Abstract
The angular dependent site-renormalized integral equation theory is developed to compute the dihedral conformation distribution and intermolecular pair distributions of n-butane at infinite dilution in a Lennard-Jones solvent. The equations take advantage of the topological diagrammatic expansion of the full angular dependent molecular system by resumming the series in conjunction with the intramolecular degree of freedom. To first order in an angular basis set, the numerical results of these site-renormalized equations are a systematic quantitative improvement over previous methods. In particular, the thermodynamics and conformational distribution of the solute are essentially indistinguishable from simulation.
Highlights
In contrast to the study of simple liquids, a significant challenge in the study of the statistical mechanics of molecular liquids is the intricate multidimensional coupling of the pair distribution functions of molecules
We presented an angle dependent site-renormalized integral equation theory for calculating the intramolecular and intermolecular pair distributions of n-butane at infinite dilution in a Lennard-Jones solvent
The equations were derived from the diagrammatic expansion of the full angular dependent molecular system of equations by resumming the series self-consistently
Summary
In contrast to the study of simple liquids, a significant challenge in the study of the statistical mechanics of molecular liquids is the intricate multidimensional coupling of the pair distribution functions of molecules. An especially encouraging recent development [13] was, through means of topological resummation or renormalization for each site in the diagrammatic expansion of the pair functions, the derivation of an exact set of integral equations for site-site models which is formally equivalent to the rotational invariant methods of Blum and Torruella [14] for single-center molecular models. In addition to the formal development, for diatomic models, the quantitative predictions of the theory using a minimal, isotropic basis, were a significant improvement over existing methods, and, since full molecular dimensionality is intrinsic to the theory, the 3D structural projections (as well as higher order projections) are a natural feature of the theory This confluence of interests, together with this special tribute to Fumio Hirata, suggests an extension to intramolecular degrees of freedom. We detail the extension of the angle dependent site-renormalized theory to n-butane in the Lennard-Jones fluid, a formally exact method for self-consistently calculating the conformation distribution of the solute, numerical results, and conclusions
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