Survey of classical density functionals for modelling hydrogen physisorption at 77K.
This work surveys techniques based on classical density functionals for modeling the quantum dispersion of physisorbed hydrogen at 77K. Two such techniques are examined in detail. The first is based on the "open ring approximation" (ORA) of Broukhno et al., and it is compared with a technique based on the semiclassical approximation of Feynman and Hibbs (FH). For both techniques, a standard classical density functional is used to model hydrogen molecule-hydrogen molecule (i.e., excess) interactions. The three-dimensional (3D) quantum harmonic oscillator (QHO) system and a model of molecular hydrogen adsorption into a graphitic slit pore at 77K are used as benchmarks. Density functional results are compared with path-integral Monte Carlo simulations and with exact solutions for the 3D QHO system. It is found that neither of the density functional treatments are entirely satisfactory. However, for hydrogen physisorption studies at 77K the ORA based technique is generally superior to the FH based technique due to a fortunate cancellation of errors in the density functionals used. But, if more accurate excess functionals are used, the FH technique would be superior.
Sweatman
M B
MB
Department of Chemical and Process Engineering, University of Strathclyde, Glasgow, G1 1XJ, United Kingdom.