화학공학소재연구정보센터
Journal of Chemical Physics, Vol.116, No.16, 6898-6909, 2002
Calculation of the group-based pressure in molecular simulations. II. Numerical tests and application to liquid water
In the preceding article [J. Chem. Phys. 116, 6880 (2002)] we developed a general formulation for the calculation of the isotropic or anisotropic group-based pressure in molecular simulations under periodic boundary conditions. Two sets of equations were derived for the calculation of the group-based virial, referred to as the "traditional" set and the "alternative" set. The new alternative set offers a number of advantages: (i) it requires no bookkeeping of group definitions in the inner loop of the nonbonded interaction calculation; (ii) the isotropic virial corresponding to each homogeneous pairwise interaction term can be computed directly from the corresponding interaction energy, without knowledge of the pairwise forces; (iii) its application to lattice-sum electrostatics is straightforward. In the present article, the validity and consistency of the different equations derived in this previous study are assessed through a series of numerical tests. In the case of particle-particle-particle-mesh electrostatics, a problem associated with the loss of accuracy of the force calculation due to volume fluctuations in constant-pressure simulations is also discussed. Finally, the new formalism is applied to constant-volume and constant-pressure simulations of systems containing 16 to 1024 simple-point-charge water molecules.