On the importance of zero-point effects in molecular level classical simulations of water

Abstract

We discuss the fundamental difficulties involved in comparing energetic results obtained via classical simulations of bulk water with the observed values. Emphasis is placed on the difference between quantum and classical dynamics, and correction techniques, which can be used to emulate quantum effects in a classical system, are investigated. We present molecular dynamics simulation results for liquid water using the ‘Thole-type’ all atom polarizable water model, which has previously been shown to give reasonable results for both ice Ih and small water clusters. We employ expressions for the density of states power spectrum in the liquid in either atomic or rigid-body coordinates that are appropriate for rigid molecule simulations. It is demonstrated that the atomic power spectra can be written as a linear combination of the center of mass and rotational power spectra via the use of the ‘coupling matrix’ of linear coefficients. This approach allows us to introduce the concept of ‘fractional degrees of freedom’ (DOF) for nuclei in rigid molecule simulation. Within this framework, it is illustrated that in a rigid water molecule the oxygen and hydrogen atoms have 2.82 and 1.59 DOF, respectively (for the TIP4P geometry). Within our suggested approach, we finally demonstrate that Debye–Waller factors can be obtained from the coupling matrix and show that quantum corrections to the structure can be accounted for by raising the temperature of the system in a classical simulation by approximately 50°, a result consistent with previous suggestions.