Canonical unified statistical model. Classical mechanical theory and applications to collinear reactions

We present a canonical-ensemble version of the unified statistical model and we apply it to calculate classical-mechanical thermal-rate constants for 11 collinear reactions of the type A+BC→AB+C. The results are compared to accurate classical dynamics. The canonical unified statistical results are always more accurate than variational transition-state theory at high enough temperature, but in two cases they significantly overestimate the recrossing corrections at low and medium temperatures.