Polarization continuum

The most popular of the SCRF methods is the polarized continuum method (PCM) developed by Tomasi and coworkers. This technique uses a numerical integration over the solute charge density. There are several variations, each of which uses a nonspherical cavity. The generally good results and ability to describe the arbitrary solute make this a widely used method. Flowever, it is sensitive to the choice of a basis set. Some software implementations of this method may fail for more complex molecules. 

OPW (orthogonalized plane wave) a band-structure computation method P89 (Perdew 1986) a gradient corrected DFT method parallel computer a computer with more than one CPU Pariser-Parr-Pople (PPP) a simple semiempirical method PCM (polarized continuum method) method for including solvation effects in ah initio calculations... 

SCF (self-consistent field) procedure for solving the Hartree-Fock equations SCI-PCM (self-consistent isosurface-polarized continuum method) an ah initio solvation method... 

Tomasi s Polarized Continuum Model (PCM) defines the cavity as the union of a series of interlocking atomic spheres. The effect of polarization of the solvent continuum is represented numerically it is computed by numerical integration rather... 

Over the years, many workers have addressed the problem of choice of cavity and the reaction field. Tomasi s polarized continuum model (PCM) defines the cavity as a series of interlocking spheres. The isodensity PCM (IPCM) defines the cavity as an isodensity surface of the molecule. This isodensity surface is determined iteratively. The self-consistent isodensity polarized continuum model (SQ-PCM) gives a further refinement in that it allows for a full coupling between the cavity shape and the electron density. 

Subsequently, DFT methods (B3LYP functional ) were employed to compute (1) natural charges from which changes in charges are mapped out for comparison with the NMR-based conclusions, (2) GIAO-NMR to predict the chemical shifts for comparison with the experimental results, and (3) nuclear-independent chemical shift (NICS) in order to evaluate relative aromaticity in different rings. Finally, solvent effects were estimated by the polarized continuum model (PCM). In selected cases, parallel DNA-binding studies (with MCF-7 human mammary... 

The intrinsic properties of pterins have also been investigated in the context of the molybdenum cofactot, in particular the population of tautomers <1997J(P2)1529>. A polar continuum model including water suggested that several possible tautomers were of similar energy and that only an or/,4o-quinonoid tautomer (the 5,6-dihydro-(3//) tautomer) was too high in energy to play a role. 

Perhaps the most widely used scheme for SCRF implementations of the Poisson equation is the surface area boundary element approach. This was first formalized by Miertus, Scrocco, and Tomasi (1981), and these authors referred to their construction as the polarized continuum model (PCM). While that name continues to find ample use in the literature, MST (the initials... 

MST Miertus-Scrocco-Toinasi (polarized continuum) model... 

Thermodynamic parameters for the benzene oxide-oxepine system are calculated at MP4(SDQ)/6-31+G //HF/ 6-31G level of theory. The effect of solvent polarity on the above equilibrium is studied using the isodensity polarized continuum method. Low polar solvents favor the oxepine formation, whereas medium to high polar solvents lead to benzene oxide formation. The transition state for the tautomerization is fully characterized and the activation energies for the forward and reverse reaction are estimated to be ca. 9.5 and 11.0 kcal mol-1, respectively. The solvent polarity exerts a reasonable effect decreasing the activation energies up to 4 kcal mol-1 <2001MI471>. 

In order to explain the high stereocontrol occurring in the iodocyclization of 3-acylamino-2-methylenealkanoates, the conformational space of the starting molecule and the potential energy surface (PES) for the cyclization reaction was explored at the DFT level the polarized continuum formalism (PCM) for chloroform was used in order to consider the solvent effect. The observed stereoselection [(9) (10)] was (de)... 

In addition to SMx and the cluster-continuum model, other continuum models have also been used to study reactions in liquids, including the polarized continuum model [133-135] (PCM), the conductor-like screening model (COSMO [136] and COSMO-RS [137,138]), the generalized COSMO [139] (GCOSMO) model, conductorlike PCM [140] (CPCM), and isodensity PCM [141] (IPCM). 

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