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Title: Trivalent Ion Hydrolysis Reactions: A Linear Free-Energy Relationship Based on Density Functional Electronic Structure Calculations

Abstract

Metal ion hydrolysis is fundamental in aqueous chemistry because of the influence of coordinating hydroxide ions on reaction rates; examples include enhanced labilization of coordinating water molecules in hydrolyzed complexes1 and stabilization of oxidized products in electron-transfer reactions involving hydrolyzed reductants.2 Moreover, the role of metal hydrolysis reactions in defining a baseline for establishing trends in metal ligand binding has motivated efforts toward comprehensive integration of Mz+ xOHy stability constants.3-5

Authors:
; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab., Richland, WA (US), Environmental Molecular Sciences Laboratory (US)
Sponsoring Org.:
US Department of Energy (US)
OSTI Identifier:
15004991
Report Number(s):
PNNL-SA-34253
Journal ID: ISSN 0002-7863; JACSAT; 1835; KP1301030; TRN: US200412%%45
DOE Contract Number:
AC06-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 121; Journal Issue: 13; Other Information: PBD: 7 Apr 1999
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ELECTRON TRANSFER; ELECTRONIC STRUCTURE; FREE ENERGY; DENSITY FUNCTIONAL METHOD; HYDROLYSIS; HYDROXIDES; CHEMICAL REACTION KINETICS; STABILITY; STABILIZATION; METALS; ENVIRONMENTAL MOLECULAR SCIENCES LABORATORY, NULL

Citation Formats

Rustad, James R., Dixon, David A., Rosso, Kevin M., and Felmy, Andrew R. Trivalent Ion Hydrolysis Reactions: A Linear Free-Energy Relationship Based on Density Functional Electronic Structure Calculations. United States: N. p., 1999. Web. doi:10.1021/ja984217t.
Rustad, James R., Dixon, David A., Rosso, Kevin M., & Felmy, Andrew R. Trivalent Ion Hydrolysis Reactions: A Linear Free-Energy Relationship Based on Density Functional Electronic Structure Calculations. United States. doi:10.1021/ja984217t.
Rustad, James R., Dixon, David A., Rosso, Kevin M., and Felmy, Andrew R. Wed . "Trivalent Ion Hydrolysis Reactions: A Linear Free-Energy Relationship Based on Density Functional Electronic Structure Calculations". United States. doi:10.1021/ja984217t.
@article{osti_15004991,
title = {Trivalent Ion Hydrolysis Reactions: A Linear Free-Energy Relationship Based on Density Functional Electronic Structure Calculations},
author = {Rustad, James R. and Dixon, David A. and Rosso, Kevin M. and Felmy, Andrew R.},
abstractNote = {Metal ion hydrolysis is fundamental in aqueous chemistry because of the influence of coordinating hydroxide ions on reaction rates; examples include enhanced labilization of coordinating water molecules in hydrolyzed complexes1 and stabilization of oxidized products in electron-transfer reactions involving hydrolyzed reductants.2 Moreover, the role of metal hydrolysis reactions in defining a baseline for establishing trends in metal ligand binding has motivated efforts toward comprehensive integration of Mz+ xOHy stability constants.3-5},
doi = {10.1021/ja984217t},
journal = {Journal of the American Chemical Society},
number = 13,
volume = 121,
place = {United States},
year = {Wed Apr 07 00:00:00 EDT 1999},
month = {Wed Apr 07 00:00:00 EDT 1999}
}
  • Metal ion hydrolysis is fundamental in aqueous chemistry because of the influence of coordinating hydroxide ions on reaction rates; examples include enhanced labilization of coordinating water molecules in hydrolyzed complexes and stabilization of oxidized products in electron-transfer reactions involving hydrolyzed reductants. Moreover, the role of metal hydrolysis reactions in defining a baseline for establishing trends in metal-ligand binding has motivated efforts toward comprehensive integration of M{sup z+}{sub x}OH{sub y} stability constants.
  • Density-functional calculations of the electronic structure and atomic positions are reported for Li{sub 2}WO{sub 4}. This compound is found to be very different from the tungstate scintillators such as PbWO{sub 4} in that both the valence and conduction bands are much less dispersive. This leads to a substantially larger band gap. The difference is understood in terms of the crystal structure, in particular, the longer O-O distances connecting the WO{sub 4} tetrahedra.
  • Based on the real-space finite-difference method, we have developed a first-principles density functional program that efficiently performs large-scale calculations on massively-parallel computers. In addition to efficient parallel implementation, we also implemented several computational improvements, substantially reducing the computational costs of O(N{sup 3}) operations such as the Gram-Schmidt procedure and subspace diagonalization. Using the program on a massively-parallel computer cluster with a theoretical peak performance of several TFLOPS, we perform electronic-structure calculations for a system consisting of over 10,000 Si atoms, and obtain a self-consistent electronic-structure in a few hundred hours. We analyze in detail the costs of the program inmore » terms of computation and of inter-node communications to clarify the efficiency, the applicability, and the possibility for further improvements.« less
  • Trivalent Ion Hydrolysis Reactions II: Analysis of Electron Density Distributions in Metal-Oxygen Bonds
  • Examining photochemical processes in solution requires understanding the solvent effects on the potential energy profiles near conical intersections (CIs). For that purpose, the CI point in solution is determined as the crossing between nonequilibrium free energy surfaces. In this work, the nonequilibrium free energy is described using the combined method of linear-response free energy and collinear spin-flip time-dependent density functional theory. The proposed approach reveals the solvent effects on the CI geometries of stilbene in an acetonitrile solution and those of thymine in water. Polar acetonitrile decreases the energy difference between the twisted minimum and twisted-pyramidalized CI of stilbene. Formore » thymine in water, the hydrogen bond formation stabilizes significantly the CI puckered at the carbonyl carbon atom. The result is consistent with the recent simulation showing that the reaction path via this geometry is open in water. Therefore, the present method is a promising way of identifying the free-energy crossing points that play an essential role in photochemistry of solvated molecules.« less