Temperature behavior of the velocity autocorrelation function in large MD models of water.

ABSTRACT

Velocity autocorrelation functions (VACFs) were calculated using the molecular dynamics method in the TIP4P/2005 and SPC/E water models of 157 464 molecules at temperatures ranging from 250 to 370 K. The large size of the models and the high accuracy of the calculations allow us to reliably compute the long-time tails of the VACFs, showing that they systematically change shape from hydrodynamic (argon-like) at high temperatures to that typical of supercooled liquids at low temperatures. These tails in the range of 2-10 ps can be well fitted by a combination of two power functions At-3/2 - Bt-ß (A, B > 0, ß ≈ 2). It is found that the amplitude of the hydrodynamic asymptote, A, approaches zero as the temperature decreases, thereby rendering the negative power-law decay,-Bt-2, the dominant term within the specified time interval. The presence of a negative -Bt-2 decay in the time interval of 2-10 ps determines the specific shape of the VACF long-time tail of water, distinguishing it from ordinary simple liquids. The amplitude B, which is always non-zero, demonstrates a slight increase with rising temperature. At medium temperatures, weak but well-defined damped oscillations are observed on the VACF in the 0.5-2 ps interval.