Polar solvent fluctuations drive proton transfer in hydrogen bonded complexes of carboxylic acid with pyridines: NMR, IR and ab initio MD study

2017 ◽  
Vol 19 (2) ◽  
pp. 1010-1028 ◽  
Author(s):  
B. Koeppe ◽  
S. A. Pylaeva ◽  
C. Allolio ◽  
D. Sebastiani ◽  
E. T. J. Nibbering ◽  
...  
Keyword(s):  
Carboxylic Acid ◽  
Proton Transfer ◽  
Ir Spectra ◽  
Ab Initio ◽  
Polar Solvent ◽  
Chloroacetic Acid ◽  
Nitrogen Bases ◽  
Ab Initio Md ◽  
Bonded Complexes ◽  
Dual Bands

Dual bands in IR spectra show that an ensemble of short-living solvatomers creates a dual-maximum distribution of proton positions in a series of strongly OHN-bonded complexes of chloroacetic acid with nitrogen bases in CD2Cl2.

Proton transfer in a short hydrogen bond caused by solvation shell fluctuations: an ab initio MD and NMR/UV study of an (OHO)− bonded system

2015 ◽  
Vol 17 (6) ◽  
pp. 4634-4644 ◽  
Author(s):  
Svetlana Pylaeva ◽  
Christoph Allolio ◽  
Benjamin Koeppe ◽  
Gleb S. Denisov ◽  
Hans-Heinrich Limbach ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Proton Transfer ◽  
Ab Initio ◽  
Aprotic Solvent ◽  
Solvation Shell ◽  
System P ◽  
Polar Aprotic Solvent ◽  
Short Hydrogen Bond ◽  
Ab Initio Md ◽  
Double Well Potential

The polar aprotic solvent fluctuations in the first solvation shell lead to a double-well potential and proton tautomerism in a low-barrier hydrogen bond.

scholarly journals Vibrational spectroscopic studies of hydrogen‒bonded complexes between 2,5-dihydroxy-P-benzoquinone and amines

2001 ◽  
Vol 15 (1) ◽  
pp. 33-44 ◽  
Author(s):  
MoustafaM. Habeeb ◽  
Hoda A. Al-Wakil ◽  
Aly El-Dissouky ◽  
Nesrine M. Refat
Keyword(s):  
Ir Spectra ◽  
Critical Behavior ◽  
Spectroscopic Studies ◽  
Base Line ◽  
Ir Absorption ◽  
Deep Minimum ◽  
Nitrogen Bases ◽  
Ft Ir ◽  
Bonded Complexes ◽  
Hydrogen Bonded

A series of 1 :1 hydrogen-bonded complexes between 2,5-dihydroxy-P-benzoquinone (DHBQ) and various nitrogen bases of different strengths were prepared. The FT-IR spectra of the prepared complexes were examined in different regions. It has been found that the protonic and carbonyl vibrations are strongly affected by protonation. The intensity of protonic vibrations was estimated, the base line was corrected by using Perkin-Elmer Paragon 1000 program. A maximum was found at pKa= 5.6 in the correlation between the intensity and pKa(amines) suggesting a critical behavior. The same value was located as a deep minimum in the correlation between the center of gravity of the protonic vibrations, vcgcm−1, and the pKaof the amines confirming the critical behavior in some of the studied complexes. The effect of the contribution of the second OH group to the IR absorption profile was discussed. Finally, the FT-IR spectra of some deuterated complexes were presented and analysed.

Correlations between ab initio and experimental data for isolated H-bonded complexes of water with nitrogen bases

1997 ◽  
Vol 410-411 ◽  
pp. 315-322 ◽  
Author(s):  
G. Maes ◽  
J. Smets ◽  
L. Adamowicz ◽  
W. McCarthy ◽  
M.K. Van Bael ◽  
...  
Keyword(s):  
Experimental Data ◽  
Ab Initio ◽  
Nitrogen Bases ◽  
Bonded Complexes

Pressure Dependence of the Proton Transfer Equilibrium in Hydrogen Bonded Complexes

1986 ◽  
Vol 41 (1-2) ◽  
pp. 225-229 ◽  
Author(s):  
Mariusz Maćkowiak ◽  
Piotr Kozioł ◽  
Jan Stankowski
Keyword(s):  
Hydrogen Bond ◽  
Proton Transfer ◽  
Pressure Dependence ◽  
Pressure Coefficient ◽  
Nitrogen Bases ◽  
Single Well ◽  
Double Well Potential ◽  
Bonded Complexes ◽  
Hydrogen Bonded

35Cl NQR measurements were carried out on complexes of pentachlorophenol with nitrogen bases as a function of pressure (up to 300 MPa) and of temperature. It is shown that the sign and magnitude of the pressure coefficient of the 35Cl NQR frequency is related to the degree of proton transfer. An anomaly in the pressure coefficient of ν (35Cl) has been observed near 50% of the proton transfer in the hydrogen bond. This anomaly is discussed assuming that the proton transfer equilibrium is pressure dependent. The fact that the transition from the double-well potential of the hydrogen bond to the single-well potential occurs in the critical manner is also taken into account.

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