The thermodynamics of solvation of a dipole in hard sphere solvents with dipoles and quadrupoles is studied by using the Padé approximation for the perturbation expansion of the solvation chemical potential and compared to Monte Carlo simulations. Solvation chemical potentials, energies, and entropies of solvation are obtained at different dipolar and quadrupolar solvent strengths. The effect of nonlinear solvation is analyzed and found not to exceed 10% in the parameter range studied. An agreement between the simulations and the analytical theory is obtained by an empirical rescaling of the triple perturbation integrals of the perturbation expansion. This rescaling does not, however, provide a quantitatively correct partitioning of the solvation free energy into the energy and entropy of solvation.
Skip Nav Destination
Article navigation
22 August 1999
Research Article|
August 22 1999
A perturbation theory for solvation thermodynamics: Dipolar–quadrupolar liquids
Dmitry V. Matyushov;
Dmitry V. Matyushov
Department of Chemistry and Henry Eyring Center for Theoretical Chemistry, University of Utah, Salt Lake City, Utah 84112
Search for other works by this author on:
Gregory A. Voth
Gregory A. Voth
Department of Chemistry and Henry Eyring Center for Theoretical Chemistry, University of Utah, Salt Lake City, Utah 84112
Search for other works by this author on:
J. Chem. Phys. 111, 3630–3638 (1999)
Article history
Received:
January 28 1999
Accepted:
May 25 1999
Citation
Dmitry V. Matyushov, Gregory A. Voth; A perturbation theory for solvation thermodynamics: Dipolar–quadrupolar liquids. J. Chem. Phys. 22 August 1999; 111 (8): 3630–3638. https://doi.org/10.1063/1.479643
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Dielectric profile at the Pt(111)/water interface
Jia-Xin Zhu, Jun Cheng, et al.
Related Content
Relationships between bridging oxygen O 17 quadrupolar coupling parameters and structure in alkali silicates
J. Chem. Phys. (May 1998)
Residual dipolar couplings between quadrupolar nuclei in high resolution solid state NMR: Description and observations in the high-field limit
J. Chem. Phys. (February 2000)
Radio-frequency-mediated dipolar recoupling among half-integer quadrupolar spins
J. Chem. Phys. (April 2000)
Fast radio-frequency amplitude modulation in multiple-quantum magic-angle-spinning nuclear magnetic resonance: Theory and experiments
J. Chem. Phys. (February 2000)
A dielectric theory of spin-lattice relaxation for nuclei with electric quadrupole moments
J. Chem. Phys. (July 1998)