Date of Original Version
Several stochastic simulations of the TIP4P [W. L. Jorgensen, J. Chandrasekhar, J. D. Madura, R. W. Impey, and M. L. Klein, J. Chem. Phys. 79, 926 (1983)] water octamer are performed. Use is made of the stereographic projection path integral and the Green’s function stereographic projection diffusion Monte Carlo techniques, recently developed in one of our groups. The importance sampling for the diffusion Monte Carlo algorithm is obtained by optimizing a simple wave function using variational Monte Carlo enhanced with parallel tempering to overcome quasiergodicity problems. The quantum heat capacity of the TIP4P octamer contains a pronounced melting peak at 160 K, about 50 K lower than the classical melting peak. The zero point energy of the TIP4P water octamer is 0.0348± 0.0002 hartree. By characterizing several large samples of configurations visited by both guided and unguided diffusion walks, we determine that both the TIP4P and the SPC [H. J. C. Berendsen, J. P. Postma, W. F. von Gunsteren, and J. Hermans, (Intermolecular Forces, Reidel, 1981). p. 331] octamer have a ground state wave functions predominantly contained within the D2d basin of attraction. This result contrasts with the structure of the global minimum for the TIP4P potential, which is an S4 cube. Comparisons of the thermodynamic and ground-state properties are made with the SPC octamer as well.
Asare, E., Musah, A.-R., Curotto, E., Freeman, D. L., & Doll, J. D. (2009). The Thermodynamic and Ground State Properties of the T1P4P Water Octamer. Journal of Chemical Physics, 131(18), 184508. doi: 10.1063/1.3259047
Available at: http://dx.doi.org/10.1063/1.3259047
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