title: Mechanisms of molecular response in the optimal control of photoisomerization.
abstract: We report on adaptive feedback control of photoinduced barrierless isomerization of 1,1'-diethyl-2,2'-cyanine in solution. We compare the effect of different fitness parameters and show that optimal control of the absolute yield of isomerization (photoisomer concentration versus excitation photons) can be achieved, while the relative isomerization yield (photoisomer concentration versus number of relaxed excited-state molecules) is unaffected by adaptive feedback control. The temporal structure of the optimized excitation pulses allows one to draw clear mechanistic conclusions showing the critical importance of coherent nuclear motion for the control of isomerization.
authors.affiliation: Department of Chemical Physics, Lund University, PO Box 124, 22100 Lund, Sweden. benjamin.dietzek@chemphys.lu.se
authors.forename: Benjamin
authors.initials: B
authors.lastname: Dietzek
authors.forename: Ben
authors.initials: B
authors.lastname: Brüggemann
authors.forename: Torbjörn
authors.initials: T
authors.lastname: Pascher
authors.forename: Arkady
authors.initials: A
authors.lastname: Yartsev
mesh_terms: D000042:Absorption; D007536:Isomerism; D010777:Photochemistry; D017785:Photons; D011804:Quinolines / Q000737:chemistry*; D013057:Spectrum Analysis
chemical_list: D011804:Quinolines; C100254:pseudoisocyanine