Control of 1,3-Cyclohexadiene Photoisomerization Using Light-Induced Conical Intersections
Jaehee KimPULSE Institute, Stanford University, Stanford, California 94304, United StatesHongli TaoPULSE Institute, Stanford University, Stanford, California 94304, United StatesJames L. WhitePULSE Institute, Stanford University, Stanford, California 94304, United StatesVladimir S. PetrovićPULSE Institute, Stanford University, Stanford, California 94304, United StatesTodd J. MartinezPULSE Institute, Stanford University, Stanford, California 94304, United StatesPhilip H. BucksbaumPULSE Institute, Stanford University, Stanford, California 94304, United States
2011en
ABI
Abstract
We have studied the photoinduced isomerization from 1,3-cyclohexadiene to 1,3,5-hexatriene in the presence of an intense ultrafast laser pulse. We find that the laser field maximally suppresses isomerization if it is both polarized parallel to the excitation dipole and present 50 fs after the initial photoabsorption, at the time when the system is expected to be in the vicinity of a conical intersection that mediates this structural transition. A modified ab initio multiple spawning (AIMS) method shows that the laser induces a resonant coupling between the excited state and the ground state, i.e., a light-induced conical intersection. The theory accounts for the timing and direction of the effect.
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Cited by 20 references