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  • 1
    Electronic Resource
    Electronic Resource
    Dynamic solvent effects in adiabatic electron-transfer reactions: role of translational modes (1990)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 94 (1990), S. 5197-5200 
    Details
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/j100376a001
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  • 2
    Electronic Resource
    Electronic Resource
    Molecular hydrodynamic theory of non-Markovian collective orientational relaxation in dense dipolar liquids (1991)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 5289-5299 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A microscopic study of the non-Markovian (or memory) effects on the collective orientational relaxation in a dense dipolar liquid is carried out by using an extended hydrodynamic approach which provides a reliable description of the dynamical processes occuring at the molecular length scales. Detailed calculations of the wave-vector dependent orientational correlation functions are presented. The memory effects are found to play an important role; the non-Markovian results differ considerably from that of the Markovian theory. In particular, a slow long-time decay of the longitudinal orientational correlation function is observed for dense liquids which becomes weaker in the presence of a sizeable translational contribution to the collective orientational relaxation. This slow decay can be attributed to the intermolecular correlations at the molecular length scales. The longitudinal component of the orientational correlation function becomes oscillatory in the underdamped limit of momenta relaxations and the frequency dependence of the friction reduce the frictional resistance on the collective excitations (commonly known as dipolarons) to make them long lived. The theory predicts that these dipolarons can, therefore, be important in chemical relaxation processes, in contradiction to the claims of some earlier theoretical studies.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.461830
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  • 3
    Electronic Resource
    Electronic Resource
    Ultrafast solvation dynamics: Molecular explanation of computer simulation results in a simple dipolar solvent (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 5126-5131 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Recently Perera and Berkowitz [J. Chem Phys. 96, 3092 (1992)] and Neria and Nitzan [J. Chem. Phys. 96, 5433 (1992)] carried out computer simulations of solvation dynamics of an ion in dense Stockmayer liquids. Both the simulations observed an ultrafast component which decays in a few tens of femtoseconds with a Gaussian time dependence. This is followed by a slow exponential-like decay with a time constant of a few picoseconds. It is shown here that many of the simulation results can be explained very well from a first principles theory with no adjustable parameter.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.463809
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  • 4
    Electronic Resource
    Electronic Resource
    Electrostriction: A density functional theory (1991)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 1168-1174 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A study of electrostriction in a dipolar liquid is carried out by using the density functional theory for inhomogeneous systems. A general expression for electrostriction due to a position-dependent electric field is derived. The expression for the electrostriction due to a constant macroscopic electric field is derived in terms of both orientational structure factors and dielectric function. This expression is found to reduce exactly to the expression derived earlier by Rasaiah, Isbister, and Stell when the proper identifications are made. A study of the change in density profile around a point ion in the dipolar liquid is carried out. It is found that the density profile is oscillatory, which is expected. However, our expression which considers only the quadratic nonlinearity in the electric field, breaks down at a very short distance from the ion. The microscopic structure of the liquid is shown to play an important role at the molecular length scales.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.461147
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  • 5
    Electronic Resource
    Electronic Resource
    Molecular theory of solvation and solvation dynamics in a binary dipolar liquid (1991)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 8367-8377 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Both the equilibrium and the dynamical aspects of solvation of a classical ion in a dense binary dipolar liquid are investigated by using a molecular theory. The theory properly includes the differing inter- and intramolecular correlations that are present in a binary mixture. As a result, the theory can explain several important aspects of the nonideality of equilibrium solvation energy (broadly known as preferential solvation) observed in experiments. We find that the nonideality of solvation depends strongly on both the molecular size and the magnitude of the dipole moment of the solvent molecules. The interactions among the solvent molecules play an important role in determining the extent of this nonideality. The dynamical calculations are based on a generalized Smoluchowski equation which has been used extensively for studies in one component liquid. For binary liquid, our study reveals rich and diverse behavior such as dependencies on the sizes, the transport coefficients and the polar properties of the components. The theory offers a detailed picture of the dependence of the solvation dynamics on the composition of the mixture. It is predicted that the dynamics of solvation in a binary liquid is, in general, nonexponential and that the details of the dynamics can be quite different from those in a one component liquid. In particular, the continuum model is found to be grossly inaccurate in describing the solvation dynamics in binary mixtures and rather extreme conditions are needed to recover the predictions of the continuum model which can be attributed to the nonideality of the solvation. The predicted results are used to study the dynamic solvent effects on the rate of an adiabatic electron transfer reaction in a binary liquid. The theoretical predictions are also compared with the available experimental results.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.460068
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  • 6
    Electronic Resource
    Electronic Resource
    Macro–micro relations in dipolar orientational relaxation: An exactly solvable model of dielectric relaxation (1990)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 1955-1958 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The relationship between the microscopic orientational relaxation time (τm) and the collective, macroscopic relaxation time (τM) of a dipolar liquid has been a subject of considerable interest. We examine this relation for the kinetic Ising model of Glauber, used recently by Skinner to describe dielectric relaxation in glassy polymers. In this model, exact solutions for both the same spin and the collective spin time correlation functions are possible. We find that these two correlation functions are entirely different from each other. The self spin correlation function is highly nonexponential, as pointed out by Glauber and by Skinner. But, the collective spin relaxation is single exponential, and the wave vector and frequency dependent dielectric function is of simple Debye form. The reason for this difference is discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.459073
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  • 7
    Electronic Resource
    Electronic Resource
    Collective excitations in a dense dipolar liquid: How important are dipolarons in the polarization relaxation of common dipolar liquids? (1990)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 6833-6839 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: It was recently proposed that collective polarization excitations, called dipolarons in analogy with the plasmons in the Coulomb systems, can exist for a long duration in a dense dipolar liquid. In this article, we present a microscopic analysis of the properties of such collective excitations, both at small and at intermediate wave vectors. The theory predicts the existence of dipolarons at values of the relevant parameters which are in good agreement with the computer simulation of Pollock and Alder. However, the predicted range of the parameter values in which the "true'' dipolaronic behavior is significant are rather too small to be important in common dipolar liquids like water, acetonitrile or methyl iodide. We find that the microscopic structure, especially the local orientational correlations and also the translational modes of the liquid, play important roles in determining the nature and the lifetime of the dipolaronic modes. Especially, these modes are more likely to occur at intermediate wave numbers if the translational contribution to the polarization relaxation is significant. The consequences of these theoretical predictions in experimental studies are discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.458269
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  • 8
    Electronic Resource
    Electronic Resource
    Solvation dynamics in a Brownian dipole lattice: A comparison between theory and computer simulation (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 9311-9320 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Papazyan and Maroncelli [J. Chem. Phys. 95, 9219 (1991)] recently reported computer simulations of solvation dynamics of an ion in a Brownian dipole lattice solvent. In the present article we compare these results to predictions of a number of theories of solvation dynamics in the diffusive limit. The frequency-dependent dielectric response functions needed as input to many of the theories are derived from further simulations of the lattice solvent [H. X. Zhou and B. Bagchi, J. Chem. Phys. 97, 3610 (1992)]. When properly applied, all of the currently popular molecular theories yield reasonable predictions for the time scale of the solvation response. The dynamical MSA model [P. G. Wolynes, J. Chem. Phys. 86, 5133 (1987)] and the memory function theory of Fried and Mukamel [J. Chem. Phys. 93, 932 (1990)] both provide nearly quantitative agreement with all aspects of the solvation dynamics observed in these simulations.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.463307
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  • 9
    Electronic Resource
    Electronic Resource
    Inertial effects in solvation dynamics (1991)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 3177-3182 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The dynamics of solvation of newly created charged species in dense dipolar liquids can proceed at a high speed with time constants often in the subpicosecond domain. The motion of the solvent molecules can be in the inertial limit at such short times. In this paper we present a microscopic study of the effects of inertial motion of solvent molecules on the solvation dynamics of a newly created ion in a model dipolar liquid. Interesting dynamical behavior emerges when the relative contribution of the translational modes in the wave-vector-dependent longitudinal relaxation time is significant. Especially, the theory predicts that the time correlation function of the solvation energy can become oscillatory in some limiting situations. In general, the dynamics becomes faster in the presence of the inertial contribution. We discuss the experimental situations where the inertial effects can be noticeable.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.459786
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  • 10
    Electronic Resource
    Electronic Resource
    Molecular expression for dielectric friction on a rotating dipole: Reduction to the continuum theory (1993)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 98 (1993), S. 3351-3355 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Recently we presented a microscopic expression for dielectric friction on a rotating dipole. This expression has a rather curious structure, involving the contributions of the transverse polarization modes of the solvent and also of the molecular length scale processes. It is shown here that under proper limiting conditions, this expression reduces exactly to the classical continuum model expression of Nee and Zwanzig [J. Chem. Phys. 52, 6353 (1970)]. The derivation requires the use of the asymptotic form of the orientation-dependent total pair correlation function, the neglect of the contributions of translational modes of the solvent, and also the use of the limit that the size of the solvent molecules goes to zero. Thus, the derivation can be important in understanding the validity of the continuum model and can also help in explaining the results of a recent computer simulation study of dielectric relaxation in a Brownian dipolar lattice.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.464107
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