Charge-transfer dynamics, nonadiabatic results

Figure 6.10 Ultrafast efficient switching in the five-state system via SPODS based on multipulse sequences from sinusoidal phase modulation (PL). The shaped laser pulse shown in (a) results from complete forward design of the control field. Frame (b) shows die induced bare state population dynamics. After preparation of the resonant subsystem in a state of maximum electronic coherence by the pre-pulse, the optical phase jump of = —7r/2 shifts die main pulse in-phase with the induced charge oscillation. Therefore, the interaction energy is minimized, resulting in the selective population of the lower dressed state /), as seen in the dressed state population dynamics in (d) around t = —50 fs. Due to the efficient energy splitting of the dressed states, induced in the resonant subsystem by the main pulse, the lower dressed state is shifted into resonance widi die lower target state 3) (see frame (c) around t = 0). As a result, 100% of the population is transferred nonadiabatically to this particular target state, which is selectively populated by the end of the pulse.

This chapter describes a general theoretical formulation for PCET and summarizes the results of applications to a wide range of different types of PCET reactions in solution and enzymes. This theoretical formulation treats the active electrons and transferring proton(s) quantum mechanically and includes the interactions among the electrons, proton(s), and solvent or protein environment. Moreover, this formulation allows the inclusion of the proton donor-acceptor motion, explicit molecular solvent and protein, and dynamical effects. The theory described here is directly applicable to nonadiabatic PCET reactions accompanied by substantial solute charge redistribution and solvent reorganization. 

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