramolecular Hydrogen Bond: DFT-MD Study of Dibenzoylmethane in Methanol Solution. in ChemPhysChem. 2019;20(21):2852-2859. doi:10.1002/cphc.201900704 .
Milovanović, Branislav, Stanković, Ivana, Petković, Milena, Etinski, Mihajlo, "Elucidating Solvent Effects on Strong Intramolecular Hydrogen Bond: DFT-MD Study of Dibenzoylmethane in Methanol Solution" in ChemPhysChem, 20, no. 21 (2019):2852-2859, https://doi.org/10.1002/cphc.201900704 . .