Role of the cavity field in nonlinear optical response in the condensed phase

Munn, R. W.; Luo, Yi; Macák, Peter; Ågren, Hans

doi:10.1063/1.1343082

Cited by 28 publications

(17 citation statements)

References 10 publications

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“…However, some optical experiments involve a strong coupling of light with the medium, giving rise to nonlinear optical effects such as second‐harmonic generation, the Kerr effect or four‐wave mixing. Quadratic and higher‐order terms of the local electric field become significant in all these cases, and it is therefore crucial to apply field‐correction factors that take into account higher‐order polarizabilities (hyperpolarizabilities) in a self‐consistent manner …”

Section: The Onsager−böttcher Treatment Of a Dipole In A Cavitymentioning

confidence: 99%

Understanding Local‐Field Correction Factors in the Framework of the Onsager−Böttcher Model

2019

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The determination of the appropriate local-field factor for quantifying the response of a molecule to an external electric field is of major importance in optical spectroscopy. Although numerous studies have dealt with the evolution of the optical properties of emitters as a function of their environment, the choice of the model used to quantify local fields is still ambiguous, and sometimes even arbitrary. In this paper, we review the Onsager-Böttcher model, which introduces the polarizability of the probe molecule as the determinant parameter for the local field factor, and we establish a simple conceptual framework encompassing all commonly used models. Finally, a discussion of published experimental research illustrates the potential of the measurement of local electric fields in dense dielectric media, as well as the subtleties involved in their interpretation.

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Section: The Onsager−böttcher Treatment Of a Dipole In A Cavitymentioning

confidence: 99%

Understanding Local‐Field Correction Factors in the Framework of the Onsager−Böttcher Model

2019

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“…•α iso, B (0) is the isotropic part of the total effective polarizability tensor of the molecular solute with respect to the macroscopic static electric field E in the presence of the other molecules. [5,[32][33][34][35][36][37][38] In general, the total static polarizabilitỹ α is (0) is given bỹ…”

Section: The Continuum Solvation Modelsmentioning

confidence: 99%

“…•α iso, B (ω) is the isotropic part of the effective dynamic polarizability with respect to the macroscopic dynamic electric field E of the optical radiation in the presence of the other molecules. [32,[34][35][36] The dynamical polarizabilityα is (ω) contains only the electronic contribution.…”

Section: The Continuum Solvation Modelsmentioning

confidence: 99%

The Role of Computational Chemistry in the Experimental Determination of the Dipole Moment of Molecules in Solution

Cammi

2019

J Comput Chem

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The methods for the experimental determination of electric dipole moment of molecules in solution from measurements of dielectric permittivity and refractive index are traditionally based on the classical Onsager model. In this model the molecular solute is approximated as a simple polarizable point dipole inside a spherical or ellipsoidal cavity of a dielectric medium representing the solvent. However, the inadequacies of the model resulting from the assumption of a simple shape of the cavity, for the evaluation of the cavity field effect, and from the uncertainty of the polarizability of the molecular solute influences the results and hampers the comparison with the electric dipole moments computed from quantum chemical solvation models. In this article we propose a new method for the experimental determination of the electric dipole moment in solution in which information from the Polarizable Continuum Model calculations are used in place of the Onsager model. The new method overcomes the limitations of this latter model regarding both the cavity field effect and the polarizability of the molecular solutes, and thus allows a coherent comparison between experimental and computed dipole moments of solvated molecules. © 2019 Wiley Periodicals, Inc.

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“…Analysis of the problem of using adequate LFFs for the interpretation of NLO experiments was also considered in refs. [22,53,54]; the calculation of the linear and nonlinear response of the system of interacting dipoles with the application of nonlinear equations of rotational diffusion with a local field effect was performed in ref. [55].…”

Section: à5mentioning

confidence: 99%

Polymer Matrix Effects on the Nonlinear Optical Response of Incorporated Chromophore: New Analytical Models

Balakina

2006

ChemPhysChem

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A new approach aimed at the modeling of the nonlinear optical (NLO) response of a dipole chromophore incorporated into a locally anisotropic, deformable, polarizable polymer matrix is suggested. The general continuum methodology is used with a specific cavity ansatz being employed; the cavity is chosen to be conformal to the characteristic ellipsoid of the generalized permittivity tensor of the polymer medium. The suggested ansatz allows the electrostatic boundary value problem to be solved analytically, and the local field experienced by the chromophore in the polymer electret to be found. Four analytically solvable models, which correspond to two singular and two nonsingular models, are considered; in two of them the chromophore is characterized by singular dipole and quadrupole moments; the other two use the approximation of the electric moment of the chromophore with that of the polarized ellipsoid. The relation between the macroscopic polymer properties and the microscopic characteristics of the NLO chromophore is established. The compliance of the obtained formulas for the local field with those of the classical Onsager approach is analyzed, and their specific features are considered.

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Role of the cavity field in nonlinear optical response in the condensed phase

Cited by 28 publications

References 10 publications

Understanding Local‐Field Correction Factors in the Framework of the Onsager−Böttcher Model

Understanding Local‐Field Correction Factors in the Framework of the Onsager−Böttcher Model

The Role of Computational Chemistry in the Experimental Determination of the Dipole Moment of Molecules in Solution

Polymer Matrix Effects on the Nonlinear Optical Response of Incorporated Chromophore: New Analytical Models

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