Does Nonadiabatic Transition State Theory Make Sense Without Decoherence?

We analyze thermal rate constants as computed with surface hopping dynamics and resolve certain inconsistencies that have permeated the literature. On one hand, according to Landry and Subotnik (J. Chem. Phys. 2012, 137, 22A513), without decoherence, direct dynamics with surface hopping overestimates the rate of relaxation for the spin-boson Hamiltonian. On the other hand, according to Jain and Subotnik (J. Chem. Phys. 2015, 143, 134107), without decoherence, a transition state theory with surface hopping underestimates spin-boson rate constants. In this Letter, we resolve this apparent contradiction. We show that, without decoherence, direct dynamics and transition state theory should not agree; agreement is guaranteed only with decoherence. We also show that, even though the effects of decoherence may be hidden for isoenergetic reactions, these decoherence failures are exposed for exothermic reactions. We believe these lessons are essential when interpreting surface hopping papers published in the literature without any decoherence corrections.