Assessing the Performance of the Diffusion Monte Carlo Method As Applied to the Water Monomer, Dimer, and Hexamer.

Abstract

The diffusion Monte Carlo (DMC) method is applied to the water monomer, dimer, and hexamer using q-TIP4P/F, one of the most simple empirical water models with flexible monomers. The bias in the time step (Δτ) and population size (Nw) is investigated. For the binding energies, the bias in Δτ cancels nearly completely, whereas a noticeable bias in Nw remains. However, for the isotope shift (e.g, in the dimer binding energies between (H2O)2 and (D2O)2), the systematic errors in Nw do cancel. Consequently, very accurate results for the latter (within ∼0.01 kcal/mol) are obtained with moderate numerical effort (Nw ∼ 10(3)). For the water hexamer and its (D2O)6 isotopomer, the DMC results as a function of Nw are examined for the cage and prism isomers. For a given isomer, the issue of the walker population leaking out of the corresponding basin of attraction is addressed by using appropriate geometric constraints. The population size bias for the hexamer is more severe, and to maintain accuracy similar to that of the dimer, Nw must be increased by ∼2 orders of magnitude. Fortunately, when the energy difference between the cage and prism is taken, the biases cancel, thereby reducing the systematic errors to within ∼0.01 kcal/mol when using a population of Nw = 4.8 × 10(5) walkers. Consequently, a very accurate result for the isotope shift is also obtained. Notably, both the quantum and isotope effects for the prism-cage energy difference are small.