Proton polarizability, dipole moment, and proton transitions of an AH...B .dblharw. A-...H+B proton-transfer hydrogen bond as a function of an external electrical field: an ab initio SCF treatment

1987 ◽  
Vol 91 (20) ◽  
pp. 5170-5177 ◽  
Author(s):  
Michael. Eckert ◽  
Georg. Zundel
Keyword(s):  
Hydrogen Bond ◽  
Dipole Moment ◽  
Proton Transfer ◽  
Ab Initio ◽  
Electrical Field ◽  
External Electrical Field

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.

Ab initio study of the structure of the hydrogen maleate anion

1993 ◽  
Vol 71 (3) ◽  
pp. 303-306 ◽  
Author(s):  
Miguel A. Ríos ◽  
Jesús Rodríguez
Keyword(s):  
Hydrogen Bond ◽  
Proton Transfer ◽  
Ab Initio ◽  
Electron Correlation ◽  
Basis Set ◽  
Ab Initio Methods ◽  
Ab Initio Study ◽  
Barrier Heights ◽  
Minimum Potential ◽  
Complete Optimization

The hydrogen maleate ion was studied by ab initio methods with complete optimization at the 3-21G, 6-31G, 6-31G**, and 6-31+G(2d,1p) levels. To study the influence of electron correlation, MP2 calculations have been done for the 6-31G** geometry. All calculations at the HF level predicted an asymmetric hydrogen bond with a double minimum potential governing transfer between the two equivalent structures. Moreover, both asymmetry and proton transfer barrier increase systematically with the power of the basis set used, with calculated barrier heights of 0.12 (3-21G), 1.59 (6-31G), 1.64 (6-31G**), and 2.00 kcal/mol (6-31+G). Only the introduction of the electron correlation at the MP2 level seems to predict a single minimum potential.

Characterization of low-barrier hydrogen bonds. 3. Hydrogen maleate. An ab initio and DFT investigation

1997 ◽  
Vol 75 (9) ◽  
pp. 1195-1202 ◽  
Author(s):  
Michael A. McAllister
Keyword(s):  
Density Functional Theory ◽  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Proton Transfer ◽  
Ab Initio ◽  
Bond Energy ◽  
Density Functional ◽  
Hydrogen Bond Energy ◽  
Functional Theory ◽  
Low Barrier Hydrogen Bonds

High-level ab initio molecular orbital and density functional theory calculations predict the existence of a very short-strong hydrogen bond in the monoanion of maleic acid (hydrogen maleate). At all levels of theory (HF, MP2, BLYP, and B3LYP) except B3PW91 the potential energy surface is predicted to contain two minima, and hence resembles a double well. The barrier to proton transfer via a symmetrical transition state is calculated to be very small at all levels of theory. In all cases the calculated zero point vibrational energy available to the system is larger than the calculated barrier for proton transfer, thus the resulting hydrogen bond formed in hydrogen maleate is predicted to be symmetrical. Using the B3PW91 functional and the 6-31 + G(d,p) basis set results in a single-well potential and a symmetrically positioned hydrogen. All correlated methods predict the gas phase hydrogen bond energy to be approximately 27 kcal/mol. Effects due to solvents were estimated using solvent cavity methods. Approximating the solvent as a dielectric continuum reduces the calculated hydrogen bond energy by roughly 6 kcal/mol at all levels of theory. Keywords: low-barrier hydrogen bonds, short-strong hydrogen bonds, hydrogen maleate, ab initio, density functional theory.

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