Zero-Point Energy Leakage in Quantum Thermal Bath Molecular Dynamics Simulations
Fuite d'énergie du point zéro dans les simulations de dynamique moléculaire utilisant le thermostat quantique
Résumé
The quantum thermal bath (QTB) has been presented as an
alternative to path-integral-based methods to introduce nuclear quantum
effects in molecular dynamics simulations. The method has proved to be
efficient, yielding accurate results for various systems. However, the QTB
method is prone to zero-point energy leakage (ZPEL) in highly anharmonic
systems. This is a well-known problem in methods based on classical
trajectories where part of the energy of the high-frequency modes is
transferred to the low-frequency modes leading to a wrong energy
distribution. In some cases, the ZPEL can have dramatic consequences on
the properties of the system. Thus, we investigate the ZPEL by testing the
QTB method on selected systems with increasing complexity in order to study
the conditions and the parameters that influence the leakage. We also analyze the consequences of the ZPEL on the structural
and vibrational properties of the system. We find that the leakage is particularly dependent on the damping coefficient and that
increasing its value can reduce and, in some cases, completely remove the ZPEL. When using sufficiently high values for the
damping coefficient, the expected energy distribution among the vibrational modes is ensured. In this case, the QTB method
gives very encouraging results. In particular, the structural properties are well-reproduced. The dynamical properties should be
regarded with caution although valuable information can still be extracted from the vibrational spectrum, even for large values of
the damping term.
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