Solvent mean force perturbations of diatomic dissociation reactions. Comparison of perturbed hard fluid and computer simulation results

de Souza, Luís E. S.; Ben-Amotz, Dor
September 1994
Journal of Chemical Physics;9/1/1994, Vol. 101 Issue 5, p4117
Academic Journal
The perturbed hard fluid model, which separates solute–solvent interactions into repulsive hard sphere and mean field attractive contributions, is applied to predict solvent effects on the thermodynamics of diatomic dissociation reactions. Theoretically predicted changes in excess Gibbs free energy (ΔG), entropy (ΔS), enthalpy (ΔH), and volume (ΔV) for the dissociation of a homonuclear diatomic dissolved in a monatomic solvent, with Lennard-Jones solute atom–solvent atom and solvent–solvent interaction potentials, are compared with computer simulation results. The perturbed hard fluid model requires only one adjustable parameter, which is determined using simulation results at a single temperature and density. This parameter is used in the prediction of reaction thermodynamics over the entire vapor, liquid, and supercritical fluid regime. Furthermore, the thermodynamics of other reactions, in which the solute atom–solvent atom attractive well depth changes upon dissociation, can be predicted by including one additional parameter, determined using only simulation results for a system with no well depth change.


Related Articles

  • Modeling of dynamic molecular solvent properties using local and cavity field approaches. Macak, Peter; Norman, Patrick; Luo, Yi; Ågren, Hans // Journal of Chemical Physics;1/22/2000, Vol. 112 Issue 4 

    Current models of solvent properties using cavity reaction field methods are analyzed and categorized in two groups according to the use of local fields or cavity fields as the perturbing fields. Analytical connections between the two approaches are derived. © 2000 American Institute of Physics.

  • A second-order perturbative correction to the coupled-cluster singles and doubles method: CCSD(2). Gwaltney, Steven R.; Head-Gordon, Martin // Journal of Chemical Physics;Aug2001, Vol. 115 Issue 5, p2014 

    Recently, we introduced a new ansatz for developing perturbative corrections to methods based on coupled-cluster theory. In this article we apply this ansatz to the coupled-cluster singles and doubles (CCSD) method, generating the CCSD(2) method. We use the CCSD(2) method to study the double...

  • On the low-lying electronic states of the molecule BeN. Ornellas, F. R.; Roberto-Neto, O.; Borin, A. C.; Machado, F. B. C. // Journal of Chemical Physics;12/15/1991, Vol. 95 Issue 12, p9086 

    Using the multireference singles and doubles configuration-interaction approach, this study presents for the first time reliable theoretical evidence of the existence of a new molecular species, BeN. Potential-energy curves, vibrational energy spacings, dissociation energies, dipole moments, and...

  • Inverted perturbation approach (IPA) potentials and adiabatic corrections of the X 1Σ+ state of the lithium hydrides near the dissociation limits. Chan, Y. C.; Harding, D. R.; Stwalley, W. C.; Vidal, C. R. // Journal of Chemical Physics;9/1/1986, Vol. 85 Issue 5, p2436 

    Laser-induced fluorescence (LIF) spectra of the A–X system of the LiH isotopes, excited by the UV lines of an argon and a krypton ion laser, were observed and analyzed. Three long LIF series of different LiH isotopes were taken with a 3.4 m high resolution spectrograph. The results were...

  • Ground states of the Mo2, W2, and CrMo molecules: A second and third order multireference perturbation theory study. Angeli, Celestino; Cavallini, Alex; Cimiraglia, Renzo // Journal of Chemical Physics;8/21/2007, Vol. 127 Issue 7, p074306 

    The potential energy curves of the molecules Mo2, W2, and CrMo have been studied ab initio using large basis sets and the “n-electron valence state perturbation theory” up to the third order in the energy. The third order results for Mo2 and W2 reproduce the equilibrium distances re...

  • Selected dissociation- and correlation-consistent configuration interaction by a perturbative criterion. Merchán, M.; González-Luque, R.; Nebot-Gil, I. // Journal of Chemical Physics;7/1/1990, Vol. 93 Issue 1, p495 

    We propose a perturbative criterion to select the most important dissociation- or correlation-consistent type of contributions to perform generalized valence bond-configuration interaction (GVB-CI) calculations, dissociation-consistent configuration interaction (DCCI) or correlation-consistent...

  • High-level ab initio studies of unimolecular dissociation of the ground-state N3 radical. Zhang, Peng; Morokuma, Keiji; Wodtke, Alec M. // Journal of Chemical Physics;1/1/2005, Vol. 122 Issue 1, p014106 

    A comprehensive study of the unimolecular dissociation of the N3 radical on the ground doublet and excited quartet potential energy surfaces has been carried out with multireference single and double excitation configuration interaction and second-order multireference perturbation methods. Two...

  • A study of the ground state of manganese dimer using quasidegenerate perturbation theory. Yamamoto, Shigeyoshi; Tatewaki, Hiroshi; Moriyama, Hiroko; Nakano, Haruyuki // Journal of Chemical Physics;3/28/2006, Vol. 124 Issue 12, p124302 

    We study the electronic structure of the ground state of the manganese dimer using the state-averaged complete active space self-consistent field method, followed by second-order quasidegenerate perturbation theory. Overall potential energy curves are calculated for the 1Σg+, 11Σu+, and...

  • Valence bond calculations of the potential energy surface for CH4→CH3+H. Wu, Wei; McWeeny, Roy // Journal of Chemical Physics;9/15/1994, Vol. 101 Issue 6, p4826 

    A valence bond study of the potential energy surface for methane CH4→CH3+H is performed at the 6–31G level using (i) a valence bond self-constituent field (VB-SCF) method; (ii) a valence bond configuration interaction (VBCI) method; and (iii) an antisymmetrized product of...


Read the Article


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

Try another library?
Sign out of this library

Other Topics