Abstract
We present an algorithm for the analytical evaluation of free energy second derivatives with respect to nuclear displacements in the framework of the polarizable continuum model (PCM). The algorithm has been obtained for two recently proposed PCM versions, namely the conductor-like and the isotropic integral equation formalism models, and it can be applied to Hartree–Fock and to density functional SCF calculations on closed- and open-shell systems. The formal derivation is shown in detail and a number of numerical tests are presented: the applications show that analytical results are in excellent agreement with those obtained numerically and, as in vacuo, the analytical procedure is far more efficient. The presented algorithm can be routinely used with an upcoming release of the Gaussian program.
Keywords
IsotropyFormalism (music)GaussianPolarizable continuum modelPolarizabilityConductorStatistical physicsOpen shellIntegral equationApplied mathematicsPhysicsClassical mechanicsMathematicsQuantum mechanicsMathematical analysisGeometrySolvationMolecule
Affiliated Institutions
Related Publications
Energy and energy derivatives for molecular solutes: Perspectives of application to hybrid quantum and molecular methods
We examine the state of the art of the solvation procedure called the polarizable continuum model (PCM), focusing our attention on the basic properties: energy of the solute, so...
Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model
A new implementation of the conductor-like screening solvation model (COSMO) in the GAUSSIAN94 package is presented. It allows Hartree−Fock (HF), density functional (DF) and pos...
Solvent Effects. 5. Influence of Cavity Shape, Truncation of Electrostatics, and Electron Correlation on ab Initio Reaction Field Calculations
We describe several improvements to the reaction field model for the ab initio determination of solvation effects. First, the simple spherical cavity model is expanded to includ...
Analytical derivatives for molecular solutes. I. Hartree–Fock energy first derivatives with respect to external parameters in the polarizable continuum model
Analytical expressions for the derivatives of the free energy of solution of molecular solutes with respect to the dielectric constant and to a parameter defining the size of th...
Analytical energy derivatives for a realistic continuum model of solvation: Application to the analysis of solvent effects on reaction paths
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 distributi...
Publication Info
- Year
- 1998
- Type
- article
- Volume
- 109
- Issue
- 15
- Pages
- 6246-6254
- Citations
- 246
- Access
- Closed
External Links
Social Impact
Altmetric
PlumX Metrics
Social media, news, blog, policy document mentions
Citation Metrics
246
OpenAlex
Cite This
Maurizio Cossi,
Vincenzo Barone
(1998).
Analytical second derivatives of the free energy in solution by polarizable continuum models.
The Journal of Chemical Physics
, 109
(15)
, 6246-6254.
https://doi.org/10.1063/1.477265
Identifiers
- DOI
- 10.1063/1.477265