Nosé–Hoover chains: The canonical ensemble via continuous dynamics

Abstract

Nosé has derived a set of dynamical equations that can be shown to give canonically distributed positions and momenta provided the phase space average can be taken into the trajectory average, i.e., the system is ergodic [S. Nosé, J. Chem. Phys. 81, 511 (1984), W. G. Hoover, Phys. Rev. A 31, 1695 (1985)]. Unfortunately, the Nosé–Hoover dynamics is not ergodic for small or stiff systems. Here a modification of the dynamics is proposed which includes not a single thermostat variable but a chain of variables, Nosé–Hoover chains. The ‘‘new’’ dynamics gives the canonical distribution where the simple formalism fails. In addition, the new method is easier to use than an extension [D. Kusnezov, A. Bulgac, and W. Bauer, Ann. Phys. 204, 155 (1990)] which also gives the canonical distribution for stiff cases.