Manipulation of Charge-Transfer States by Molecular Design:Perspective from“Dynamic Exciton”

作     者：Hiroshi Imahori Yasuhiro Kobori Hironori Kaji 

作者机构：Department of Molecular EngineeringGraduate School of EngineeringKyoto UniversityNishikyokuKyoto 615-8510Japan Institute for Integrated Cell-Material Sciences(WPI-iCeMS)Kyoto UniversitySakyo-kuKyoto 606-8501Japan Molecular Photoscience Research Center and Department of ChemistryGraduate School of ScienceKobe UniversityNada-kuKobe 657-8501Japan Institute for Chemical ResearchKyoto UniversityUjiKyoto 611-0011Japan 

出 版 物：《Accounts of Materials Research》 (材料研究述评（英文）)

年 卷 期：2021年第2卷第7期

页      面：501-514页

学科分类：07[理学] 070202[理学-粒子物理与原子核物理] 0702[理学-物理学] 

基　　金：This work was supported by Grant-in Aids for Transformative Research Areas(A) “Dynamic Exciton:Emerging Science and Innovation(20A201)”(JSPS KAKENHI Grant Numbers JP20H05831(H.I.) JP20H05832(H.I.) JP20H05835(Y.K.) and JP20H05840(H.K.)) 

主　　题：excited vibrational collective 

摘      要：CONSPECTUS:“Dynamic exciton,an umbrella term concept in photochemistry,plays an important role in nature,science,and technology,especially in photoinduced and electrically induced electron transfer(ET)between a donor(D)and an acceptor(A).Typically,an exciton in molecular D−A systems is considered a locally excited(LE)state of a donor(D*)or an acceptor(A*)molecule,but let us extend the terminology of“excitonto an integrated class of LE,charge-transfer(CT),and charge-separated(CS)*** degree of CT(0−100%),spin multiplicity,and D−A interaction(i.e.,electronic coupling)are pivotal factors in the“exciton.Another important aspect of the“excitonis strongly related to the“dynamicaspect of the“excitonby movement of atomic nuclei(i.e.,vibration,rotation,and fluctuation)and their collective motions controlling behaviors of electrons and spins by the passage of *** concept of“dynamic excitonshould cover a wide variety of the photochemical phenomena that are all essential for the energy conversion devices and processes including various kinds of living *** these,a huge amount of the nuclear motional modes may cooperatively be entangled to electronic ***,the idea behind“dynamic excitonincludes usage of the cooperation between nuclear motions and the spin−orbital,as electron−phonon coupling for innovative designs of the energy conversion materials and *** this,it is particularly important to examine how this wide variety of the motions plays roles on electronic couplings,intermediate geometries and mobilities,exciton energies,CT characters,and so *** draw researchers’attention to this aspect of the vibronic effect,like the entropy role by collective movement of side chains of the conjugated polymer to modulate the electronic coupling time-dependently at the charge delocalization and dissociation,which is reinforced three-dimensionally at the D/A domain interface of organic photovoltaics(OPVs).In addition,to realize the ultimate high