E.S.R. evidence for the planarity of the t-butyl radical |
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Authors: | MCR Symons |
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Institution: | Department of Chemistry , The University , Leicester, LE1 7RH |
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Abstract: | Monte Carlo calculations are reported for the radial distribution function g 2(r; λ) of a fluid in which the intermolecular pair potential is u ref(r) + λu p(r)], u ref(r) being the Weeks-Chandler-Andersen (WCA) reference fluid, and u ref(r) + u p(r)] being the Lennard-Jones (6, 12) fluid. The calculations are performed for λ values in the range 0 to 1, at the state condition ρσ3 = 0·80, kT/ε = 0·719. It is shown that at high densities the perturbation expansion of g 2(r; λ = 1) about g 2(r; λ = 0) is rapidly convergent, but that the corresponding expansion for y 2(r; λ) = exp βu(r; λ)] × g 2(r; λ) is not. In addition Monte Carlo estimates of the individual terms that contribute to the first-order perturbation term, (?g 2/?λ)λ=0, are presented. It is shown that these terms are individually large, but that (?g 2/?λ)λ=0 is small because there is strong cancellation between the various terms. Consequently, the calculation of (?g 2/?λ)λ=0 is highly sensitive to the approximation used to evaluate the individual terms. |
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