Atom charge transfer in molecular polarizabilities: application of the Olson-Sundberg model to aliphatic and aromatic hydrocarbons

Applequist, Jon

doi:10.1021/j100124a039

Cited by 100 publications

(123 citation statements)

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“…Indeed the distances are so short that the major contributions come from higher order DID interactions. Irrespective to the relative success of the method, various authors [22,23,24] have modified the scheme adding mono-pole polarizability, and/or using non isotropic atomic polarizability, and/or separating atoms of the same species on the base of chemical bonds. Only a few attempts have been made so far to use the Applequist formalism to calculate the experimental spectra [16], and with doubtful improvements.…”

Section: Polarizability Modelsmentioning

confidence: 99%

Orientational and induced contributions to the depolarized Rayleigh spectra of liquid and supercooled ortho-terphenyl

Mossa

Ruocco

Sampoli

2002

The Journal of Chemical Physics

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The depolarized light scattering spectra of the glass forming liquid ortho-terphenyl have been calculated in the low frequency region using molecular dynamics simulation. Realistic system's configurations are produced by using a recent flexible molecular model and combined with two limiting polarizability schemes, both of them using the dipole-induced-dipole contributions at first and second order. The calculated Raman spectral shape are in good agreement with the experimental results in a large temperature range. The analysis of the different contributions to the Raman spectra emphasizes that the orientational and the collision-induced (translational) terms lie on the same time-scale and are of comparable intensity. Moreover, the cross terms are always found to be an important contribution to the scattering intensity.

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Section: Polarizability Modelsmentioning

confidence: 99%

Orientational and induced contributions to the depolarized Rayleigh spectra of liquid and supercooled ortho-terphenyl

Mossa

Ruocco

Sampoli

2002

The Journal of Chemical Physics

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“…It calculates tensor effective anisotropic point polarizabilities by the method of Applequist et al [19,20,[48][49][50]. One considers the molecule as being made up of N atoms (i, j, k,…), each of which acts as a point particle located at the nucleus and responds to an electric field only by the induction of a dipole moment which is a linear function of the local field.…”

Section: Interacting Induced Dipoles Polarization Model For Molecularmentioning

confidence: 99%

“…Modern theoretical chemistry, with the help of powerful computers, can attempt to become a substitute for difficult experimental determinations [18]. Classical models such as the dipole interaction model and its improvements, which were investigated among others by Applequist [19,20] are able to predict molecular polarizabilities with surprising accuracy. Because of their simplicity they can be conveniently implemented in molecular force fields to account for the non-additivity effects in the intermolecular interactions [14][15][16][21][22][23].…”

Section: Introductionmentioning

confidence: 99%

Polarization by the effect of a small torsional change in the benzothiazole (A)-benzobisthiazole (B) oligomer A-B13-A

1999

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Abstract:We use a method for the calculation of the molecular dipole ( µ ) and quadrupole ( θ ) moments and dipole-dipole ( α ), dipole-quadrupole ( A ) and quadrupole-quadrupole ( C ) polarizabilities which we have successfully applied to the benzothiazole (A)-benzobisthiazole (B) linear oligomer A-B 13 -A. Two model rotational isomers have been characterized: (1) the fully-planar (000) conformation; and (2) a rotational isomer with each unit rotated in the range 1 − 10° in the same direction (+++). For isomer 000, µ is smaller than for +++. The calculation of α , A and C has been carried out by the interacting induced dipoles polarization model that calculates tensor effective anisotropic point polarizabilities (method of Applequist et al.). The values of A are specially sensitive to µ which varies under rotation. This fact explains the great values of A x xx , for the +++ polar isomer. It is found that small torsional changes can enhance solubility by a clear increasing of the hydrophilic accessible surface area. However, the torsion of the oligomer varies the value of µ and so modifies α , C , and, specially, A . For conformer +++, polarization effects occur even when each unit is rotated only φ = 1°. The observed effect is an increase in µ and, hence, in α , C , and, specially, A .

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“…However, this model gave a good (within 10%) agreement with experiment for medium polarizabilities and an unsatisfactory agreement for the main components of polarizability and anisotropy. This concept was further developed in [8], with anisotropic effects included, and then in [9], where the repulsion of electrons was taken into account.Further complication and modification of the model, made in [10,11], failed to improve significantly the agreement between the quantities mentioned. The last study employing this model and some of its preceding modifications was performed in 1999.…”

mentioning

confidence: 99%

“…Further complication and modification of the model, made in [10,11], failed to improve significantly the agreement between the quantities mentioned. The last study employing this model and some of its preceding modifications was performed in 1999.…”

mentioning

confidence: 99%

Relationship between the Relative Permittivity of Nonpolar Gases and Ionization Potential of Molecules

Zevatskii

2005

Russ J Appl Chem

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A method is suggested for relating the relative permittivity, ionization potential, polarizability, and linear dimensions of nonpolar molecules. This was demonstrated for the example of inert gases, some spherical-and symmetric-top molecules, and linear molecules.Taking into account the polarizability of organic molecules and ions is important when describing quantitatively the mechanisms and rates of nonradical reactions. The energy of intermolecular dispersion interaction is directly related to the polarizabilities of molecules under consideration. The influence of the dispersion interaction on the reactivity was analyzed in [13 6]. The polarizabilities are commonly determined by extrapolation methods from the refractive index (using the Lorentz3Lorenz formula) and from the relative permittivities of substances. The most accurate values of the molecular polarizability can be obtained from the above parameters determined for the gaseous state, i.e., the case in which the contribution of intermolecular interactions can be neglected.In analysis of models of the molecular polarizability, attention is attracted by the fact that the influence exerted by the field of the induced dipole on the atomic polarization is disregarded in the literature concerned with nonpolar molecules. An attempt to consider this factor was made in [7]. However, an important point is that the field of the induced dipole is considered in a superposition with that of the permanent dipole for polar molecules. Atoms are regarded as isotropically polarized points, and the induced dipole moment of a molecule is represented aswhere A i is the polarizability tensor of ith atom, and T ij is the tensor of a field created by the induced dipole, which can be written in the matrix form aswhere r is the distance between ith and jth atoms;x, y, z, components of the vector running from point i to point j in the Cartesian coordinates. The expression in the brackets reflects the total field at ith atom, constituted by the externally applied field and the field of all induced dipoles of the system. However, this model gave a good (within 10%) agreement with experiment for medium polarizabilities and an unsatisfactory agreement for the main components of polarizability and anisotropy. This concept was further developed in [8], with anisotropic effects included, and then in [9], where the repulsion of electrons was taken into account.Further complication and modification of the model, made in [10,11], failed to improve significantly the agreement between the quantities mentioned. The last study employing this model and some of its preceding modifications was performed in 1999. The average and principal components of polarizability, calculated in this study for amino acids and peptides, coincided with the expected values only within an order of magnitude. This is natural, because the field of the induced dipole for polar molecules is three orders of magnitude lower than the field of the permanent dipole. Therefore, the model of polarizability of nonpolar molecule...

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Atom charge transfer in molecular polarizabilities: application of the Olson-Sundberg model to aliphatic and aromatic hydrocarbons

Cited by 100 publications

References 14 publications

Orientational and induced contributions to the depolarized Rayleigh spectra of liquid and supercooled ortho-terphenyl

Orientational and induced contributions to the depolarized Rayleigh spectra of liquid and supercooled ortho-terphenyl

Polarization by the effect of a small torsional change in the benzothiazole (A)-benzobisthiazole (B) oligomer A-B13-A

Relationship between the Relative Permittivity of Nonpolar Gases and Ionization Potential of Molecules

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