Thermodynamic properties of polarizable Stockmayer fluids: perturbation theory and simulation

Kriebel, Christian

doi:10.1080/00268979650026532

Cited by 26 publications

(7 citation statements)

References 34 publications

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“…In this way, the dipolar spectral shift is represented as the sum of two terms corresponding to the two separate time scales of the solvent: (i) the difference of the solvation chemical potentials Δμ ∞ of solvation by the fast electronic degrees of freedom and (ii) the work of changing the solute dipolar in the frozen reaction field Φ in g of the inertial solvent modes where Φ in g is related to the inertialess part of the solvation chemical potential by the expression In order to get the shift, we need the response function μ (2) . We apply to this end the Padé form of the response function μ (2) recently proposed by us 28b as an extension of the Stell et al. 64a,b theory of dipolar liquids and the Wertheim ansatz 64c of incorporating the liquid polarizability. The latter replaces the polarizable liquid of coupled induced dipoles with a fictitious fluid with effective dipole moments calculated in a self-consistent manner.…”

Section: Calculation Proceduresmentioning

confidence: 99%

“…The spectral shift stemming from differential solvation of ground, m g , and excited, m e , dipolar states of the solute is given by the relation 13b determined through the static P = P ( r 0 , y ,η) and high-frequency P ∞ = P ∞ ( r 0 , y ∞ ,η) Padé response functions depending on the reduced solute size r 0 = R 0 /σ + 1 / 2 , liquid-packing density η, and the dielectric parameters y = (4π/9)β pm‘ 2 + (4π/3)ρα s and y ∞ = (4π/3)ρα s of the liquid state solvent dipole moment m‘ and the polarizability α s (the explicit relations for the Padé response functions P and P ∞ are given in Appendix B). The renormalized solvent dipole moment m‘ was calculated from its vacuum value in the framework of Wertheim theory 64c…”

Section: Calculation Proceduresmentioning

confidence: 99%

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A Thermodynamic Analysis of the π* andE_T(30) Polarity Scales

1997

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The solvent-induced UV−vis spectral shifts in 4-nitroanisole and pyridinium N-phenoxide betaine-30 dyes utilized in the famous π* and E T(30) polarity scales, respectively, are analyzed by molecular theories in terms of long-range solute−solvent interactions due to induction, dispersion, and dipole−dipole forces. The solvent-induced shift is represented as a sum of the differential solute−solvent internal energy and the differential energy of binding the solvent molecules in the solute vicinity. The aim of the study is 3−fold: (i) to clarify and quantify the relative effects of the three types of interactions, (ii) to elicit the magnitude of the effect of specific forces, and (iii) to evaluate the contribution of the differential solvent binding to the spectral shift. For (i), the dye properties directing the weighting are the size and the differences in both polarizability and dipole moment between ground and excited states. Accordingly, the distinctions π* vs E T(30) derive from the different sizes (4.5 vs 6.4 Å), dramatically different polarizability enhancement upon excitation (6 vs 61 Å3), and opposite changes in the dipole moment (+8.2 vs −8.6 D) of the two dyes. As a key result, the importance of dispersion forces to the spectral shift even in highly polar liquids is emphasized. While the contributions of dispersions and inductions are comparable in the π* scale, inductions are clearly overshadowed by dispersions in the E T(30) values. Both effects reinforce each other in π*, producing the well-known red shift. For the E T(30) scale, the effects due to dispersion and dipolar solvation have opposite signs making the red shift for nonpolar solvents switch to the blue for polar solvents. For (ii), there is overall reasonable agreement between theory and experiment for both dyes, as far as the nonpolar and select solvents are concerned, but there are also discrepant solvent classes. Thus, the predicted E T(30) values for protic solvents are uniformly too low, revealing a decrease in H-bonding interactions of the excited state with lowered dipole moment. Further, the calculated π* values of aromatic and chlorinated solvents are throughout too high, and this is explained by an increase in charge-transfer interactions of the more delocalized excited state. For (iii), the differential solvent binding energies have been extracted from experimental thermochromic data. For strongly polar fluids, the solute−solvent component of the shift overshadows that from the solvent binding energy variation. In nonpolar and weakly polar liquids the two parts are comparable for 4-nitroanisole, but the latter is still small for betaine-30. Experimental and calculated values in the present work parameters for betaine-30 are applied to calculating solvent reorganization energies λs of intramolecular electron transfer. λs is separated into polar activation by the solvent permanent dipoles and nonpolar activation due to induction and dispersion forces. Experimental reorganization energies due to the classical solvent and solute modes ...

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Section: Calculation Proceduresmentioning

confidence: 99%

Section: Calculation Proceduresmentioning

confidence: 99%

A Thermodynamic Analysis of the π* andE_T(30) Polarity Scales

1997

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“…The renormalized fluid is one with the effective dipole moment (rather than the value in vacuo) and with no polarizability, and the problem is thus rephrased in terms of two‐body and three‐body correlations. The theory was extended to mixtures and comprehensively described by Venkatasubramanian et al,20 Joslin et al,21 and Gray et al22 If we restrict our considerations to bulk properties (excluding the dielectric behavior of a fluid), the RPT, despite its elegance, was next applied only a decade later, when Kriebel and Winkelmann23–25 developed an equation of state for polarizable spherical and polarizable two‐center Lennard‐Jones molecules with embedded dipole moment. They used a simplified implementation of RPT and compared their model to their own molecular simulation data.…”

Section: Introductionmentioning

confidence: 99%

An equation of state contribution for polar components: Polarizable dipoles

2006

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“…For the free energy, a Padé approximant can be given with free energy perturbation terms that can be calculated if one knows the g 0 radial distribution function of the reference HS system. The exact forms of these perturbation integrals can be found elsewhere [21,36].…”

Section: The Molecular Approachmentioning

confidence: 99%

“…Notable exceptions in this trend of specification are the works of Kriebel and Winkelmann [36,37] who gave a systematic study of the thermodynamic properties of the PSTM [36] and the polarizable dipolar two-centred Lennard-Jones (LJ) fluid [37]. Nevertheless, they did not have interest in the dielectric properties of these systems.…”

Section: Introductionmentioning

confidence: 99%

Dielectric constant of the polarizable dipolar hard sphere fluid studied by Monte Carlo simulation and theories

Valisko¹,

Boda²

2005

Condens. Matter Phys.

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A systematic Monte Carlo (MC) simulation and perturbation theoretical (PT) study is reported for the dielectric constant of the polarizable dipolar hard sphere (PDHS) fluid. We take the polarizability of the molecules into account in two different ways. In a continuum approach we place the permanent dipole of the molecule into a sphere of dielectric constant ∞ in the spirit of Onsager. The high frequency dielectric constant ∞ is calculated from the Clausius-Mosotti relation, while the dielectric constant of the polarizable fluid is obtained from the Kirkwood-Fröhlich equation. In the molecular approach, the polarizability is built into the model on the molecular level, which makes the interactions non-pairwise additive. Here we use Wertheim's renormalized PT method to calculate the induced dipole moment, while the dielectric constant is calculated from our recently introduced formula [22]. We also apply a series expansion for the dielectric constant both in the continuum and the molecular approach. These series expansions ensure a better agreement with simulation results. The agreement between our MC data and the PT results in the molecular approach is excellent for low to moderate dipole moments and polarizabilities. At stronger dipolar interactions ergodicity problems and anizotropic behaviour appear where simulation results become uncertain and the theoretical approach becomes invalid.

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Thermodynamic properties of polarizable Stockmayer fluids: perturbation theory and simulation

Cited by 26 publications

References 34 publications

A Thermodynamic Analysis of the π* andE_T(30) Polarity Scales

A Thermodynamic Analysis of the π* andE_T(30) Polarity Scales

An equation of state contribution for polar components: Polarizable dipoles

Dielectric constant of the polarizable dipolar hard sphere fluid studied by Monte Carlo simulation and theories

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Thermodynamic properties of polarizable Stockmayer fluids: perturbation theory and simulation

Cited by 26 publications

References 34 publications

A Thermodynamic Analysis of the π* andET(30) Polarity Scales

A Thermodynamic Analysis of the π* andET(30) Polarity Scales

An equation of state contribution for polar components: Polarizable dipoles

Dielectric constant of the polarizable dipolar hard sphere fluid studied by Monte Carlo simulation and theories

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Product

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A Thermodynamic Analysis of the π* andE_T(30) Polarity Scales

A Thermodynamic Analysis of the π* andE_T(30) Polarity Scales