Polarized continuum models

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... 

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). 

VBPCM Valence bond polarized continuum model. A VB computational method that incorporates solvent effect by using the PCM solvation model. The method can be coupled with VBSCF, BOVB, and VBCI. 

Current efforts in quantum-chemical modeling of the influence of solvents may be divided into two distinct approaches. The first, the supermolecular approximation, involves the explicit consideration of solvent molecules in quantum-chemical calculations. Another possibility for simulating solvent influence is to replace the explicit solvent molecules with a continuous medium having a bulk dielectric constant. Models of this type are usually referred to as polarized continuum models (PCMs). 

Tautomeric equilibrium in aqueous cw-malonaldehyde, see reaction 1 in Figure 8-4, is a prototypical reaction extensively studied in the gas phase but still relatively unknown in solution. In fact, despite the large number of NMR experiments [52,53,54] and quantum chemical calculations [55] with the polarized continuum model (PCM), [1] the actual stability of czT-malonaldehyde is not well clarified, although the trans isomer should be the predominant form in water. Secondly, the involvement of the light proton in the reaction may in principle provide relevant quantum effects even in condensed phase. All these complications did not prevent this reaction to be used as a prototypical system for theoretical studies of intramolecular proton transfer in condensed phase by several investigators [56,57,58,59,60] including ourselves. 

Over the last years, the basic concepts embedded within the SCRF formalism have undergone some significant improvements, and there are several commonly used variants on this idea. To exemplify the different methods and how their results differ, one recent work from this group [52] considered the sensitivity of results to the particular variant chosen. Due to its dependence upon only the dipole moment of the solute, the older approach is referred to herein as the dipole variant. The dipole method is also crude in the sense that the solute is placed in a spherical cavity within the solute medium, not a very realistic shape in most cases. The polarizable continuum method (PCM) [53,54,55] embeds the solute in a cavity that more accurately mimics the shape of the molecule, created by a series of overlapping spheres. The reaction field is represented by an apparent surface charge approach. The standard PCM approach utilizes an integral equation formulation (IEF) [56,57], A variant of this method is the conductor-polarized continuum model (CPCM) [58] wherein the apparent charges distributed on the cavity surface are such that the total electrostatic potential cancels on the surface. The self-consistent isodensity PCM procedure [59] determines the cavity self-consistently from an isodensity surface. The UAHF (United Atom model for Hartree-Fock/6-31 G ) definition [60] was used for the construction of the solute cavity. 

Calculations of the ionization potentials of the DNA bases have been reported using a polarized continuum model [95], The results are seen to nicely agree with... 

While these studies give good estimates for the IPs, it has been shown that the properties of DNA components are affected by the first few waters of hydration which mimic the first hydration shell around the molecule. For example, each water that acts as a net hydrogen bond donor to a base results in an elevation of the IP while each water that acts as a net hydrogen bond acceptor will tend to lower the IP [54], The solvation model, e.g., PCM (polarized continuum model), which takes into account the effect of the bulk solvent on the solute lacks these specific interactions and has the effect of substantially lowering the IP. Nevertheless, these first waters need to be included for a good accounting of IPs and EAs. 

Alternatively, reaction field calculations with the IPCM (isodensity surface polarized continuum model) [73,74] can be performed to model solvent effects. In this approach, an isodensity surface defined by a value of 0.0004 a.u. of the total electron density distribution is calculated at the level of theory employed. Such an isodensity surface has been found to define rather accurately the volume of a molecule [75] and, therefore, it should also define a reasonable cavity for the soluted molecule within the polarizable continuum where the cavity can iteratively be adjusted when improving wavefunction and electron density distribution during a self consistent field (SCF) calculation at the HF or DFT level. The IPCM method has also the advantage that geometry optimization of the solute molecule is easier than for the PISA model and, apart from this, electron correlation effects can be included into the IPCM calculation. For the investigation of Si compounds (either neutral or ionic) in solution both the PISA and IPCM methods have been used. [41-47]... 

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