Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Proton transfer in short hydrogen bonded complex caused by solvation shell fluctuations: ab initio MD and NMR/UV study of an (OHO)- bonded system. / Pylaeva, Svetlana; Allolio, Christoph; Koeppe, Benjamin; Denisov, Gleb S.; Limbach, Hans-Heinrich; Sebastiani, Daniel; Tolstoy, Peter M.
в: Physical Chemistry Chemical Physics, Том 17, № 6, 2015, стр. 4934-4944.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Proton transfer in short hydrogen bonded complex caused by solvation shell fluctuations: ab initio MD and NMR/UV study of an (OHO)- bonded system
AU - Pylaeva, Svetlana
AU - Allolio, Christoph
AU - Koeppe, Benjamin
AU - Denisov, Gleb S.
AU - Limbach, Hans-Heinrich
AU - Sebastiani, Daniel
AU - Tolstoy, Peter M.
PY - 2015
Y1 - 2015
N2 - We present a joint experimental and quantum chemical study on the influence of solvent dynamics on the protonation equilibrium in a strongly hydrogen bonded phenol-acetate complex in CD2Cl2. Particular attention is given to the correlation of the proton position distribution with the internal conformation of the complex itself and with fluctuations of the aprotic solvent. Specifically, we have focused on a complex formed by 4-nitrophenol and tetraalkylammonium-acetate in CD2Cl2. Experimentally we have used combined low-temperature H-1 and C-13 NMR and UV-vis spectroscopy and showed that a very strong OHO hydrogen bond is formed with proton tautomerism (PhOH center dot center dot center dot-OAc and PhO-center dot center dot center dot HOAc forms, both strongly hydrogen bonded). Computationally, we have employed ab initio molecular dynamics (70 and 71 solvent molecules, with and without the presence of a counter-cation, respectively). We demonstrate that the relative motion of the counter-cation and the "free"
AB - We present a joint experimental and quantum chemical study on the influence of solvent dynamics on the protonation equilibrium in a strongly hydrogen bonded phenol-acetate complex in CD2Cl2. Particular attention is given to the correlation of the proton position distribution with the internal conformation of the complex itself and with fluctuations of the aprotic solvent. Specifically, we have focused on a complex formed by 4-nitrophenol and tetraalkylammonium-acetate in CD2Cl2. Experimentally we have used combined low-temperature H-1 and C-13 NMR and UV-vis spectroscopy and showed that a very strong OHO hydrogen bond is formed with proton tautomerism (PhOH center dot center dot center dot-OAc and PhO-center dot center dot center dot HOAc forms, both strongly hydrogen bonded). Computationally, we have employed ab initio molecular dynamics (70 and 71 solvent molecules, with and without the presence of a counter-cation, respectively). We demonstrate that the relative motion of the counter-cation and the "free"
U2 - 10.1039/c4cp04727c
DO - 10.1039/c4cp04727c
M3 - Article
VL - 17
SP - 4934
EP - 4944
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 6
ER -
ID: 4002864