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Approximative “one particle” bridge function B (1) ( r ) for the theory of simple fluids



New properties for the one particle bridge function B (1) ( r ) B ( 1 ) ( r ) , which are necessary to the calculation of the excess chemical potential β μ ex β μ ex , are derived for the hard sphere fluid. The method, which only requires the knowledge of the bridge function B (2) ( r ) B ( 2 ) ( r ) , is based on an investigation of the correlation function dependence on the Kirkwood charging parameter. In this framework, the unavoidable question of topological homotopy is addressed. As far as B (2) ( r ) B ( 2 ) ( r ) is considered as exact, this work provides useful information on B (1) ( r ) B ( 1 ) ( r ) in the well identified dynamical regimes of the hard sphere fluid. Signatures of the transitions between these regimes are identified on the trends of B (1) ( r ) B ( 1 ) ( r ) . This approach provides self-consistent results for β μ ex β μ ex that agree very well with simulation data.



The Journal of Chemical PhysicsAmerican Institute of Physics

Published: Jun 7, 2007

Keywords: liquid theory; chemical potential; statistical mechanics; liquid structure

DOI: 10.1063/1.2737046

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