Time-Correlation-Function Expressions for Nonlinear Chemical Rate Constants

Abstract

Construction of a statistical mechanical ensemble to represent a homogeneous system not in chemical equilibrium is discussed. The consequences of the chemical driving forces are obtained as formal time‐correlation‐function expressions for both linear‐ and higher‐order chemical‐reaction rate constants. Onsager‐type reciprocal relations appear to exist for only the linear coefficients. Implications on the validity of using thermodynamic potentials for nonequilibrium systems are discussed.