scholarly journals Recent Developments of Computational Methods for pKa Prediction Based on Electronic Structure Theory with Solvation Models

J ◽  
2021 ◽  
Vol 4 (4) ◽  
pp. 849-864
Author(s):  
Ryo Fujiki ◽  
Toru Matsui ◽  
Yasuteru Shigeta ◽  
Haruyuki Nakano ◽  
Norio Yoshida
Keyword(s):  
Free Energy ◽  
Electronic Structure ◽  
Gibbs Energy ◽  
Acid Dissociation ◽  
Structure Theory ◽  
Protonation Reaction ◽  
Before And After ◽  
Recent Developments ◽  
Deprotonation Reaction ◽  
Solvation Models

The protonation/deprotonation reaction is one of the most fundamental processes in solutions and biological systems. Compounds with dissociative functional groups change their charge states by protonation/deprotonation. This change not only significantly alters the physical properties of a compound itself, but also has a profound effect on the surrounding molecules. In this paper, we review our recent developments of the methods for predicting the Ka, the equilibrium constant for protonation reactions or acid dissociation reactions. The pKa, which is a logarithm of Ka, is proportional to the reaction Gibbs energy of the protonation reaction, and the reaction free energy can be determined by electronic structure calculations with solvation models. The charge of the compound changes before and after protonation; therefore, the solvent effect plays an important role in determining the reaction Gibbs energy. Here, we review two solvation models: the continuum model, and the integral equation theory of molecular liquids. Furthermore, the reaction Gibbs energy calculations for the protonation reactions require special attention to the handling of dissociated protons. An efficient method for handling the free energy of dissociated protons will also be reviewed.

Fundamental Studies of Plutonium Aging

MRS Bulletin ◽  
2001 ◽  
Vol 26 (9) ◽  
pp. 679-683 ◽  
Author(s):  
Brian D. Wirth ◽  
Adam J. Schwartz ◽  
Michael J. Fluss ◽  
Maria J. Caturla ◽  
Mark A. Wall ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Conduction Band ◽  
Ambient Pressure ◽  
Radioactive Decay ◽  
Bound State ◽  
Environmental Safety ◽  
Structure Theory ◽  
Cubic Phase ◽  
High Symmetry ◽  
Safety And Health

Plutonium metallurgy lies at the heart of science-based stockpile stewardship. One aspect is concerned with developing predictive capabilities to describe the properties of stockpile materials, including an assessment of microstructural changes with age. Yet, the complex behavior of plutonium, which results from the competition of its 5f electrons between a localized (atomic-like or bound) state and an itinerant (delocalized bonding) state, has been challenging materials scientists and physicists for the better part of five decades. Although far from quantitatively absolute, electronic-structure theory provides a description of plutonium that helps explain the unusual properties of plutonium, as recently reviewed by Hecker. (See also the article by Hecker in this issue.) The electronic structure of plutonium includes five 5f electrons with a very narrow energy width of the 5f conduction band, which results in a delicate balance between itinerant electrons (in the conduction band) or localized electrons and multiple lowenergy electronic configurations with nearly equivalent energies. These complex electronic characteristics give rise to unique macroscopic properties of plutonium that include six allotropes (at ambient pressure) with very close free energies but large (∼25%) density differences, a lowsymmetry monoclinic ground state rather than a high-symmetry close-packed cubic phase, compression upon melting (like water), low melting temperature, anomalous temperature-dependence of electrical resistance, and radioactive decay. Additionally, plutonium readily oxidizes and is toxic; therefore, the handling and fundamental research of this element is very challenging due to environmental, safety, and health concerns.

Disordering of MgAl2O4 spinel from first principles

2000 ◽  
Vol 64 (2) ◽  
pp. 311-317 ◽  
Author(s):  
M. C. Warren ◽  
M. T. Dove ◽  
S. A. T. Redfern
Keyword(s):  
Free Energy ◽  
Electronic Structure ◽  
First Principles ◽  
Large Scale ◽  
Experimental Measurements ◽  
Zero Temperature ◽  
Macroscopic Models ◽  
Tetrahedral Sites ◽  
Degree Of Order ◽  
Good Agreement

AbstractAt high temperature, MgAl2O4 spinel is stabilized by disorder of Mg and Al between octahedral and tetrahedral sites. This behaviour has been measured up to 1700 K in recent neutron experiments, but the extrapolation of subsequently fitted thermodynamic models is not reliable. First principles simulation of the electronic structure of such minerals can in principle accurately predict disorder, but would require unfeasibly large computing resources. We have instead parameterized on-site and short-ranged cluster potentials using a small number of electronic structure simulations at zero temperature. These potentials were then used in large-scale statistical simulations at finite temperatures to predict disordering thermodynamics beyond the range of experimental measurements. Within the temperature range of the experiment, good agreement is obtained for the degree of order. The entropy and free energy are calculated and compared to those from macroscopic models.

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