6.2.2. Definition of Effective Properties 3064 6.3. Response Properties to Magnetic Fields 3066 6.3.1. Nuclear Shielding 3066 6.3.2. Indirect Spin−Spin Coupling 3067 6.3.3. EPR Parameters 3068 6.4. Properties of Chiral Systems 3069 6.4.1. Electronic Circular Dichroism (ECD) 3069 6.4.2. Optical Rotation (OR) 3069 6.4.3. VCD and VROA 3070 7. Continuum and Discrete Models 3071 7.1. Continuum Methods within MD and MC Simulations 3072

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Quantum mechanical continuum solvation models.

Implicit Solvation Models: Equilibria, Structure, Spectra, and Dynamics.

The polarizable continuum model (PCM) is a computational method originally formulated 30 years ago but still today it represents one of the most successful examples among continuum solvation models. Such a success is mainly because of the continuous improvements, both in terms of computational efficiency and generality, made by all the people involved in the PCM project. The result of these efforts is that nowadays, PCM, with all its different variants, is the default choice in many computational codes to couple a quantum–mechanical (QM) description of a molecular system with a continuum description of the environment. In this review, a brief presentation of the main methodological and computational aspects of the method will be given together with an analysis of strengths and critical issues of its coupling with different QM methods. Finally, some examples of applications will be presented and discussed to show the potentialities of PCM in describing the effects of environments of increasing complexity. © 2012 John Wiley & Sons, Ltd.

Polarizable continuum model

Theoretical Methods for the Description of the Solvent Effect in Biomolecular Systems.

A new charge model, called Charge Model 4 (CM4), and a new continuum solvent model, called Solvation Model 6 (SM6), are presented Using a database of aqueous solvation free energies for 273 neutrals, 112 ions, and 31 ion−water clusters, parameter sets for the mPW0 hybrid density functional of Adamo and Barone (Adamo, C; Barone, V J Chem Phys 1998, 108, 664−675) were optimized for use with the following four basis sets:  MIDI!6D, 6-31G(d), 6-31+G(d), and 6-31+G(d,p) SM6 separates the observable aqueous solvation free energy into two different components:  one arising from long-range bulk electrostatic effects and a second from short-range interactions between the solute and solvent molecules in the first solvation shell This partition of the observable solvation free energy allows SM6 to effectively model a wide range of solutes For the 273 neutral solutes in the test set, SM6 achieves an average error of ∼050 kcal/mol in the aqueous solvation free energies For solutes, especially ions, that hav

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SM6: A Density Functional Theory Continuum Solvation Model for Calculating Aqueous Solvation Free Energies of Neutrals, Ions, and Solute-Water Clusters.

Some calculations are presented using a recently developed version of the ab initio polarizable continuum model that includes electron correlation in the representation of the solute. Calculations were carried out to estimate the self-consistent field electronic solvation energies and one-electron properties of several molecules. Comparison is made of results at several levels of approximation.

Polarizable continuum model calculations including electron correlation in the ab initio wavefunction

A procedure to estimate the basis set superposition error is proposed avoiding the overestimation of the counterpoise correction in the van der Waals interactions Numerical calculations were carried out in the Ne ⋅⋅⋅ Ne complex at the SCF level

About the overestimation of the basis set superposition error on interaction energy calculations for van der Waals systems

A simple model is presented for the vibrational treatment of diatomic molecules in solution using the basic polarizable continuum method.

Applications of the basic polarizable continuum model. A study of the vibrational properties of diatomic solutes

This work puts forward the adaptation of the molecular cavity size in the bosom of a solvent, useful in the SCF-LCAO-MO treatment of the solute-solvent interactions following the continuum model and taking into account the basis set used and the electronic characteristics of the solute

Solute-solvent interactions. Adaptation of the cavity size as a function of the basis set

The results of the calculation on the C∞v He–H2 van der Waals molecule by employing the diagrammatic many‐body theory to treat the electron correlation effects are reported in this paper. The use of the partial counterpoise method to compute the self‐consistent field (SCF) and correlation energies, when a moderate basis set is employed, may lead to a reliable description of the potential curve for the van der Waals (VDW) system.

The polarization‐function counterpoise method. An application of the diagrammatic perturbation theory to the He–H2 molecule in the region of the van der Waals minimum

S. Tolosa

Papers

Polarizable continuum model calculations including electron correlation in the ab initio wavefunction

About the overestimation of the basis set superposition error on interaction energy calculations for van der Waals systems

Applications of the basic polarizable continuum model. A study of the vibrational properties of diatomic solutes

Solute-solvent interactions. Adaptation of the cavity size as a function of the basis set

The polarization‐function counterpoise method. An application of the diagrammatic perturbation theory to the He–H2 molecule in the region of the van der Waals minimum