Springer Theses Recognizing Outstanding Ph.D. Research Thomas Scheby Kuhlman The Non-Ergodic Nature of Internal Conversion An Experimental and Theoretical Approach Springer Theses Recognizing Outstanding Ph.D. Research For furthervolumes: http://www.springer.com/series/8790 Aims and Scope The series ‘‘Springer Theses’’ brings together a selection of the very best Ph.D. theses from around the world and across the physical sciences. Nominated and endorsed by two recognized specialists, each published volume has been selected for its scientific excellence and the high impact of its contents for the pertinent fieldofresearch.Forgreateraccessibilitytonon-specialists,thepublishedversions includeanextendedintroduction,aswellasaforewordbythestudent’ssupervisor explaining the special relevance of the work for the field. 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Thomas Scheby Kuhlman The Non-Ergodic Nature of Internal Conversion An Experimental and Theoretical Approach Doctoral Thesis accepted by the Technical University of Denmark 123 Author Supervisors Dr. ThomasScheby Kuhlman Prof.Dr. KlausB. Møller Department of Chemistry Department of Chemistry Technical University ofDenmark Technical University ofDenmark Kgs. Lyngby Kgs. Lyngby Denmark Denmark Prof.Dr. TheisI.Sølling Department of Chemistry Universityof Copenhagen Copenhagen Denmark ISSN 2190-5053 ISSN 2190-5061 (electronic) ISBN 978-3-319-00385-6 ISBN 978-3-319-00386-3 (eBook) DOI 10.1007/978-3-319-00386-3 SpringerChamHeidelbergNewYorkDordrechtLondon LibraryofCongressControlNumber:2013938178 (cid:2)SpringerInternationalPublishingSwitzerland2013 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpartof the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation,broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,andtransmissionor informationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar methodology now known or hereafter developed. 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While the advice and information in this book are believed to be true and accurate at the date of publication,neithertheauthorsnortheeditorsnorthepublishercanacceptanylegalresponsibilityfor anyerrorsoromissionsthatmaybemade.Thepublishermakesnowarranty,expressorimplied,with respecttothematerialcontainedherein. Printedonacid-freepaper SpringerispartofSpringerScience+BusinessMedia(www.springer.com) Parts of this thesis have been published in the following journal articles: I Coherent Motion Reveals Non-Ergodic Nature of Internal Conversion between Excited States T. S. Kuhlman, T. I. Sølling, K. B. Møller, ChemPhysChem 13, 820–827 (2012) II BetweenEthyleneandPolyenes-TheNon-AdiabaticDynamicsofcis-Dienes T.S.Kuhlman,W.J.Glover,T.Mori,K.B.Møller,T.J.Martínez,Faraday Discuss. 157, 193–212 (2012) III Symmetry, Vibrational Energy Redistribution and Vibronic Coupling: The Internal Conversion Processes of Cycloketones T. S. Kuhlman, S. P. A. Sauer, T. I. Sølling, K. B. Møller, J. Chem. Phys. 137, 22A522 (2012) IV Surprising Intrinsic Photostability of the Disulfide Bridge Common in Proteins A. B. Stephansen, R. Y. Brogaard, T. S. Kuhlman, L. B. Klein, J. B. Christensen, T. I. Sølling, J. Am. Chem. Soc. 134, 20279–20281 (2012) V Pulling the Levers of Photophysics: How Structure Controls the Rate of Energy Dissipation T.S.Kuhlman,M.Pittelkow,T.I.Sølling,K.B.Møller,Angew.Chem.Int. Ed. 52, 2247–2250 (2013) Partsofthisthesisarediscussedinthefollowingmanuscriptsinpreparation: VI Applying the Full Multiple Spawning Code to Absorption Spectroscopy T. S. Kuhlman, A. Witt, C. Evenhuis, K. B. Møller, T. J. Martínez, to be submitted to J. Chem. Phys. (2013) VII Simulating the Time-Resolved Photoelectron Spectrum of Cyclobutanone T. S. Kuhlman, T. I. Sølling, K. B. Møller, to be submitted to Chem. Phys. Lett. (2013) VIII PhotoinducedDynamics ofCyclopentadiene: TheRoleofSubstitutionatthe sp3-Position T. J. A. Wolf, T. S. Kuhlman, O. Schalk, A.-N. Unterreiner, T. J. Martínez, K. B. Møller, A. Stolow, in preparation (2013) v Supervisors’ Foreword Thedeactivationofelectronicallyexcitedstatesisanextremelyimportantprocess in all branches of science that involve the interaction between light and matter. Whether it is in solar cells or when DNA is exposed to light, the mechanism by which the systems disperse the energy is pivotal for the subsequent faith of the involved molecules. If the initially excited electronic state stays energized for an extended period of time, new and effective pathways for decomposition open up. With femtosecond resolution it is possible to study the fastest of events in chemistry—suchasforexamplethetransitionfromoneelectronicallyexcitedstate to another, which is the focus of this thesis. Using both experimental and theo- reticalmethodsThomasS.Kuhlmanhasnaileddownthattheelectronictransition proceeds before the entire set of available degrees offreedom are active. It is as simpleasthat!Withanoutstandingnewtreatmentofourexperimentaldataithas even been possible to map out which degrees of freedom are in play during the electronic transition and thus devise a recipe to speed up or slow down an elec- tronic transition. There is no doubt that this finding will extend far into a broad range of chemical disciplines that deal with light and we are therefore happy that thethesiswillreachamuchbroaderaudiencethoughtheSpringeraward.Wecan reveal that the idea has already given rise to a very promising study that explains why the tertiary structure of proteins has survived evolution; the reason is simply thataspecificandthushighlynon-statisticaldecaypathwayexists.Beforewegive awaytheendingofthestorywecannotencourageyouenoughtoreadaboutallof the findings in this truly outstanding thesis. Lyngby, March 2013 Klaus B. Møller Copenhagen Theis I. Sølling vii Preface ThisthesishasbeensubmittedtotheDepartmentofChemistry,TechnicalUniversity of Denmark, in partial fulfillment of the requirements for the Ph.D. degree in the subjectofChemistry.TheworkpresentedhereinwascarriedoutattheDepartment ofChemistry,TechnicalUniversityofDenmark,andtheDepartmentofChemistry, University of Copenhagen, over the period from January 2010 to December 2012 under the joint supervision of Prof. Klaus B. Møller and Prof. Theis I. Sølling. Inaddition,workwascarriedoutinthegroupofProf.ToddJ.Martínez,Department of Chemistry and PULSE Institute, Stanford University, and SLAC National AcceleratorLaboratory,duringaseven-monthstayin2011. ix Acknowledgments Asisthecasewithmanythingsinlife,mywayintotheworldofultrafastchemical dynamics was not the result of a well thought out plan but was due to a combi- nationofchanceandopportunity.Iamverygratefultohaveendedupinafruitful academic environment under the supervision of two very different supervisors, KlausB.MøllerandTheisI.Sølling.KlausandTheisinmanywayscomplement eachotherassupervisorsandscientistswhichhasallowedmetotakeoncombined theoretical and experimental endeavors during my Ph.D. studies. I am grateful to KlausandTheisforthemanystimulatingdiscussionsandfortheopportunitiesand support they have provided during the last three years. During my Ph.D. studies, I was fortunate to be able to visit the group of Prof. Todd J. Martínez at Stanford University. The large research group and the strong academic environment at Stanford University provided the basis for a great sci- entific experience. I am in particular grateful to Alexander Witt, Christian Even- huis,ToshifumiMori,andWillGloverforfruitfulcollaborationsandtotherestof the group, in particular Christine Isborn, for making my time in California very enjoyable. At the University of Copenhagen, I have had the pleasure to share the office B416 with many other students as well as an occasional post.doc. In particular, IwouldliketogivethankstoChristerBisgaardwhoverypatientlyshowedmethe wayaroundthelaserlaboratoryandalwaystookhistimetoanswermyquestions. I am grateful to Rasmus Brogaard, Martin Rosenberg, and Ditte Linde for con- tributing to the thriving scientific and social environment in B416. Asmus Dohn and Jakob Petersen as well as Chuan-Cun Shu and Ulf Lorenz, withwhomIsharedanofficeattheTechnicalUniversityofDenmark,arethanked for the many good times at DTU. Overthecourseofthelastthreeyears,Ihavehadthepleasuretocollaboratewith several people who have generously assisted me with their knowledge and skills. I would like to thank Stephan P. A. Sauer and Michael Pittelkow, University of Copenhagen, for collaboration on the computational and experimental aspects of the cycloketone project, respectively, Oliver Schalk, Ludwig Maximilian Univer- sity of Munich, and Thomas Wolf, Karlsruhe Institute of Technology, for collab- oration on the cyclopentadiene project, and Senior Lecturer Graham Worth, UniversityofBirmingham,forprovidingadevelopmentalversionoftheHeidelberg xi xii Acknowledgments MCTDH code. Prof. Jure Demsar and Michael Koerber, University of Konstanz, and Verner Thorsmølle, Rutgers University, are thanked for the continuing col- laboration on the pentacene project which is not presented in this thesis but has neverthelessamassedsomeofmytimeandattentionduringthelastthreeyears. Finally, I am eternally grateful to my girlfriend Anja Kopalska for her tireless support in particular during the last part of the studies. Copenhagen, December 2012 Thomas Scheby Kuhlman