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The conventional Nosé-Hoover type deterministic thermostat scheme for controlling temperature by configurational variables (Braga-Travis (BT) thermostat) is non-ergodic for systems with a few degrees of freedom. While for the original Nosé-Hoover kinetic thermostat ergodicity has been achieved by controlling the higher order moments of kinetic energy, the issues of nonergodicity of BT thermostat persists. In this paper, we introduce two new measures of configurational temperature (second and third order) based on the generalized temperature-curvature relationship and obtain a family of deterministic thermostatting schemes by selectively (and simultaneously) controlling the different orders of temperatures through pseudo-friction terms. The ergodic characteristics of the proposed thermostats are tested using a single harmonic oscillator through statistical (normality of joint distributions at different Poincare sections) as well as dynamical tests (difference of the minimum and maximum largest Lyapunov exponent). Our results indicate that simultaneously controlling the first and the second order configurational temperatures (C1,2 thermostat) is sufficient to make the dynamics ergodic. A 2000 particle Lennard-Jones system is subjected to (i) equilibrium and (ii) sudden temperature change under BT and C1,2 thermostatting schemes. The C1,2 thermostat is found to be more robust than the BT thermostat without increasing computational costs. [ABSTRACT FROM AUTHOR]

Expressions for reaction rate constants in multidimensional chemical systems are derived by applying semiclassical approximation to the quantum path integrals of the ImF formulation of reaction rate theory. First, the transverse degrees of freedom orthogonal to the reaction coordinate are treated within the steepest descent approximation, after which the semiclassical approximation is applied to the remaining reaction coordinate. Thus derived, the semiclassical expressions account for the multidimensional nature of quantum effects and accurately incorporate nuclear quantum effects such as multidimensional tunneling and zero point energies. The obtained expressions are applicable in the broad temperature range from the deep tunneling to high-temperature regimes. The present paper provides derivation of the semiclassical instanton expressions proposed by Kryvohuz [J. Chem. Phys. 134, 114103 (2011)]. [ABSTRACT FROM AUTHOR]