Modeling Water Exchange on an Aluminum Polyoxocation

Modeling Water Exchange on an Aluminum Polyoxocation

For the first time, water exchange on a polymeric complex has been modeled using a combination of gas-phase ab initio calculations and molecular dynamics (MD) simulations. The GaO4Al12(OH)24(H2O)12 7+(aq) ion (GaAl12) was chosen because high-quality experimental data exist, including an activation e...

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Veröffentlicht in:The journal of physical chemistry. B 2005-12, Vol.109 (50), p.23771-23775
Hauptverfasser: Stack, Andrew G, Rustad, James R, Casey, William H
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Sprache:eng
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ALUMINIUM
ENTHALPY
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
SIMULATION
SOLVENTS
WATER
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container_title The journal of physical chemistry. B
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creator Stack, Andrew G
Rustad, James R
Casey, William H
description For the first time, water exchange on a polymeric complex has been modeled using a combination of gas-phase ab initio calculations and molecular dynamics (MD) simulations. The GaO4Al12(OH)24(H2O)12 7+(aq) ion (GaAl12) was chosen because high-quality experimental data exist, including an activation enthalpy (+63 ± 7 kJ/mol) and an activation volume (+3 ± 1 cm3/mol). We took a two-step approach. First, the local solvent structure and the initial states for reaction were inferred from the molecular dynamics simulations. Second, we used this information to evaluate initial-state structures in the ab initio calculations. The energy differences between the initial and transition states from the ab initio calculations varied from +59 kJ/mol to +53 kJ/mol depending upon details, closely approximating the activation enthalpy.
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subjects ALUMINIUM
ENTHALPY
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
SIMULATION
SOLVENTS
WATER
title Modeling Water Exchange on an Aluminum Polyoxocation
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