Laser control of reactions of photoswitching functional molecules.
Laser control schemes of reactions of photoswitching functional molecules are proposed based on the quantum mechanical wave-packet dynamics and the design of laser parameters. The appropriately designed quadratically chirped laser pulses can achieve nearly complete transitions of wave packet among electronic states. The laser parameters can be optimized by using the Zhu-Nakamura theory of nonadiabatic transition. This method is effective not only for the initial photoexcitation process but also for the pump and dump scheme in the middle of the overall photoswitching process. The effects of momentum of the wave packet crossing a conical intersection on the branching ratio of products have also been clarified. These control schemes mentioned above are successfully applied to the cyclohexadiene/hexatriene photoisomerization (ring-opening) process which is the reaction center of practical photoswitching molecules such as diarylethenes. The overall efficiency of the ring opening can be appreciably increased by using the appropriately designed laser pulses compared to that of the natural photoisomerization without any control schemes.
Tamura
Hiroyuki
H
Departement de Chimie, Ecole Normale Superieeeure, 24 rue Lhomond, F-75231 Paris cedex 05, France. tamuura@chimie.ens.fr
Nanbu
Shinkoh
S
Ishida
Toshimasa
T
Nakamura
Hiroki
H