Quantum Mechanical Polarizable Continuum Model Approach to the Kerr Effect of Pure Liquids

Cappelli, Chiara; Mennucci, Benedetta; Cammi, Roberto; Rizzo, Antonio

doi:10.1021/jp053097q

Cited by 30 publications

(39 citation statements)

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“…There exists, therefore, a formal difference between the macroscopic spectroscopic response of the solution sample, which is defined in terms of the Maxwell field, and the response of the molecule in the cavity within a dielectric medium, which depends instead on the field locally acting on the molecule in the cavity. However, as already pointed out in the literature, [13][14][15][38][39][40][41][42][43][44] in order to gain a reliable connection between the microscopic properties of the molecule and the macroscopic response, it is compulsory to account for the difference between the Maxwell and the cavity fields.…”

Section: Introductionmentioning

confidence: 99%

Towards an accurate description of anharmonic infrared spectra in solution within the polarizable continuum model: Reaction field, cavity field and nonequilibrium effects

Cappelli

Lipparini

Bloino

et al. 2011

The Journal of Chemical Physics

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We present a newly developed and implemented methodology to perturbatively evaluate anharmonic vibrational frequencies and infrared (IR) intensities of solvated systems described by means of the polarizable continuum model (PCM). The essential aspects of the theoretical model and of the implementation are described and some numerical tests are shown, with special emphasis towards the evaluation of IR intensities, for which the quality of the present method is compared to other methodologies widely used in the literature. Proper account of an incomplete solvation regime in the treatment of the molecular vibration is also considered, as well as inclusion of the coupling between the solvent and the probing field (cavity field effects). In order to assess the quality of our approach, comparison with experimental findings is reported for selected cases.

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Section: Introductionmentioning

confidence: 99%

Towards an accurate description of anharmonic infrared spectra in solution within the polarizable continuum model: Reaction field, cavity field and nonequilibrium effects

Cappelli

Lipparini

Bloino

et al. 2011

The Journal of Chemical Physics

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“… T melt 78 ; Density (ρ): Ben 79 , Tol 36 , PhOH 80 , pCr 81 , Pyrr 39 , Py 82 ; Enthalpy of vaporization (Δ vap H ): Ben 67 , Tol 78 , PhOH 80 , Pyrr 83 , Py 84 ; Isothermal compressibility (κ T ): Ben 85 , Tol 86 , PhOH 78 , pCr 87 , Pyrr 76 , Py 88 ; Isothermal expansion (α p ): Ben 85 , Tol 85 , PhOH 89 , pCr 90 , Pyrr 76 , Py 88 ; Dielectric constant (ε): Ben 91 , Tol 92 , PhOH 80 , pCr 93 , Pyrr 94 , Py 95 …”

Section: Figurementioning

confidence: 99%

A Kirkwood–Buff force field for the aromatic amino acids

Ploetz

Smith

2011

Phys. Chem. Chem. Phys.

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In a continuation of our efforts to develop a united atom non-polarizable protein force field based upon the solution theory of Kirkwood and Buff i.e., the Kirkwood-Buff Force Field (KBFF) approach, we present KBFF models for the side chains of phenylalanine, tyrosine, tryptophan, and histidine, including both tautomers of neutral histidine and doubly-protonated histidine. The force fields were specifically designed to reproduce the thermodynamic properties of mixtures over the full composition range in an attempt to provide an improved description of intermolecular interactions. The models were developed by careful parameterization of the solution phase partial charges to reproduce the experimental Kirkwood-Buff integrals for mixtures of solutes representative of the amino acid sidechains in solution. The KBFF parameters and simulated thermodynamic and structural properties are presented for the following eleven binary mixtures: benzene + methanol, benzene + toluene, toluene + methanol, toluene + phenol, toluene + p-cresol, pyrrole + methanol, indole + methanol, pyridine + methanol, pyridine + water, histidine + water, and histidine hydrochloride + water. It is argued that the present approach and models provide a reasonable description of intermolecular interactions which ensures that the required balance between solute-solute, solute-solvent, and solvent-solvent distributions is obtained.

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“…A quantum mechanical approach to the "local field" problem has been formulated for PCM for several optical and spectroscopic properties. 20,21,25,26,[41][42][43][44] The foundations for the PCM approach to the "local field" problem rely upon the assumption that the "effective" field experienced by the molecule in the cavity can be seen as the sum of a reaction field term and a cavity field term. The reaction field is connected to the response (polarization) of the dielectric to the solute charge distribution, whereas the cavity field depends on the polarization of the dielectric induced by the applied field once the cavity has been created.…”

Section: Theorymentioning

confidence: 99%

Solvent Effects on Raman Optical Activity Spectra Calculated Using the Polarizable Continuum Model

Pecul¹,

Lamparska²,

Cappelli

et al. 2006

J. Phys. Chem. A

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The integral equation formulation of the polarizable continuum model (IEFPCM) has been extended to the calculation of solvent effects on vibrational Raman optical activity spectra. Gauge-origin independence of the differential scattering intensities of right and left circularly polarized light is ensured through the use of London atomic orbitals. Density functional theory (DFT) calculations have been carried out for bromochlorofluoromethane, methyloxirane, and epichlorhydrin. The results indicate that solvent effects on the ROA differential scattering intensities can be substantial, and vary in sign and magnitude for different vibrational modes. It is demonstrated that both direct and indirect effects are important in determining the total solvent effects on the ROA differential scattering intensities. Local field effects are shown to be in general small, whereas electronic nonequilibrium solvation has a profound effect on the calculated solvent effects compared to an equilibrium solvation model. For molecules with several conformations, the changes in the relative stability of the different conformers also lead to noticeable changes in the ROA spectra.

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Quantum Mechanical Polarizable Continuum Model Approach to the Kerr Effect of Pure Liquids

Cited by 30 publications

References 50 publications

Towards an accurate description of anharmonic infrared spectra in solution within the polarizable continuum model: Reaction field, cavity field and nonequilibrium effects

Towards an accurate description of anharmonic infrared spectra in solution within the polarizable continuum model: Reaction field, cavity field and nonequilibrium effects

A Kirkwood–Buff force field for the aromatic amino acids

Solvent Effects on Raman Optical Activity Spectra Calculated Using the Polarizable Continuum Model

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