Quantum energy flow unimolecular reaction kinetics

The effective Hamiltonian approach clearly shows the important role of intramolecular energy flow in the quantum dynamics of unimolecular dissociation. It suggests that unless intramolecular energy flow is dominantly rapid, there exist two drastically different time scales in the reaction dynamics. This is consistent with the classical concept that nonstatistical behavior in intramolecular energy flow, such as bottleneck effects, can dramatically alter the kinetics of unimolecular reaction. 

We have explored in this chapter how quantum mechanical energy flow in moderate-sized to large molecules influences kinetics of unimolecular reactions and thermal conduction. In the first part of this chapter we addressed vibrational energy flow in moderate-sized molecules, and we also discussed its influence on kinetics of conformational isomerization. In the second part we examined the dynamics of vibrational energy flow through clusters of water molecules and through proteins, and we computed thermal transport coefficients for these objects. 

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