TY - JOUR

T1 - A molecular site-site integral equation that yields the dielectric constant

AU - Dyer, Kippi M.

AU - Perkyns, John S.

AU - Stell, George

AU - Pettitt, B. Montgomery

N1 - Funding Information:
We gratefully acknowledge the support of the several agencies responsible for funding this work. K.M.D., J.S.P., and B.M.P. acknowledge the support of the Robert A. Welch Foundation (E1028) and the NIH (GM037657). G.S. acknowledges the support of the Division of Chemical Sciences, Office of Basic Energy Sciences, Office of Energy Research, U.S. Department of Energy. B.M.P. thanks Martin Karplus for a thoughtful reading of an early version of this work.

PY - 2008

Y1 - 2008

N2 - Our recent derivation [K. M. Dyer, J. Chem. Phys. 127, 194506 (2007)] of a diagrammatically proper, site-site, integral equation theory using molecular angular expansions is extended to polar fluids. With the addition of atomic site charges we take advantage of the formal long-ranged potential field cancellations before renormalization to generate a set of numerically stable equations. Results for calculations in a minimal (spherical) angular basis set are presented for the radial distribution function, the first dipolar (110) projection, and the dielectric constant for two model diatomic systems. All results, when compared to experiment and simulation, are a significant quantitative and qualitative improvement over previous site-site theories. More importantly, the dielectric constant is not trivial and close to simulation and experiment.

AB - Our recent derivation [K. M. Dyer, J. Chem. Phys. 127, 194506 (2007)] of a diagrammatically proper, site-site, integral equation theory using molecular angular expansions is extended to polar fluids. With the addition of atomic site charges we take advantage of the formal long-ranged potential field cancellations before renormalization to generate a set of numerically stable equations. Results for calculations in a minimal (spherical) angular basis set are presented for the radial distribution function, the first dipolar (110) projection, and the dielectric constant for two model diatomic systems. All results, when compared to experiment and simulation, are a significant quantitative and qualitative improvement over previous site-site theories. More importantly, the dielectric constant is not trivial and close to simulation and experiment.

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U2 - 10.1063/1.2976580

DO - 10.1063/1.2976580

M3 - Article

C2 - 19044929

AN - SCOPUS:51749093938

VL - 129

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 10

M1 - 104512

ER -