  Chemical reaction rates must increasingly be determined in systems that
evolve under the control of external stimuli. In these systems, when a reactant
population is induced to cross an energy barrier through forcing from a
temporally varying external field, the transition state that the reaction must
pass through during the transformation from reactant to product is no longer a
fixed geometric structure, but is instead time-dependent. For a periodically
forced model reaction, we develop a recrossing-free dividing surface that is
attached to a transition state trajectory [T. Bartsch, R. Hernandez, and T.
Uzer, Phys. Rev. Lett. 95, 058301 (2005)]. We have previously shown that for
single-mode sinusoidal driving, the stability of the time-varying transition
state directly determines the reaction rate [G. T. Craven, T. Bartsch, and R.
Hernandez, J. Chem. Phys. 141, 041106 (2014)]. Here, we extend our previous
work to the case of multi-mode driving waveforms. Excellent agreement is
observed between the rates predicted by stability analysis and rates obtained
through numerical calculation of the reactive flux. We also show that the
optimal dividing surface and the resulting reaction rate for a reactive system
driven by weak thermal noise can be approximated well using the transition
state geometry of the underlying deterministic system. This agreement persists
as long as the thermal driving strength is less than the order of that of the
periodic driving. The power of this result is its simplicity. The surprising
accuracy of the time-dependent noise-free geometry for obtaining transition
state theory rates in chemical reactions driven by periodic fields reveals the
dynamics without requiring the cost of brute-force calculations.
