The orientational correlation parameter for liquid CS2, C6H6 and C6F6

Battaglia, Maurice R.; Cox, T. I.; Madden, Paul A.

doi:10.1080/00268977900101041

Cited by 87 publications

(29 citation statements)

References 27 publications

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“…50 We therefore conclude that the combination of the Bonnaud potential and any of the distributed polarizability models tested here does an excellent job in reproducing the low-frequency Raman spectrum of benzene. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 5.…”

Section: Comparison Of Simulation and Experimentsmentioning

confidence: 92%

Assessing Polarizability Models for the Simulation of Low-Frequency Raman Spectra of Benzene

2014

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Optical Kerr effect (OKE) spectroscopy is a widely used technique for probing the low-frequency, Raman-active dynamics of liquids. Although molecular simulations are an attractive tool for assigning liquid degrees of freedom to OKE spectra, the accurate modeling of the OKE and the motions that contribute to it relies on the use of a realistic and computationally tractable molecular polarizability model. Here we explore how the OKE spectrum of liquid benzene, and the underlying dynamics that determines its shape, are affected by the polarizability model employed. We test a molecular polarizability model that uses a point anisotropic molecular polarizability and three other models that distribute the polarizability over the molecule. The simplest and most computationally efficient distributed polarizability model tested is found to be sufficient for the accurate simulation of the many-body polarizability dynamics of this liquid. We further find that the atomic-to-molecular polarizability transformation approximation [Hu et al. J. Phys. Chem. B 2008, 112, 7837-7849], used in conjunction with this distributed polarizability model, yields OKE spectra whose shapes differ negligibly from those calculated without this approximation, providing a substantial increase in computational efficiency.

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Section: Comparison Of Simulation and Experimentsmentioning

confidence: 92%

Assessing Polarizability Models for the Simulation of Low-Frequency Raman Spectra of Benzene

2014

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“…͑4͒ of Ref. 30 for the Kerr constant describing electric field-induced birefringence in a system of axially symmetric molecules.…”

Section: ͑11͒mentioning

confidence: 99%

Computer simulation of the linear and nonlinear optical properties of liquid benzene: Its local fields, refractive index, and second nonlinear susceptibility

Janssen

Bomont

Theodorou

et al. 1999

The Journal of Chemical Physics

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. Computer simulation of the linear and nonlinear optical properties of liquid benzene : its local fields, refractive index and second nonlinear susceptibility. Journal of Chemical Physics, 110(13), 6463-6474. DOI: 10.1063/1.478549 General rightsCopyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Molecular dynamics ͑MD͒ simulation and subsequent analysis of the macroscopic polarization developed in response to ''a posteriori'' applied electric fields or of spontaneous fluctuations in the instantaneous polarization under zero applied field is used to assess the nonlinear optical properties of a polarizable liquid. Three strategies are proposed for the electrostatic analysis, all using as input static ''gas phase'' ͑hyper͒polarizabilities, obtained from ab initio calculations. All three strategies are shown to accurately reproduce the experimentally measured refractive index and second nonlinear susceptibility of liquid benzene. The simulation also predicts the distribution of orientations and magnitudes of the local electric fields experienced by the molecules in the liquid, and the nonlinear contributions to the local fields. This approach gives an 8% higher estimate of the second nonlinear susceptibility of liquid benzene than the Lorentz local field factor approach, in better agreement with experimental values.

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“…Both of these compounds have only small orientational correlations 67,68 and can be approximated by the spherical Lennard-Jones potential quite well. At the same time, the assumption that n-decane is orientationally averaged at room temperature is clearly too optimistic.…”

Section: Resultsmentioning

confidence: 99%

Predicting Solvation Free Energies Using Parameter-Free Solvent Models

2016

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We present a new approach for predicting solvation free energies in non-aqueous solvents. Utilizing the corresponding states principle, we estimate solvent LennardJones parameters directly from their critical points. Combined with atomic solutes and pressure corrected three-dimensional reference interaction site model (3D-RISM/PC+), the model gives accurate predictions for a wide range of non-polar solvents, including olive oil. The results, obtained without electrostatic interactions and with a very coarse-grained solvent provide an interesting alternative to widely used and heavily parametrized models.

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The orientational correlation parameter for liquid CS₂, C₆H₆ and C₆F₆

Cited by 87 publications

References 27 publications

Assessing Polarizability Models for the Simulation of Low-Frequency Raman Spectra of Benzene

Assessing Polarizability Models for the Simulation of Low-Frequency Raman Spectra of Benzene

Computer simulation of the linear and nonlinear optical properties of liquid benzene: Its local fields, refractive index, and second nonlinear susceptibility

Predicting Solvation Free Energies Using Parameter-Free Solvent Models

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