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Rotational memory function of SPC/E water.

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Memory functions for water dipole rotations were calculated using molecular dynamics simulations. Results show single-particle and collective dynamics are nearly identical, validating dielectric spectroscopy theories.

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Area of Science:

  • Condensed matter physics
  • Molecular dynamics
  • Dielectric spectroscopy

Background:

  • Memory effects are crucial for condensed matter dynamics, influencing relaxation processes via memory functions.
  • Memory functions for water dipole rotations have not been directly computed from molecular dynamics simulations.

Purpose of the Study:

  • To calculate memory functions for single-dipole rotations and collective dipole moment dynamics in SPC/E water.
  • To validate theories connecting dielectric spectroscopy, single-particle dynamics, and collective relaxation.

Main Methods:

  • Molecular dynamics simulations were employed to compute memory functions.
  • Calculations focused on single-dipole rotations and the overall sample dipole moment.

Main Results:

  • Normalized memory functions for single-particle and collective dipole dynamics were found to be nearly identical.
  • A short memory time (≲1 fs) was determined for water dipole rotations.
  • An analytical equation for the rotational memory time was derived.

Conclusions:

  • The findings validate theories used in dielectric spectroscopy, particularly the link between collective and single-particle relaxation times.
  • The study confirms that the dielectric function does not contain dynamic information beyond that in the single-dipole correlation function.
  • Rotational diffusion models are justified for describing single molecular dipole dynamics in bulk water due to the short memory time.