Dissipation and dynamics in ultrafast intersystem crossings

The effects of dynamics and dissipation on ultrafast intersystem crossings are studied for a dissipative two-level system coupled to a local vibronic mode. A method of amplitude damping of the wave packet is presented that accounts better for the position of the wave packet and avoids spurious transitions between potential wells. It is demonstrated that Fermi’s golden rule, the typical semiquantitative approach to extract population transfer rates from potential landscapes, only holds under limited conditions. Generally, the effects of dynamics and dissipation lead to deviations from the expected exponential population transfer, strong changes in transfer times and total population transfer, and significant recurrence or “spill back” of the wave packet.The effects of dynamics and dissipation on ultrafast intersystem crossings are studied for a dissipative two-level system coupled to a local vibronic mode. A method of amplitude damping of the wave packet is presented that accounts better for the position of the wave packet and avoids spurious transitions between potential wells. It is demonstrated that Fermi’s golden rule, the typical semiquantitative approach to extract population transfer rates from potential landscapes, only holds under limited conditions. Generally, the effects of dynamics and dissipation lead to deviations from the expected exponential population transfer, strong changes in transfer times and total population transfer, and significant recurrence or “spill back” of the wave packet.