Abstract
Analytical expressions for the first and second derivatives of the Hartree–Fock energy have been derived in case of a solvated system simulated by a multipolar charge distribution embedded in a cavity of arbitrary shape and a solvent represented by a dielectric continuum. A computer code has been written on these bases. It allows geometry optimizations and more generally the determination of the critical points of the potential energy surface for a molecular system interacting with a solvent as easily as in the case of an isolated molecule. The use of this code is illustrated by the computation of the main features of the reaction path of a Menshutkin-type reaction in various solvents. The results compare pretty well with those obtained by a full Monte Carlo simulation of the solvent by Gao. This agreement supports the idea that solvents, including water, can be safely modeled by a continuum. The advantage of such models rests in the fact that they allow refined computations on the solute at a minimum computational expense.
Keywords
SolvationComputationMonte Carlo methodSolventStatistical physicsComputational chemistrySolvent effectsChemistryImplicit solvationDielectricSolvent modelsPhysicsComputer scienceQuantum mechanicsAlgorithmMathematicsOrganic chemistry
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Publication Info
- Year
- 1996
- Type
- article
- Volume
- 104
- Issue
- 23
- Pages
- 9437-9444
- Citations
- 63
- Access
- Closed
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Cite This
Valérie Dillet,
Daniel Rinaldi,
Juan Bertrán
et al.
(1996).
Analytical energy derivatives for a realistic continuum model of solvation: Application to the analysis of solvent effects on reaction paths.
The Journal of Chemical Physics
, 104
(23)
, 9437-9444.
https://doi.org/10.1063/1.471688
Identifiers
- DOI
- 10.1063/1.471688