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1、Coherent Control,Coherent Control attempts to control a chemical reaction with light,usually a cleverly shaped ultrashort laser pulse.Why its hard:IVR.Using shaped pulses and an iterative approach.,Conventional methods of chemical control,Much can be done,but not everything wed like.,Coherent Contro
2、l,Chemical reactions proceed in a manner determined by the molecular Hamiltonian.What if wed like to change this and make different products?Bring in a light frequency to excite a bond wed like to break.But its not so easy!Theres a lot more to it.A long-held dream of chemists.Its now coming true.Sha
3、ped ultrashort pulses are the key.,Coherent control slides mostly thanks to Gustav Gerber,University of Wurzberg,GermanyMargaret Murnane and Henry Kapteyn,JILARobert Levis,Temple University,IVR occurs on a few-fs time scale,so long pulses excite entire molecule,and the weakest bond breaks,no matter
4、which bond was excited.,Excite one bond,A few fs later,however,the entire molecule is vibrating.,Intramolecular Vibrational Redistribution,The bond vibrates,Single-parameter control,Surprisingly,these simple methods often work,but they are not general.,Coherent control:Using shaped ultrashort pulses
5、 to control the reaction,Can an ultrashort pulse cause a molecule to vibrate in such a way as to break the bond of our choice?,The physics of coherent control,Molecule,E-field of Laser,Perturbed System,Wave-function,Potential,The pulse electric field perturbs the molecule and potentially dissociates
6、 it.,The trick is to compute the required pulse electric field.,Trying to do the theory for coherent control,H system=H molecule+H radiation+H interaction,H radiation,known,First,we need to know the complete Hamiltonian for the molecule and radiation:,For all but the simplest molecules,its hopeless
7、to solve the problem.,We could try to solve the problem theoretically,but its easier to just do it iteratively in the lab.,Pulse-shaping is important for coherent control.,Genetic algorithm for coherent control,This algorithm was developed for computer optimization,but,for coherent control,it can be
8、 implemented as part of an experiment.,A genetic algorithm can minimize the pulse length.,Using a learning algorithm to perform coherent control,Coherent control of a simple gas phase reaction,Shaped Pulse,CO2,CCl4,CCl2O,Reaction under study,Murnane and Kapteyn,University of Colorado,H3C,CH3,C,O,+,+
9、,Coherent control with acetone(gas phase),Levis and coworkers,Acetone can be broken into various pieces.A laser pulse could help.,CH3CO+,60,40,20,0,Normalized Ion Intensity,Acetone+,CH3CO+,generation,22,10,3,0,70,60,50,40,30,20,10,Goal:Optimize CH3CO+at 43 amu,Optimizing one acetone photo-fragment,S
10、cience 2001,292,709,Levis and coworkers,Maximization of the relevant photo-fragment occurs rapidly.,Science 2001,292,709,Levis and coworkers,=,100,80,60,40,20,CH3CO+Signal,25,20,15,10,5,0,Generation Number,H3C-C-CH3,CH3CO+CH3,O,C,O,CH3,C,O,CH3,+,C,O,CH3,+,Manipulating the dissociation yields in acet
11、ophenone,Different pulse shapes can optimize different photo-fragments.,Levis and coworkers,1.6,1.4,1.2,1.0,0.8,0.6,Generation,Ratio:C7H5O/C6H5,Normalized ion intensity and ratio,Normalized ion intensity and ratio,Generation,Ratio:C6H5/C7H5O,2.2,2.0,1.8,1.6,1.4,1.2,1.0,C,O,CH3,100 kcal/mole,85 kcal/
12、mole,Reversing the ratio:Increasing the phenyl yield,Levis and coworkers,Optimizing the phenyl fragment yield also works.,enhance,suppress,What do these pulses look like?,Levis and coworkers,The pulse that maximizes the ratio of the two fragments.Interestingly,a very simple pulse maximizes the pheny
13、l radical(but not the ratio).,SHG FROG trace,Molecules are not isotropic,so pulse polarization shaping is important.,A complex polarization-shaped pulse,Coherent polarization control of a complex molecule in the gas phase,Gerber and coworkers,Coherent control is here!,It works,not only in the gas ph
14、ase,where dephasing times are long,but also in the liquid phase.This is potentially very useful!Almost any wavelength will do,as high intensity broadens the energy levels significantly,making all processes effectively resonant.Rabitz has shown that it is robust and should occur for essentially all s
15、ystems.By determining the precise field that optimizes the desired product,we also learn about the molecule.Coherent control has applications far beyond chemistry.,Successful closed-loop coherent control experiments in physics and chemistry,(1)Fluorescence spectrum manipulation(Wilson,1997)(2)Atomic
16、 excitation tailoring(Bucksbaum,1999)(3)Vibrational excitation tailoring in polymers(Motzkus,2002)(4)Molecular fragmentation selectivity(Gerber,1998;Levis&Rabitz,2001)(5)Molecular rearrangement selectivity(Levis&Rabitz,2001)(6)Chemical discrimination(Gerber,2001)(7)High harmonic X-ray tailoring(Murn
17、ane&Kapteyn,2000)(8)Ultrafast solid-state optical switching(Keller,2000)(9)Distortion-free transmission of pulses in optical fibers(Omenetto,2001)(10)Decoherence management(Walmsley,2002)(11)Photosynthetic bacteria energy transfer(Herek and Motzkus 2002)By 2003,50 systems have been successfully controlled.,
