Inclusion of nonequilibrium continuum solvation effects in variational transition state theory

Truhlar, Donald G.; Schenter, Gregory K.; Garrett, Bruce C.
April 1993
Journal of Chemical Physics;4/1/1993, Vol. 98 Issue 7, p5756
Academic Journal
We define a general set of effective solvent coordinates for reactions in solution that should be especially well suited for polar solvents. No specific functional form is assumed for the variation of charges with motions along or orthogonal to the reaction coordinate, and as a consequence the formalism allows the treatment of arbitrary reaction types using electronic structure calculations for the solute charge distribution. A critical assumption of the theory is that the nonequilibrium polarization field may be represented in terms of the adiabatic polarization fields that arise for linear geometric displacements. The results are combined with the Cartesian-coordinate canonical variational transition state theory presented previously to provide a general method for including both equilibrium and nonequilibrium solvation effects of a nondissipative, continuum-dielectric solvent in practical calculations of rate constants.


Related Articles

  • Equilibrium and nonequilibrium solvation and solute electronic structure. I. Formulation. Kim, Hyung J.; Hynes, James T. // Journal of Chemical Physics;10/1/1990, Vol. 93 Issue 7, p5194 

    A theoretical formulation is developed to describe the electronic structure of an immersed solute, electrostatically coupled to a polar and polarizable solvent. The solvent is characterized, in the dielectric continuum approximation, by electronic and orientational polarizations. Starting from a...

  • Solvation dynamics and electronic structure development of coumarin 120 in methanol: A theoretical modeling study. Ando, Koji // Journal of Chemical Physics;9/22/1997, Vol. 107 Issue 12, p4585 

    Electronic structure evolution of an organic dye coumarin 120 coupled to polar solvation dynamics is examined by combining ab initio electronic structure calculations and molecular dynamics (MD) simulations. Sets of nonorthogonal Hartree-Fock molecular orbitals optimized in vacuo and in...

  • Modeling solvation effects in real-space and real-time within density functional approaches. Delgado, Alain; Corni, Stefano; Pittalis, Stefano; Rozzi, Carlo Andrea // Journal of Chemical Physics;2015, Vol. 143 Issue 14, p1 

    The Polarizable Continuum Model (PCM) can be used in conjunction with Density Functional Theory (DFT) and its time-dependent extension (TDDFT) to simulate the electronic and optical properties of molecules and nanoparticles immersed in a dielectric environment, typically liquid solvents. In this...

  • Ion solvation in clusters. Rips, Ilya; Jortner, Joshua // Journal of Chemical Physics;7/1/1992, Vol. 97 Issue 1, p536 

    Solvent size effects on ion solvation in clusters of polar molecules are explored. Expressions for the adiabatic and the vertical solvation energies of an ion imbedded in a cluster are derived within the framework of the mean-spherical approximation (MSA). The short-range order in the finite...

  • Density functional solvation model based on CM2 atomic charges. Tianhai Zhu; Jiabo Li // Journal of Chemical Physics;11/22/1998, Vol. 109 Issue 20, p9117 

    Evaluates the use of SM5 solvation model in conjunction with high-level electronic structure calculations. Presentation of several implementations based on density-functional theory; Employment of fixed solute geometries in solvation calculations; Description of the electric polarization in the...

  • Reference interaction site model self-consistent field study for solvation effect on carbonyl compounds in aqueous solution. Ten-no, Seiichiro; Hirata, Fumio; Kato, Shigeki // Journal of Chemical Physics;5/15/1994, Vol. 100 Issue 10, p7443 

    In the previous study, Chem. Phys. Lett. 214, 391 (1993), we developed a new computational procedure for the solvation effect on the electronic structure of solute based upon the reference interaction site model (RISM) integral equation and the Hartree–Fock equation. The method enables us...

  • Equilibrium and nonequilibrium solvation and solute electronic structure. II. Strong coupling limit. Kim, Hyung J.; Hynes, James T. // Journal of Chemical Physics;10/1/1990, Vol. 93 Issue 7, p5211 

    The formulation developed in the preceding paper [H. J. Kim and J. T. Hynes, J. Chem. Phys. 93, 5194 (1990)] is applied to describe the electronic structure and spectroscopic features of a model symmetric electron–donor–acceptor solute system D-A⇋DA- in solution in the...

  • Electronic and optical properties of BaTiO[sub 3] and SrTiO[sub 3]. Ahuja, R.; Eriksson, O.; Johansson, B. // Journal of Applied Physics;8/15/2001, Vol. 90 Issue 4, p1854 

    We have used the linear muffin-tin-orbital method, without geometrical approximations, to calculate the electronic structure of tetragonal BaTiO and cubic SrTiO. Using our self-consistent potential, we have calculated the frequency-dependent dielectric function and the reflectivity...

  • Charge penetration in dielectric models of solvation. Chipman, Daniel M. // Journal of Chemical Physics;6/22/1997, Vol. 106 Issue 24, p10194 

    Studies charge penetration in dielectric models of solvation. Solute electrostatic potential in vacuum; Solute electrostatic potential in solvent; Volume polarization; Surface polarization; Total polarization charge; Neglect of volume polarization; Previous methods of charge renormalization;...


Read the Article


Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics