Path-integral dynamics of water using curvilinear centroids

Abstract

We develop a path-integral dynamics method for water that resembles centroid molecular dynamics (CMD), except that the centroids are averages of curvilinear, rather than Cartesian, bead coordinates. The curvilinear coordinates are used explicitly only when computing the potential of mean force, the components of which are re-expressed in terms of Cartesian “quasicentroids” (so-called because they are close to the Cartesian centroids). Cartesian equations of motion are obtained by making small approximations to the quantum Boltzmann distribution. Simulations of the infrared spectra of various water models over 150–600 K show these approximations to be justified: for a two-dimensional OH-bond model, the quasicentroid molecular dynamics (QCMD) spectra lie close to the exact quantum spectra, and almost on top of the Matsubara dynamics spectra; for gas-phase water, the QCMD spectra are close to the exact quantum spectra; for liquid water and ice (using the q-TIP4P/F surface), the QCMD spectra are close to the CMD spectra at 600 K and line up with the results of thermostated ring-polymer molecular dynamics and approximate quantum calculations at 300 and 150 K. The QCMD spectra show no sign of the CMD “curvature problem” (of erroneous red shifts and broadening). In the liquid and ice simulations, the potential of mean force was evaluated on-the-fly by generalizing an adiabatic CMD algorithm to curvilinear coordinates; the full limit of adiabatic separation needed to be taken, which made the QCMD calculations 8 times more expensive than partially adiabatic CMD at 300 K, and 32 times at 150 K (and the intensities may still not be converged at this temperature). The QCMD method is probably generalizable to many other systems, provided that collective bead-coordinates can be identified that yield compact mean-field ring-polymer distributions.