We describe a general theory for surface-catalyzed bimolecular reactions in responsive nanoreactors, catalytically active nanoparticles coated by a stimuli-responsive "gating" shell, whose permeability controls the activity of the process. We address two archetypal scenarios encountered in this system: the first, where two species diffusing from a bulk solution react at the catalyst's surface, ...

The reaction A + B −→ B is studied when the reactants diffuse in phase space, i.e. their dynamics is described by the Langevin equation. The steadystate rate constants are calculated for both the target (static A and mobile B’s) and trapping (mobile A and static B’s) problems when the reaction is assumed to occur at the first contact. For Brownian dynamics (i.e., ordinary diffusion), the rate c...

Progress has been made in probing the femtosecond dynamics of transition states of chemical reactions.* The “half-collision” case of unimolecular reactions has been experimentally investigated for a number of systems and much theoretical work has already been developed.2 For bimolecular reactions, the case of full collision, the zero of time is a problem which makes the femtosecond temporal res...

ion reaction, after the ZPE contributions are included there is no barrier in the effective potential along the reaction coordinate, so important variational effects are expected. Both VMEP and the vibrationally adiabatic potential are plotted along the path in Figure 1. At room temperature the maximum of the free energy (see eq 2.4.36) is located at s* CVT ) -0.364 a0, whereas s* μVT is energy...

Mechanisms of bimolecular chemical reactions in solution are amenable to study on picosecond timescales, both by transient absorption spectroscopy and by computer simulation. The dynamics of exothermic reactions of CN radicals and of Cl and F atoms with organic solutes in commonly used solvents are contrasted with the corresponding dynamics in the gas phase. Many characteristics of the gas-phas...