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(1)  RulesofMolecularSelfOrganization: Emergence,ControlandPredictability    . .  CarstenL.Rohr München2011 . .

(2) .  . .

(3)  RulesofMolecularSelfOrganization: Emergence,ControlandPredictability     Dissertation amLehrstuhlfürExperimetalphysik Prof.J.O.Rädler FakultätfürPhysik LudwigMaximiliansUniversitätMünchen   CarstenL.Rohr Juni2011 . .

(4)               Betreuer:Dr.B.Hermann Erstgutachter:Prof.Dr.JoachimO.Rädler Zweitgutachter:PDDr.MarkusLackinger DatumderPrüfung:15.6.2011 .

(5) . Contents ZUSAMMENFASSUNG. III. ABSTRACT. V. 1. 1. INTRODUCTION 1.1 MISSINGRULESANDPREDICTABILITY 1.2 AIMSOFTHETHESIS 1.3 STRUCTUREOFTHETHESIS. 2. 1 3 4. SELFORGANIZATION. 5. 2.1 CONCEPT 2.2 MOLECULARSELFORGANIZATION. 5 6. 3 3.1 3.2 3.3 3.4 3.5 3.6 4. SCANNINGTUNNELINGMICROSCOPY. 9. SCANNINGTUNNELINGMICROSCOPY TUNNELTHEORY TUNNELINGTHROUGHMOLECULARADLAYERS SUBSTRATES SOLUTIONCASTING IMAGEPROCESSING. 9 13 17 19 20 22. MOLECULARSYSTEMS. 25. 4.1 SUPRAMOLECULARCHEMISTRY 4.2 FRÉCHETDENDRONS 5 5.1 5.2 5.3 5.4. 25 26. COMPLEXENERGYLANDSCAPES. 29. ENERGYLANDSCAPES METASTABLESTATES PHASETRANSFORMATIONS EMERGENCE. 29 30 31 31. . ‹.

(6) Contents 6. COMPUTATIONALTOOLS 6.1 FORCEFIELDSINMOLECULARMECHANICSSIMULATIONS 6.2 DENSITYFUNCTIONALTHEORYSIMULATIONS 6.3 INTERACTIONSITEMODELINMONTECARLOSIMULATIONS. 7. CONCEPTSOFSELFORGANIZEDMOLECULES 7.1 2DSYMMETRYGROUPS 7.2 CHIRALITY 7.3 HIERARCHICALORGANIZATION. 33 34 35 38 41 41 45 46. 8. SUMMARIESOFPUBLICATIONS. 49. 9. PUBLICATIONS. 55. 9.1 SIZEMATTERSINOSTWALD´SRULEOFSTAGES:MULTIPHASETRANSFORMATIONSCAUSEDBY STRUCTURALCOMPLEXITY 55 9.2 MOLECULARJIGSAW:PATTERNDIVERSITYENCODEDBYELEMENTARYGEOMETRICAL FEATURES 59 9.3 MOLECULARSELFORGANIZATION:PREDICTINGTHEPATTERNDIVERSITYANDLOWEST ENERGYSTATEOFCOMPETINGORDERINGMOTIFS 67 9.4 PREDICTINGTHEINFLUENCEOFAP2SYMMETRICSUBSTRATEONMOLECULARSELF 75 ORGANIZATIONWITHANINTERACTIONSITEMODEL 9.5 SIMULATINGPATTERNSFORMOLECULARSELFORGANIZATIONONSURFACESUSING INTERACTIONSITEMODELS 91 9.6 MULTIHIERARCHICALASSEMBLYVIAMOLECULARFLEXIBILITY 101 9.7 SURFACECONTROLOFCHIRALITY,ORIENTATIONANDHIERARCHICALASSEMBLYOFSELF 109 ORGANIZEDMONOLAYERS 9.8 AVERSATILEFRÉCHETDENDRONCOMPOUNDUNIFIESHOSTGUESTANDTEMPLATED HETEROGENEOUSSELFASSEMBLY 115 10. PERSPECTIVES. 10.1 FROMPREDICTIONANDCOMPLEXITYINSELFORGANIZATION 10.2 TOWARDSDESIGNANDFUNCTIONALITY. 125 127. REFERENCES. 129. APPENDIX. 141. A  B. BOOKCHAPTER:DIESUCHENACHDEMTIEFSTENTAL:SELBSTORGANISATIONVON MOLEKÜLENINGESCHLOSSENENSYSTEMEN ORGANICSUPERCONDUCTORSREVISITED. ACKNOWLEDGMENTS. ‹‹. 125. 141 165 173.

(7) . Zusammenfassung ‹‡•‡ ”„‡‹– •–‡ŽŽ– †‹‡ ”ƒ‰‡ ƒ Š †‡” ‘”Š‡”•ƒ‰„ƒ”‡‹– ˜‘ ‘’Ž‡š‡ •‡Ž„•–‘”‰ƒ‹•‹‡”–‡ ‘Ž‡òŽ—•–‡” —† ˜‡”•— Š– ‹– ‹Žˆ‡ ˜‘ ‘‰‹–‹˜‡ •¡–œ‡ —† ‹—Žƒ–‹‘•‡–Š‘†‡ –™‘”–‡ œ— ‰‡„‡Ǥ ƒœ— ™—”†‡ †‹‡ ‘”†—‰‡˜‘ ”± Š‡–Ǧ‡†”‘‡ǡ†‡’Šƒ•‡”‡‹ Š•–‡œ™‡‹†‹‡•‹‘ƒŽ‡ ›•–‡ǡ‹––‡Ž•ƒ•–‡”–—‡Ž‹”‘•‘’‹‡ƒ„‰‡„‹Ž†‡–Ǥ‹•Š‡”ˆòŠ”‡†‹‡ˆ‡ŠŽ‡†‡ ‡‰‡Ž ‘†‡” ‹—Žƒ–‹‘‡ ˆò” ‘Ž‡—Žƒ”‡ ‡Ž„•–‘”‰ƒ‹•ƒ–‹‘ œ— ‡‹‡ ‘Ž‡òŽǦ ‡•‹‰ƒ Š†‡‡”•— ŠǦ—†Ǧ

(8) ””–—Ǧ”‹œ‹’Ǥ‹––‡Ž•Žƒ”‡”Ž‰‘”‹–Š‡Ú‡ Ú‰Ž‹ Š‡—•‰¡‰‡˜‘”†‡š’‡”‹‡–˜‘”Š‡”œ—•ƒ‰–™‡”†‡ǡ™ƒ•‡‹‰‡œ‹‡Ž–‡• š’‡”‹‡–†‡•‹‰‡”Ú‰Ž‹ Š–Ǥ‹‡•‡”„‡‹–‰Ž‹‡†‡”–•‹ Š‹†”‡‹‡‹Ž„‡”‡‹ Š‡ǣ 1. Verstehen und Kontrolle der Eigenschaften und Phasenvielfalt von Fréchet Dendronen x ‹‡ –‡”•— Š—‰ ‡‹‡” ‡‹Š‡ ˜‘ ¡ŠŽ‹ Š‡ ‘Ž‡òŽ‡ ‹– •–‡‹‰‡†‡” ‘’Ž‡š‹–¡– ‡”‰‹„–ǡ †ƒ•• „‡‹ †‡” ™ƒ†Ž—‰ ˜‘ ‡–ƒ•–ƒ„‹Ž‡ —•‰ƒ‰•—•–‡” œ—” –Š‡”‘†›ƒ‹• Š‡ †ƒ‘”†—‰ ‹– ‰”Ú釔‡” ‘’Ž‡š‹–¡– • Š”‹––™‡‹•‡ ‡Š” ™‹• Š‡—•–‡” ƒ‰‡‘‡ ™‡”†‡Ǥ ‹‡•‡ ‘’Ž‡š‹–¡–•ƒ„Š¡‰‹‰‡‹– †‡” ˜‘ •–™ƒŽ† ˜‘” ͳͲͲ ƒŠ”‡ ƒ—ˆ‰‡•–‡ŽŽ–‡ –—ˆ‡”‡‰‡Ž ™‹”† ƒŽ• ‡”‰‡œ’Š¡‘‡ ‡”Ž¡”–ǡ †ƒ• †—” Š ‡‹‡œ—‡Š‡†œ‡”ˆ—” Š–‡”‡‡”‰‹‡Žƒ†• Šƒˆ–‡–•–‡Š–Ǥ x ”± Š‡–Ǧ‡†”‘‡ ‡”œ‡—‰‡ ‹– ƒ•–‘Ž‡òŽ‡ •‘™‘ŠŽ ‹”–Ǧ ƒ•–Ǧ ‘”†—‰‡ ƒŽ• ƒ— Š ’‘Ž›‘”’Š‡ —•–‡” ‹ „Š¡‰‹‰‡‹– ˜‘ †‡” ‡Ž‡–”‘‹• Š‡ –”—–—” †‡• ƒ•–‘Ž‡òŽ•Ǥ ‹‡• ‹•– †ƒ• ‡”•–‡ ƒŽǡ †ƒ•• ‡‹ ‘Ž‡òŽ †‹‡•‡ „‡‹†‡ Žƒ••‡ †‡” Š‡–‡”‘‰‡‡ —•–‡”„‹Ž†—‰ ˜‡”‡‹–Ǥ ”Ž¡”–™‹”††‹‡•‡”ˆˆ‡–†—” Š†‡†—ƒŽ‡‡ Š•‡Ž™‹”—‰• Šƒ”ƒ–‡”†‡• ‘Ž‡òŽ•Ǥ 2. EntwicklungeinesMonteCarloModellszurMustervorhersage x ‹ •–ƒ” ƒ„•–”ƒŠ‹‡”–‡• ‡ Š•‡Ž™‹”—‰•‘†‡ŽŽ ˜‘ ”± Š‡–Ǧ‡†”‘‡ ™‹”†ƒ—ˆ†‡”ƒ•‹•˜‘‘Ž‡—Žƒ”‡ Šƒ‹Ǧ‹—Žƒ–‹‘‡‡–™‹ ‡Ž–Ǥ‹‡•‡• ‘†‡ŽŽ’”‘‰‘•–‹œ‹‡”–‹‘–‡Ǧƒ”Ž‘Ǧ‹—Žƒ–‹‘‡‹ Š–—”Šƒ•‡˜‹‡ŽˆƒŽ–ǡ ‹‹‹.

(9)  •‘†‡” ƒ— Š †‡”‡ Ž‘ƒŽ‡ —† ‰Ž‘„ƒŽ‡ ‘”†—‰‡ ‹ o„‡”‡‹•–‹—‰ ‹–†‡š’‡”‹‡–Ǥ x ‹‡ ‡‹–‡”‡–™‹ Ž—‰ †‡• ‡ Š•‡Ž™‹”—‰•‘†‡ŽŽ• ‹– —–‡”Ǧ • Š‹‡†Ž‹ Š‡ ‘ˆ‘”ƒ–‹‘‡ ”‡’”‘†—œ‹‡”– †ƒ• ‘’Ž‡š‡•–‡ —•–‡” ‡šƒ–ǡ œ—•¡–œŽ‹ Š œ— †‡ „‡”‡‹–• ‰‡ˆ—†‡‡ Šƒ•‡Ǥ ‹‡ ‡”‰‹‡ƒƒŽ›•‡ †‡• ‘†‡ŽŽ• œ‡‹‰–ǡ †ƒ•• †‹‡ ‹‡†”‹‰•–‡ ‡”‰‹‡ ˆò” †ƒ•Œ‡‹‰‡ —•–‡” ‰‡ˆ—†‡ ™‹”†ǡ†ƒ•†‡–Š‡”‘†›ƒ‹• Š‡†œ—•–ƒ†‹š’‡”‹‡–‡–•’”‹ Š–Ǥ x ‹– ‹Žˆ‡ †‡• ‘†‡ŽŽ• ™‡”†‡ †‹‡ ‡”™ƒ”–‡–‡ ‘”†—‰‡ ƒ—ˆ ‡‹‡ ‘†‹ˆ‹œ‹‡”–‡ pʹǦ•›‡–”‹• Š‡ —„•–”ƒ– ˜‘”Š‡”‰‡•ƒ‰–ǡ †‹‡ ‹ †‡” ‘Ž‰‡ ƒ— Š ‡š’‡”‹‡–‡ŽŽ „‡•–¡–‹‰– ™‡”†‡Ǥ ƒ‹– ™‡”†‡ ‡”•–ƒŽ‹‰ †‹‡ •‡Ž„•–Ǧ ‘”‰ƒ‹•‹‡”–‡—•–‡”ˆò”‡—‡‡š’‡”‹‡–‡ŽŽ‡‡†‹‰—‰‡’”‘‰‘•–‹œ‹‡”–Ǥ 3. Auffinden von allgemeinen Beziehungen zwischen molekularem Baustein und resultierendemMuster x ƒ• Š‹‡”ƒ” Š‹• Š‡ –•–‡Š‡ †‡” —•–‡”ǡ ‰‡‘’’‡Ž– ‹– ‡‹‡ ‡‘„‹ƒ–‹‘•’”‘œ‡•• †‡” ƒ—•–‡‹‡ ƒ—ˆ Œ‡†‡” ‹‡”ƒ” Š‹‡‡„‡‡ǡ ˆòŠ”– œ— †‡” ‰‡ˆ—†‡‡ Šƒ•‡˜‹‡ŽˆƒŽ–Ǥ ‹‡• ‹•– †ƒ• ‡”•–‡ ‡‹•’‹‡Ž ˆò” —Ž–‹Š‹‡”ƒ” Š‹• Š‡‘”†—‰‹ʹǦ•‡Ž„•–‘”‰ƒ‹•‹‡”–‡›•–‡‡Ǥ x ”—†Ž‡‰‡†‡ ‹‰‡• Šƒˆ–‡ †‡” ‘Ž‡òŽ„ƒ—•–‡‹‡ ™‹‡ •›‡–”‹‡ǡ —Ž–‹’Ž‡ ‡ Š•‡Ž™‹”—‰‡ —† Ž‡š‹„‹Ž‹–¡– „‡†‹‰‡ —•–‡”‡‹‰‡• Šƒˆ–‡ ™‹‡‘–ƒ–‹‘••›‡–”‹‡ǡŠ‹‡”ƒ” Š‹• Š‡‘”†—‰‡—†—Ž–‹’Ž‡Šƒ•‡Ǥ x ‹– ‹Žˆ‡ ‡‹‡” ˜‡”¡†‡”–‡ „‡”ˆŽ¡ Š‡ ™‡”†‡ †—” Š †‹‡•‡ ”‹œ‹’‹‡ ‰‡œ‹‡Ž–†‹‡Š‹”ƒŽ‹–¡–ǡ”‹‡–‹‡”—‰—†‘”†—‰•Š‹‡”ƒ” Š‹‡‡‹‡•—•–‡”• ˜‡”¡†‡”–Ǥ ò” ‡‹‡ ƒ—•ˆòŠ”Ž‹ Š‡”‡ —•ƒ‡ˆƒ••—‰ †‡” ‹ ƒŠ‡ †‹‡•‡” ”„‡‹– ‡–•–ƒ†‡‡‡”Úˆˆ‡–Ž‹ Š—‰‡™‹”†ƒ—ˆƒ’‹–‡Žͻ˜‡”™‹‡•‡Ǥ  . ‹˜.

(10) . Abstract Š‹• –Š‡•‹• †‡• ”‹„‡• ƒ’’”‘ƒ Š‡• ™‹–Š ‘’—–ƒ–‹‘ƒŽ ƒ• ™‡ŽŽ ƒ• ‘‰‹–‹˜‡ ‡–Š‘†•–‘’ƒ––‡”’”‡†‹ –‹‘ǡ†‡”‹˜‹‰”—Ž‡•ˆ‘”ʹ‘Ž‡ —Žƒ”•‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘ ˆ”‘ ƒ Žƒ”‰‡ •‡– ‘ˆ • ƒ‹‰ –—‡Ž‹‰ ‹ ”‘• ‘’› ‹ƒ‰‡• ‘ ƒ •‡– ‘ˆ ”± Š‡– ‡†”‘‘Ž‡ —Ž‡•Ǥ ’ –‘ †ƒ–‡ —†‡”•–ƒ†‹‰ ƒ† †‹”‡ –‹‰ •‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘ ‘ˆ •—’”ƒ‘Ž‡ —Žƒ”‘‘Žƒ›‡”•„ƒ•‡†‘‹‘˜ƒ–‹˜‡‘†‡Ž‹‰ƒ’’”‘ƒ Š‡•’”‡•‡–•ƒ ƒŒ‘” ’”‡”‡“—‹•‹–‡ ˆ‘” ”‡Ž‹ƒ„Ž‡ ƒ’’Ž‹ ƒ–‹‘• –‘™ƒ”†• •—”ˆƒ ‡ ˆ— –‹‘ƒŽ‹œƒ–‹‘ǡ •‡•‘”•ǡ ƒ–ƒŽ›•‹•ǡƒ•™‡ŽŽƒ•‘Ž‡ —Žƒ”‡Ž‡ –”‘‹ †‡˜‹ ‡•ǤŠ‡”‡‹•ƒ—”‰‡ˆ‘”ƒ —†‡”•–ƒ†‹‰‘ˆ•‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘”ƒ–Š‡”–Šƒˆ‘ŽŽ‘™‹‰ƒ–”‹ƒŽƒ†‡””‘”‡–Š‘†Ǥ Ž–Š‘—‰ŠƒŽŽ–Š‡ˆ‘” ‡• ‘–”‹„—–‹‰–‘‘Ž‡ —Žƒ”•‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘ƒ”‡‘™ǡ‘ •›•–‡ƒ–‹  ƒ’’”‘ƒ Šǡ ”—Ž‡ „ƒ•‡† ‘” •‹—Žƒ–‹‘ „ƒ•‡†ǡ ƒ ’”‡†‹ – –Š‡ ’”‘’‡”–‹‡• ‘ˆ–Š‡‘„•‡”˜‡†’ƒ––‡”•‹ƒ†˜ƒ ‡Ǥ ”± Š‡– ‡†”‘• ‡šŠ‹„‹– –Š‡ Š‹‰Š‡•– ’Šƒ•‡ ˜ƒ”‹‡–› ˆ‘” ‘Ž‡ —Žƒ” •‡ŽˆǦ ‘”‰ƒ‹œƒ–‹‘‘•—”ˆƒ ‡•ƒ†ƒ”‡‹˜‡•–‹‰ƒ–‡†„›• ƒ‹‰–—‡Ž‹‰‹ ”‘• ‘’› ƒ† —Ž–‹’Ž‡ ‘†‡Ž‹‰ –‡ Š‹“—‡•Ǥ Š‹• ’ƒ––‡” †‹˜‡”•‹–› ‹• Š‡”‡ ˆ‘—† –‘ •–‡ ˆ”‘–Š‡ˆ‹”•–‹•–ƒ–‘ˆ—Ž–‹ǦŠ‹‡”ƒ” Š‹ ƒŽƒ••‡„Ž›ˆ‘—†ˆ‘”ʹ‘Ž‡ —Žƒ”•‡ŽˆǦ ‘”‰ƒ‹œƒ–‹‘ ƒ—•‡† „› –Š‡ ‘Ž‡ —Ž‡•Ʋ Š‹‰Š ‘ˆ‘”ƒ–‹‘ƒŽ ˆ”‡‡†‘Ǥ  ‘’ƒ”‹•‘„‡–™‡‡‘Ž‡ —Ž‡•‘ˆ‹ ”‡ƒ•‹‰ ‘’Ž‡š‹–›•Š‘™•–Šƒ––Š‡’ƒ––‡” †‹˜‡”•‹–›‹•–Š‡”‡•—Ž–‘ˆ‡‡”‰‡––”ƒ•‹‡–•–ƒ–‡•†—‡–‘ƒ‹ ”‡ƒ•‹‰Ž›”—‰‰‡† ‡‡”‰›Žƒ†• ƒ’‡Ǥ

(11)  –Š‹• –Š‡•‹• ƒ ‹–‡”ƒ –‹‘Ǧ•‹–‡ ‘†‡Ž ‹• †‡˜‡Ž‘’‡† –Šƒ– •— ‡••ˆ—ŽŽ› ‘†‡•‡• –Š‡ ‡••‡–‹ƒŽ ‘Ž‡ —Žƒ” ’”‘’‡”–‹‡• ‘ˆ –Š‡ ”± Š‡– ‡†”‘•ǡ ƒ• †‡–‡”‹‡† „› —Ž–‹• ƒŽ‡ ‘†‡Ž‹‰Ǥ

(12)  ƒ ‘–‡ ƒ”Ž‘ ƒ’’”‘ƒ Š –Š‹• ‘†‡Ž •— ‡••ˆ—ŽŽ› ’”‡†‹ –• –Š‡ ˜ƒ”‹‘—• Ž‘ ƒŽ ƒ† ‰Ž‘„ƒŽ ‘”†‡”‹‰ ‘–‹ˆ• ‘ˆ ”± Š‡– ‡†”‘ •‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘Ǥ Š‹• ‘ˆ‹”• –Šƒ– ‘Ž› ‰‡‘‡–”› ƒ• ™‡ŽŽ ƒ• ƒ ˆ‡™ •ƒŽ‹‡–™‡ƒ‹–‡”ƒ –‹‘•‹–‡•‡ ‘†‡–Š‡•‡•–”— –—”ƒŽ‘–‹ˆ•Ǥ Š‡ †‹ˆˆ‡”‡– ˆ‘”• ‘ˆ ‘”‰ƒ‹œƒ–‹‘ ”‡ƒ–‡† „› ”± Š‡– ‡†”‘• ™‡”‡ ‘†‡Ž‡†ƒ†”‡Ž‡˜ƒ–ˆ‡ƒ–—”‡•‹–Š‡‘”†‡”‹‰•™‡”‡‹†‡–‹ˆ‹‡†Ǥ ‡‡”ƒŽ„—‹Ž†‹‰ ˜.

(13)  „Ž‘ ’”‘’‡”–‹‡• ‘—Ž†„‡†‡–‡”‹‡†–Šƒ–Ž‡ƒ†–‘•’‡ ‹ˆ‹ ˆ‡ƒ–—”‡•‘ˆŠ‹‰Š‡”Ž‡˜‡Ž •–”— –—”‡•ǡˆ‘”‡šƒ’Ž‡•›‡–”›ǡŠ‹‡”ƒ” Š‹ ƒŽƒ••‡„Ž›ƒ†‘”‹‡–ƒ–‹‘•Ǥ ”‘ –Š‹• ‹•‹‰Š– ‰‡‡”ƒŽ ”—Ž‡• ‰‘˜‡”‹‰ ‘Ž‡ —Žƒ” •‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘ ‘—Ž† „‡ †‡–‡”‹‡†ǤŠ‹•‹’Ž‹‡•–Šƒ–„ƒ•‹ ’”‘’‡”–‹‡•‘ˆ–Š‡„—‹Ž†‹‰„Ž‘ •‡ ‡••‹–ƒ–‡ –Š‡’”‘’‡”–‹‡•‘ˆ–Š‡”‡•—Ž–‹‰’ƒ––‡”Ǥ ƒ•–Ž›–Š‡•‡‹•‹‰Š–•™‡”‡‡’Ž‘›‡†„› ”‡ƒ–‹‰ƒ•—”ˆƒ ‡‘†‹ˆ‹‡†™‹–Šn ƒŽƒ‡•–‘ Šƒ‰‡–Š‡•—”ˆƒ ‡Ʋ• Šƒ”ƒ –‡”‹•–‹ •ǤŠ‡’‘••‹„Ž‡ƒ••‡„Ž›’ƒ––‡”•‘ –Š‹• •—”ˆƒ ‡ ™‡”‡ ’”‡†‹ –‡† —•‹‰ –Š‡ ‹–‡”ƒ –‹‘ •‹–‡ ‘†‡Ž ƒ† •— ‡••‹˜‡ ‡š’‡”‹‡–• ˆ‘—† ƒ Šƒ‰‡ ‹ ’ƒ––‡” •›‡–”›ǡ ‘”‹‡–ƒ–‹‘ ƒ† Š‹‡”ƒ” Š‹ ƒŽ ƒ••‡„Ž›Ǥ ‹–Š –Š‡•‡ ‹•‹‰Š–• ƒ† ‘†‡ŽŽ‹‰ –‘‘Ž• Šƒ‰‡• ‹ †‡•‹‰‹‰ ƒ ‡™ ‘Ž‡ —Žƒ” „—‹Ž†‹‰ „Ž‘  ƒ –ƒ‡ ’Žƒ ‡Ǥ ‘”‡ –‹‡ •’‡– ‹ ˆ”‘– ‘ˆ –Š‡ ™Š‹–‡„‘ƒ”†ǡ ™‹ŽŽ Ž‡ƒ† –‘ ƒ ‘”‡ ‘• ‹‘—• ƒ† ‘”‡ ‘–”‘ŽŽ‡† ˆ‘” ‘ˆ •‡ŽˆǦ ‘”‰ƒ‹œƒ–‹‘Ǥ. ˜‹.

(14) 1. Introduction. 1.1 Missingrulesandpredictability Š‡ ’”‘ ‡•• ‘ˆ •‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘ ‹• –Š‡ ™ƒ› „› ™Š‹ Š ƒ–—”‡ ”‡ƒ–‡• ‘’Ž‡š‹–› ˆ”‘ –Š‡ ‹ƒ‹ƒ–‡ ™‘”Ž† ‘ˆ ‰ƒŽƒš‹‡•ǡ •ƒ† †—‡• ƒ† ‘Ž‡ —Ž‡• –‘ –Š‡Ž‹˜‹‰”‡ƒŽ‘ˆ‡„”ƒ‡•ǡ•™ƒ”†›ƒ‹ •ƒ† ‘• ‹‘—•‡••ȏͳȐǤ‘Ž‡ —Žƒ” •‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘’”‘˜‹†‡•‘‡‘ˆ–Š‡–™‘ƒ’’”‘ƒ Š‡•–‘ ”‡ƒ–‡•–”— –—”‡•ƒ––Š‡ ƒ‘• ƒŽ‡Ǥ  “…selfassemblyisoneofthefewpracticalstrategiesformakingensembles ofnanostructures.ItwillthereforebeanessentialpartofnanotechnologyǤdz  ǤŠ‹–‡•‹–‡•ȏʹȐ   •—”ˆƒ ‡ –Š‡ ‘”‰ƒ‹œƒ–‹‘ ‘ˆ •—’”ƒ‘Ž‡ —Žƒ” ‘‘Žƒ›‡”• ‘•–‹–—–‡• ƒ ƒŒ‘” ŠƒŽŽ‡‰‡‹’‘”–ƒ–ˆ‘”•—”ˆƒ ‡ˆ— –‹‘ƒŽ‹œƒ–‹‘ȏ͵Ȑǡ•‡•‘”•ǡȏͶȐ ƒ–ƒŽ›•‹•ǡȏͷȐƒ† ‘Ž‡ —Žƒ” ‡Ž‡ –”‘‹  †‡˜‹ ‡•ȏ͸ȐǤ

(15)  ”‡ ‡– ›‡ƒ”• ”‡•‡ƒ” Š Šƒ• — ‘˜‡”‡† ƒ ‡‘”‘—• ˜ƒ”‹‡–› ‘ˆ ’ƒ––‡”• ™Š‹ Š ƒ”‡ ‘„‹‡† ‹ –Š‡ –™‘ †‹‡•‹‘ƒŽ •–”— –—”ƒŽ †ƒ–ƒ„ƒ•‡ ʹȏ͹ȐǤ

(16)  ”‡ƒ•‹‰Ž› †‹ˆˆ‡”‡– ’ƒ––‡”• ƒ”‡ ”‡ƒ–‡† „› ‘‡ ƒ†–Š‡•ƒ‡‘Ž‡ —Ž‡ȏͺǦͳͶȐǡŽ‡ƒ†‹‰–‘ ‘‡š‹•–‡ ‡ƒ††›ƒ‹ ƒŽ„‡Šƒ˜‹‘”Ž‹‡ ’Šƒ•‡–”ƒ•ˆ‘”ƒ–‹‘•ȏͳͷȐǤ  DzOnce the mechanisms controlling the selfordering phenomena are fully understood,theselfassemblyandgrowthprocessescanbesteeredtocreate a wide range of surface nanostructures from metallic, semiconducting and molecularmaterials.dz Ǥ‡”ƒ† ‘Ǧ™‘”‡”•ǡȏ͵ȐǤ  Š‹••–ƒ–‡‡–„›‡”†‡• ”‹„‡•–Š‡’‘••‹„‹Ž‹–‹‡•‘ˆ‘Ž‡ —Žƒ”•‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘ ƒ†”ƒ‹•‡•–Š‡ƒ‹’”‡”‡“—‹•‹–‡ǡunderstandingǡˆ‘”–Š‹•†‡˜‡Ž‘’‡–ǤŠ‡ƒ‹ ͳ.

(17) Ph.D.ThesisCarstenRohr †‹ˆˆ‹ —Ž–›Ž‹‡•‹ƒ‹‰”‡Ž‹ƒ„Ž‡’”‡†‹ –‹‘•ȏͳ͸Ȑƒ† ‘–”‘ŽŽ‹‰ȏͳ͹Ȑ–Š‡ ‘’Ž‡š ‘Ž‡ —Žƒ”‘”†‡”‹‰‘–Š‡ƒ‘‡–‡”• ƒŽ‡Ǥ•†‡ ‡›–‡”’—–‹–„Ž—–Ž›‹ʹͲͲͺǣ  DzWhenfacedwiththequestionhowagivenmoleculeisgoingtoadsorbona wellknown surface, the answer is often vague and most often the “Idon’t know”approachisthemosthonestoneǤdz Ǥ†‡ ‡›–‡”ƒ† ‘Ǧ™‘”‡”•ȏͳͺȐ  Š‹•”ƒ‹•‡•–Š‡“—‡•–‹‘‘ˆŠ‘™–‘†‡ƒŽ™‹–Š–Š‹•— ‡”–ƒ‹–›ƒ† ‘’Ž‡š‹–›Ǥ‡ Š‡‹ ƒŽ ƒ’’”‘ƒ Š ‹• –‘ ”‡†— ‡ ‘’Ž‡š‹–› „› ”‡ƒ–‹‰ ˜‡”› •’‡ ‹ˆ‹  ‡›ǦŽ‘  ‹–‡”ƒ –‹‘•ƒ––Š‡ƒ’’Ž‹‡†‘Ž‡ —Ž‡•–‘ƒ˜‘‹†— ‡”–ƒ‹–›‹–Š‡‘—– ‘‡ȏͳͻǦʹͳȐǤ Š‹• –‡ –‘ȏͳ͸Ȑ ƒ’’”‘ƒ Š †‡ƒŽ• ™‹–Š ‘’Ž‡š‹–› „› •‹’Ž‹ˆ›‹‰ ‹–Ǥ –Š‡” ƒ’’”‘ƒ Š‡• –‘ —†‡”•–ƒ† ’ƒ––‡” ˆ‘”ƒ–‹‘ ‹ ‘Ž‡ —Žƒ” •‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘ ”‡Ž› ‘–Š‡•Šƒ’‡‘ˆ–Š‡‘Ž‡ —Ž‡ȏʹʹȐˆ‘”ƒ‡š’Žƒƒ–‹‘Ǥ ‘†‡Ž‹‰ ƒ’’”‘ƒ Š‡• –‘ —†‡”•–ƒ† •’‡ ‹ˆ‹  •‡ŽˆǦ‘”‰ƒ‹œ‡† •›•–‡• Ž‹‡ †‡•‹–›Ǧˆ— –‹‘ƒŽǦ–Š‡‘”›ȏʹ͵ǡ ʹͶȐ ‘” ‘Ž‡ —Žƒ” ‡ Šƒ‹ • ‘” †›ƒ‹ •ȏʹͷǦʹ͹Ȑ —•—ƒŽŽ› ’”‘˜‹†‡ ƒ ‡š’Žƒƒ–‹‘ after –Š‡ ‡š’‡”‹‡– Šƒ• „‡‡ ’‡”ˆ‘”‡†ǡ •‹ ‡ ”ƒ†‘ •–ƒ”–‹‰ ‘ˆ‹‰—”ƒ–‹‘• ‡š ‡‡† –Š‡ ‘’—–ƒ–‹‘ƒŽ ’‘™‡” ƒ˜ƒ‹Žƒ„Ž‡Ǥ ‘ƒ”•‡ ‰”ƒ‹‹‰ ™‹–Š ‹–‡”ƒ –‹‘ •‹–‡ ‘†‡Žȏʹͺǡ ʹͻȐ ‘” ‘–Š‡” •‹’Ž‹ˆ‹‡† ‘†‡Ž• ‹’Ž‡‡–‡† ˆ‘” ‘–‡ ƒ”Ž‘ ‡–Š‘†•ȏʹͷǦʹ͹Ȑ ‘—Ž† ’”‡•‡– ƒ ’‘••‹„Ž‡ ƒŽ–‡”ƒ–‹˜‡Ǥ‡˜‡”–Š‡Ž‡••’”‡†‹ –‹˜‡‡–Š‘†•ƒ”‡•–‹ŽŽ‹••‹‰Ǥ  “… the increasing complexity of the assembly units used makes it generally more difficult to control the supramolecular organization and predict the assembling mechanisms. This creates a case for developing novel analysis methodsandevermoreadvancedmodelingtechniques” †‡‹–ƒƒ† ‘Ǧ™‘”‡”•ȏ͵ͲȐ  Š‡†‡˜‡Ž‘’‡–‘ˆ’”‡†‹ –‹˜‡ ‘’—–‡”•‹—Žƒ–‹‘•™‘—Ž†‘†‘—„– Šƒ‰‡–Š‡ ƒ’’”‘ƒ Š ˆ‘” •›–Š‡•‹œ‹‰ ‘Ž‡ —Ž‡• ˆ‘” •‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘Ǥ —– ‡˜‡ ‘”‡ ƒ’’‡ƒŽ‹‰™‘—Ž†„‡–Š‡†‡”‹˜ƒ–‹‘‘ˆ•‹’Ž‡”—Ž‡•‰‘˜‡”‹‰–Š‡•‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘ ’”‘ ‡••ǤŠ‹•™‘—Ž†”‡’Žƒ ‡–Š‡ —””‡––”‹ƒŽƒ†‡””‘”ƒ’’”‘ƒ Šˆ‘”•›–Š‡•‹œ‹‰ –Š‡”‹‰Š–‘Ž‡ —Ž‡–Šƒ–‘”‰ƒ‹œ‡•‹ƒ•’‡ ‹ˆ‹ ƒ‡”Ǥ  DzEngineeringisnoteasy.Itrequiresasetofruleswhichallowspredictingthe outcomeoftheselfassemblyprocesswithahighdegreeofreliability.” Ǥ†‡ ‡›–‡”ƒ† ‘Ǧ™‘”‡”•ȏͳͺȐ  ʹ.

(18) Chapter1:Introduction “Through progressive discovery, understanding, and implementation of the rules that govern the evolution from inanimate to animate matter and beyond,wewillultimatelyacquiretheabilitytocreatenewformsofcomplex matter.” ǤǤ‡ŠǡȏͶȐ  Š‡•‡”—Ž‡•™‘—Ž†‘–‘Ž›Šƒ˜‡–‘ ‘˜‡”’”‘’‡”–‹‡•Ž‹‡•›‡–”›ǡ Š‹”ƒŽ‹–›ȏ͵ͳǦ ͵͵Ȑ ƒ† Š‹‡”ƒ” Š›ȏ͵ͶȐ ™‹–Š‹ •‡ŽˆǦ‘”‰ƒ‹œ‡† ’ƒ––‡”• „—– ‹‰Š– ƒŽ•‘ ‰‘ ‹–‘ –Š‡ ‘”‡ ‘’Ž‡š”‡ƒŽ‘ˆŠ‡–‡”‘‰‡‡‘—•ƒ••‡„Ž›ȏ͵ͷǦͶͲȐǤ Š‹•‘’‡•–Š”‡‡“—‡•–‹‘•ˆ‘”–Š‹•–Š‡•‹•ǣ  ͳǤ ‘™ ƒ–Š‡‡™ ‘’Ž‡š‹–›‹•‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘„‡‡š’Žƒ‹‡†ǫ ʹǤ

(19) •‹–’‘••‹„Ž‡–‘’”‡†‹ –‘Ž‡ —Žƒ”’ƒ––‡”‹ƒ†˜ƒ ‡—•‹‰•‹—Žƒ–‹‘•ǫ ͵Ǥ Šƒ–ƒ”‡–Š‡”—Ž‡•‰‘˜‡”‹‰‘Ž‡ —Žƒ”•‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘ǫ. 1.2 AimsoftheThesis ͳǤ Understand the mechanisms behind the phase variety and complex phase transformationsobservedinFréchetDendrons.  ”± Š‡– ‡†”‘• •Š‘™ –Š‡ Š‹‰Š‡•– ’Šƒ•‡ ˜ƒ”‹‡–› ˆ‘” ‘Ž‡ —Žƒ” •‡ŽˆǦ ‘”‰ƒ‹œƒ–‹‘ ‘ •—”ˆƒ ‡•Ǥ Š‡ ’ƒ––‡”• ‘‡š‹•– ƒ† ’Šƒ•‡ –”ƒ•ˆ‘” ‘ –Š‡ •—”ˆƒ ‡™‹–Š‹‹—–‡•–‘Š‘—”•ǤŠ‡‹ˆŽ—‡ ‡•‘ˆ–Š‡‘Ž‡ —Žƒ”ˆŽ‡š‹„‹Ž‹–›ƒ•™‡ŽŽ ƒ• –Š‡ ’”‘’‡”–‹‡• ‘ˆ –Š‡ ‘Ž‡ —Žƒ” „—‹Ž†‹‰ „Ž‘ • ƒ”‡ ”‡‰ƒ”†‡† ƒ• ’‘••‹„Ž‡ ”‡ƒ•‘•ǤŠ‡–‡’‘”ƒŽƒ†‡‡”‰‡–‹ ”‡Žƒ–‹‘•Š‹’„‡–™‡‡–Š‡’Šƒ•‡•‘ˆ•’‡ ‹ˆ‹  ‘Ž‡ —Ž‡• ‹• ‹˜‡•–‹‰ƒ–‡†Ǥ  ‘’ƒ”‹•‘ „‡–™‡‡ ‘Ž‡ —Ž‡• ‘ˆ ‹ ”‡ƒ•‹‰ ‘’Ž‡š‹–›‡š’Ž‘”‡•–Š‡“—‡•–‹‘‘ˆ‡‡”‰‡ ‡™‹–Š‹•‡ŽˆǦ‘”‰ƒ‹œ‡†•›•–‡•Ǥ  ʹǤ Develop in cooperation a simulation model capable of predicting the pattern varietyoftheFréchetDendronsystem.  ‘ ˆƒ” ‹– Šƒ• „‡‡ ‹’‘••‹„Ž‡ –‘ ’”‡†‹ – –Š‡ ’ƒ––‡” ˆ‘” ƒ •‡ŽˆǦ‘”‰ƒ‹œ‡† ‘‘Žƒ›‡” ’”‹‘” –‘ –Š‡ ‡š’‡”‹‡–Ǥ

(20)  –Š‹• –Š‡•‹• ƒ ‹–‡”ƒ –‹‘ •‹–‡ ‘†‡Ž ‹• †‡˜‡Ž‘’‡† ‹ ‘‘’‡”ƒ–‹‘ ™‹–Š –Š‡‘”‹•–•Ǥ Š‹• •‹—Žƒ–‹‘ ƒ’’”‘ƒ Š †”ƒ•–‹ ƒŽŽ› ”‡†— ‡•–Š‡‘Ž‡ —Žƒ” ‘’Ž‡š‹–›–‘‹ ”‡ƒ•‡–Š‡—„‡”‘ˆ•‹—Žƒ–‡†‘Ž‡ —Ž‡• ƒ• ™‡ŽŽ ƒ• –Š‡ •‹—Žƒ–‹‘ –‹‡ • ƒŽ‡Ǥ Š‡•‡ –™‘ ‘†‹–‹‘• ƒ”‡ ’”‡”‡“—‹•‹–‡• ˆ‘” –Š‡’‘••‹„Ž‡’”‡†‹ –‹‘‘ˆ’ƒ––‡”•ˆ”‘ƒ—‘”†‡”‡†•–ƒ–‡ǤŠ‡‘†‡Ž‹•–‡•–‡† ‘–Š‡’Šƒ•‡”‹ Š ”± Š‡–‡†”‘•›•–‡Ǥ ͵.

(21) Ph.D.ThesisCarstenRohr ͵Ǥ Abstract rules of selforganization from the complex behavior of Fréchet Dendronswhicharealsoapplicabletoothermolecules. —Ž‡•‰‘˜‡”‹‰‘”‡ ‘’Ž‡šˆ‘”•‘ˆ•‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘ǡŽ‹‡Š‹‡”ƒ” Š‹ ƒŽ ƒ••‡„Ž›ǡ ƒ”‡ ƒ„•‡– ƒ† ƒ –”‹ƒŽ ƒ† ‡””‘” ƒ’’”‘ƒ Š ’”‡˜ƒ‹Ž• ™Š‡ ƒ •’‡ ‹ˆ‹  ’ƒ––‡” ‘—– ‘‡ ‹• †‡•‹”‡†Ǥ ‡”‡ –Š‡ †‹ˆˆ‡”‡– ˆ‘”• ‘ˆ ’ƒ––‡”• ”‡ƒ–‡† „› ”± Š‡– ‡†”‘• ƒ”‡ ‘†‡Ž‡† ƒ† ‘‘ ˆ‡ƒ–—”‡• ‹ –Š‡ ‘”†‡”‹‰• ƒ”‡ ‹†‡–‹ˆ‹‡†ǤŠ‡†‡”‹˜‡†”—Ž‡•ƒ”‡ Š‡ ‡†ƒ‰ƒ‹•––Š‡Ž‹–‡”ƒ–—”‡‘ˆ•‡ŽˆǦ‘”‰ƒ‹œ‡† •›•–‡•ƒ†’‘••‹„Ž‡‡š’‡”‹‡–ƒŽ”‡ƒŽ‹œƒ–‹‘•ƒ”‡–‡•–‡†Ǥ. 1.3 StructureoftheThesis ˆ–‡”ƒ ‘•‹†‡”ƒ–‹‘‘ˆ–Š‡ —””‡–”‡•‡ƒ” Šƒ†–Š‡‹†‡–‹ˆ‹ ƒ–‹‘‘ˆ‡› “—‡•–‹‘•ǡ–Š‡ƒ‹•‘ˆ–Š‹•–Š‡•‹•ƒ”‡™‘”‡†‘—–‹ Šƒ’–‡”‘‡ǤŠ‡–Š‡•‹•‹•–Š‡ †‹˜‹†‡†‹–‘–™‘Žƒ”‰‡’ƒ”–•ǡ‘‡‹–”‘†— ‹‰ ‘ ‡’–•ƒ†–‡ Š‹“—‡•‹’‘”–ƒ– –‘–Š‡–‘’‹ ǡ™Š‹Ž‡–Š‡•‡ ‘†ŠƒŽˆ ‘’”‹•‡•–Š‡”‡•—Ž–•‘ˆ–Š‡”‡•‡ƒ” ŠǤ Š‡ Šƒ’–‡”• ‹ –Š‡ ˆ‹”•– ŠƒŽˆ ƒ”‡ ‰”‘—’‡† „› –‘’‹ Ǥ

(22)  –Š‡ „‡‰‹‹‰ Šƒ’–‡”–™‘‹–”‘†— ‡••‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘‹‰‡‡”ƒŽƒ†–Š‡‘”‡•’‡ ‹ˆ‹ ƒŽŽ›ˆ‘” ‘Ž‡ —Žƒ”‘‘Žƒ›‡”•Ǥ ‹–Š –Š‹•‰‡‡”ƒŽ ‘ ‡’– ‘˜‡”‡†ǡ –Š‡ ‡š’‡”‹‡–ƒŽ •‹–‡ ‡ ‘’ƒ••‹‰ –Š‡ • ƒ‹‰ –—‡Ž‹‰ ‹ ”‘• ‘’‡ ȋȌ ƒ† ‹–• „ƒ ‰”‘—† –Š‡‘”› ƒ† ‹ƒ‰‡ ƒ “—‹•‹–‹‘ ƒ”‡ ‹–”‘†— ‡† ‹ Šƒ’–‡” –Š”‡‡Ǥ Š‡ ‘Ž‡ —Žƒ” ƒ•’‡ – ‹• ‹–”‘†— ‡† ‹ Šƒ’–‡” ˆ‘—” †‡ˆ‹‹‰ •—’”ƒ‘Ž‡ —Žƒ” Š‡‹•–”› ƒ† –Š‡ ‡’Ž‘›‡† •›•–‡ ‘ˆ ”± Š‡– ‡†”‘•Ǥ Š‡ ‘‡ –‹‘ „‡–™‡‡ ‡‡”‰› Žƒ†• ƒ’‡•ǡ’Šƒ•‡–”ƒ•ˆ‘”ƒ–‹‘•ƒ†‡‡”‰‡ ‡‹•‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘‹•ƒ†‡‹ Šƒ’–‡” ˆ‹˜‡Ǥ  Š‡ „ƒ•‹• ˆ‘” –Š”‡‡ †‹ˆˆ‡”‡– •‹—Žƒ–‹‘ ƒ’’”‘ƒ Š‡• ‘Ž‡ —Žƒ” ‡ Šƒ‹ •ǡ†‡•‹–›ˆ— –‹‘ƒŽ–Š‡‘”›ƒ†‹–‡”ƒ –‹‘•‹–‡‘†‡Ž‹‰ƒ”‡‡š’Žƒ‹‡† ‡š–‹ Šƒ’–‡”•‹šǤ

(23) –Š‡Žƒ•– Šƒ’–‡”•‡˜‡ǡ–Š”‡‡’”‘’‡”–‹‡•‘ˆ•‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘ǡ ƒ‡Ž›•›‡–”›ǡ Š‹”ƒŽ‹–›ƒ†Š‹‡”ƒ” Š›™‹ŽŽ„‡†‹• —••‡†Ǥ

(24)  –Š‡ „‡‰‹‹‰ ‘ˆ –Š‡ ”‡•—Ž–• –Š‡ ’—„Ž‹ ƒ–‹‘• ƒ”‡ „”‹‡ˆŽ› •—ƒ”‹œ‡†Ǥ Š‡ ˆ‹”•– •–ƒ”–• ™‹–Š ‡‡”‰‡– ’Šƒ•‡• ˆ‘” ‹ ”‡ƒ•‹‰ ‘Ž‡ —Žƒ” ‘’Ž‡š‹–›Ǥ Š‡ ‡š– ˆ‘—” ’—„Ž‹ ƒ–‹‘• ‹–”‘†— ‡ ƒ† –Š‡ Š‹‰ŠŽ‹‰Š– †‹ˆˆ‡”‡– ƒ•’‡ –• ‘ˆ ƒ ‹–‡”ƒ –‹‘ •‹–‡ ‘†‡Ž ™Š‹ Š •— ‡••ˆ—ŽŽ› ”‡’”‘†— ‡• ƒ ‡š’‡”‹‡–ƒŽ ’ƒ––‡” ˜ƒ”‹‡–› ƒ† ’”‡†‹ –• ”‡•—Ž–• ’”‹‘” –‘ –Š‡ ‡š’‡”‹‡–Ǥ Š‡ ˆ‘ŽŽ‘™‹‰ –™‘ ’—„Ž‹ ƒ–‹‘• ‹–”‘†— ‡ ”—Ž‡• ˆ‘” ‘Ž‡ —Žƒ” •‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘ ƒ† —–‹Ž‹œ‡ ƒ ‘†‹ˆ‹‡† •—”ˆƒ ‡ ƒ••‡„Ž›Ǥ Š‡ Žƒ•– ’—„Ž‹ ƒ–‹‘ ‘„‹‡• –™‘ ’”‡˜‹‘—•Ž› •‡’ƒ”ƒ–‡ ˆ‹‡Ž†• ‘ˆ Š‡–‡”‘‰‡‡‘—• •‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘Ǥ

(25)  –Š‡ ‡†–Š‡•‡ ˆ‹†‹‰• ƒ”‡ ’—–‹–‘ ‘–‡š–ƒ†’‘••‹„Ž‡ˆ—–—”‡’”‘•’‡ –•ƒ”‡†‹• —••‡†Ǥ Š‡ƒ’’‡†‹šˆ‡ƒ–—”‡•ƒ’‘’—Žƒ”• ‹‡ ‡„‘‘ Šƒ’–‡”‘‡‡”‰‡ ‡ƒ†ƒ ’—„Ž‹ ƒ–‹‘ƒ„‘—–‘”‰ƒ‹ •—’‡” ‘†— –‘”•ǡ‘–’ƒ”–‘ˆ–Š‹•–Š‡•‹•Ǥ Ͷ.

(26) 2. SelfOrganization. 2.1 Concept ƒ––‡” ˆ‘”ƒ–‹‘ ƒ† †‡•–”— –‹‘ ƒ”‡ –Š‡ –™‘ „ƒ•‹  ’”‘ ‡••‡• †”‹˜‹‰ Šƒ‰‡‹‘—”—‹˜‡”•‡Ǥ‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘”‡ˆ‡”•–‘ƒ Žƒ••‘ˆ’ƒ––‡”ˆ‘”ƒ–‹‘‹ ƒ™‹†‡”ƒ‰‡‘ˆ•›•–‡•ȏʹȐǡˆ”‘‹ƒ‹ƒ–‡‘„Œ‡ –•–‘•‡ŽˆǦ†‡–‡”‹‡†ƒ‰‡–•–Š‡ ‹†‹˜‹†—ƒŽ’ƒ”–•ƒ”‡ ‘‡ –‡†„›–Š‡’”‘ ‡••‘ˆ’ƒ––‡”ˆ‘”ƒ–‹‘–Šƒ–Ž‡ƒ†•–‘ –Š‡ ”‡ƒ–‹‘‘ˆ•–”— –—”‡ƒ†‘”†‡”™‹–Š‹ǤŠ‹•’”‘ ‡••‹•‹–‡”ƒŽƒ†Šƒ’’‡• „›‹–‡”ƒ –‹‘•‹Š‡”‡––‘–Š‡•›•–‡ǡ”‡“—‹”‹‰‘‡š–‡”ƒŽ‹ˆŽ—‡ ‡•–‘†”‹˜‡ –Š‡’ƒ––‡”ˆ‘”ƒ–‹‘Ǥ‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘‹•‘ˆ–‡†‡ˆ‹‡†„›™Šƒ–‹–‹•‘–Ǥ

(27) •‡ŽˆǦ ‘”‰ƒ‹œ‡† •›•–‡• –Š‡”‡ ‹• ‘ ‰Ž‘„ƒŽ ’Žƒ †‹”‡ –‹‰ –Š‡ ‹†‹˜‹†—ƒŽ ’ƒ”–•ǡ ‘ ‡š–‡”ƒŽ „Ž—‡’”‹– ‘” –‡’Žƒ–‡ǡ ‘ ‘”†‡” ‹’‘•‡† „› ƒ› •‘”– ‘ˆ ‘—–•–ƒ†‹‰ Ž‡ƒ†‡” ‘” ‰—‹†‡ǡ –Š‘—‰Š –Š‡”‡ ‹‰Š– „› ƒ •‡ŽˆǦ‘”‰ƒ‹œ‡† Š‹‡”ƒ” Š‹ ƒŽ ‘”†‡”ǡ •‡‡ Šƒ’–‡”͹Ǥ͵Ǥ ˜‡”›—•‡ˆ—Ž†‡ˆ‹‹–‹‘ˆ‘”•‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘‹•‰‹˜‡„› ‘––ƒƒœ‹‡ȏͳȐǣ DzSelforganization is a process in which pattern at the global level of a system emergessolelyfromnumerousinteractionsamongthelowerlevelcomponentsof the system. Moreover, the rules specifying interactions among the system's components are executed using only local information, without reference to the globalpattern.Inshort,thepatternisanemergentpropertyofthesystem,rather than a property imposed on the system by an external ordering influence.” Š‹• †‡ˆ‹‹–‹‘”‡“—‹”‡•–Š‡ƒ’’‡ƒ”ƒ ‡‘ˆƒ’ƒ––‡”™‹–Š‹ƒ•›•–‡ǤŠ‡’ƒ––‡” ƒ „‡•’ƒ–‹ƒŽ‘”–‡’‘”ƒŽ‹ƒ–—”‡‘”ƒ ‘„‹ƒ–‹‘‘ˆ„‘–ŠǤ

(28) –‡‡†•–‘„‡’”‡•‡– ƒ––Š‡‰Ž‘„ƒŽŽ‡˜‡Ž‘ˆ–Š‡•›•–‡Ǥ•‡ŽˆǦ‘”‰ƒ‹œ‡†•›•–‡”‡“—‹”‡•—Ž–‹’Ž‡’ƒ”–• ƒ†ƒ‡ƒ•‘ˆ‹–‡”ƒ –‹‘„‡–™‡‡–Š‡’ƒ”–•‘ˆ–Š‡•›•–‡ǡ™Š‹ Š ƒ„‡†‹”‡ – ‘”‹†‹”‡ –‹–‡”ƒ –‹‘ǤŠ‡’ƒ––‡”‹•‘–•–”— –—”‡†„›ƒ‘—–•‹†‡‹ˆŽ—‡ ‡„—– „› –Š‡ ‹–‡”ƒ –‹‘• „‡–™‡‡ –Š‡ ‘’‘‡–•Ǥ ‡˜‡”–Š‡Ž‡•• ƒ ‘—–•‹†‡ ‹ˆŽ—‡ ‡ ȋ–‡’‡”ƒ–—”‡ Šƒ‰‡ǡ’”‡†ƒ–‘”‡– ǤȌ ƒ–”‹‰‰‡”ƒ’ƒ––‡”‘”’ƒ––‡” Šƒ‰‡ǤŠ‡ ͷ.

(29) Ph.D.ThesisCarstenRohr ‹–‡”ƒ –‹‘• ˆ‘ŽŽ‘™ ”—Ž‡•ǡ ™Š‹ Š ƒ”‡ •–”‹ –Ž› Ž‘ ƒŽ ‹ ƒ–—”‡ǡ ‰Ž‘„ƒŽ –‡’Žƒ–‡• ‘” ’Žƒ• ‹ –Š‹• †‡ˆ‹‹–‹‘Ǥ ƒ•–Ž› –Š‡ ’ƒ––‡” ƒ „› Šƒ”ƒ –‡”‹œ‡† ƒ• ƒ ‡‡”‰‡– ’”‘’‡”–›ǡ•‡‡ Šƒ’–‡”ͷǤͶǤ.  Figure 1. Fish schools and individual directives: Š‡ •‡ŽˆǦ ‘”‰ƒ‹œƒ–‹‘ „‡Šƒ˜‹‘” ‘ˆ ˆ‹•Š • Š‘‘Ž• ‹• †”‹˜‡ „› –Š”‡‡ ”—Ž‡• –Šƒ– ‹†‹˜‹†—ƒŽ•ƒ†Š‡”‡–‘‹–Š‡‹”Ž‘ ƒŽ‡˜‹”‘‡–ǤƒȌ–ƒ›‹–Š‡ ‡–‡” ‘ˆ –Š‡ ‰”‘—’Ǥ „Ȍ ‡ƒ˜‡ •’ƒ ‡ ˆ‘” ƒ‡—˜‡”‹‰Ǥ Ȍ ƒ– Š –Š‡ ‘˜‡‡–†‹”‡ –‹‘‘ˆ›‘—”Ž‘ ƒŽ‡‹‰Š„‘”•Ǥ Š‹•†‡ˆ‹‹–‹‘™‹ŽŽŠ‡”‡„‡‹ŽŽ—•–”ƒ–‡†„›• Š‘‘Ž•‘ˆˆ‹•ŠǤŠ‡‹†‹˜‹†—ƒŽˆ‹•Š ˆ‘” ƒ •’ƒ–‹ƒŽ ƒ””ƒ‰‡‡– ‘ˆ ƒ Ž‘•‡† •™ƒ” ™‹–Š ”‡‰—Žƒ” †‹•–ƒ ‡• –‘ –Š‡‹” ‡ƒ”‡•–‡‹‰Š„‘”•ƒ†ƒ‰‡‡”ƒŽ•™ƒ”†‹”‡ –‹‘ǤŠ‡‹–‡”ƒ –‹‘‘ˆ–Š‡†‹ˆˆ‡”‡– ‹†‹˜‹†—ƒŽ•™‹–Š‹ƒ• Š‘‘Ž‹•‰‘˜‡”‡†„›–Š”‡‡”—Ž‡•ǤŠ‡•‡”—Ž‡••–”‹ –Ž›ƒ’’Ž› –‘–Š‡Ž‘ ƒŽ‡˜‹”‘‡–‘ˆ–Š‡‹†‹˜‹†—ƒŽǡ•‡‡ˆ‹‰—”‡ͳǤͳǤ–ƒ›‹–Š‡ ‡–‡”‘ˆ–Š‡ ‰”‘—’ ȋ˜‘‹† —‘ —’‹‡† •’ƒ ‡ ƒ”‘—† ›‘—ȌǤ ʹǤ ‡ƒ˜‡ ȋŽ‘ ƒŽȌ •’ƒ ‡ ˆ‘” ƒ‡—˜‡”‹‰Ǥ ͵Ǥ ƒ– Š –Š‡ ‘˜‡‡– †‹”‡ –‹‘ ‘ˆ ›‘—” Ž‘ ƒŽ ‡‹‰Š„‘”•Ǥͳ ‘ ‹–‡”ƒŽ‰Ž‘„ƒŽ’Žƒ‘”‡š–‡”ƒŽ–‡’Žƒ–‡ ”‡ƒ–‡•–Š‹•„‡Šƒ˜‹‘”Ǥ

(30) –Š‡ˆ‘ŽŽ‘™‹‰ǡ–Š‹•†‡ˆ‹‹–‹‘‘ˆ•‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘™‹ŽŽ‘™„‡ƒ’’Ž‹‡†–‘ –Š‡‘”†‡”‹‰’Š‡‘‡ƒ‘ˆ‘Ž‡ —Žƒ”•›•–‡•Ǥ . 2.2 MolecularSelfOrganization ‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘ƒ––Š‡‘Ž‡ —Žƒ”Ž‡˜‡Ž‹•‘‡‘ˆ–™‘ƒ’’”‘ƒ Š‡•–‘ ”‡ƒ–‡ •–”— –—”‡• ƒ– –Š‡ ƒ‘‡–‡” • ƒŽ‡Ǥ Š‡ ”‘—–‡ ‡’Ž‘›‡† „› ‘Ž‡ —Žƒ” •‡ŽˆǦ ‘”‰ƒ‹œƒ–‹‘ǡƒŽ•‘‘™ƒ•„‘––‘Ǧ—’ƒ’’”‘ƒ Šǡ ”‡ƒ–‡• ‘’Ž‡š•–”— –—”‡•‘—– . ͳŠ‹•–Š‹”†”—Ž‡‹•ˆ‘—†‹ˆŽ‘ •‘ˆ„‹”†•‘”• Š‘‘Ž•‘ˆˆ‹•Šǡ„—–‹•‹••‹‰‹•™ƒ”•‘ˆ‹•‡ –•ǤŠ‡”‡ˆ‘”‡. ‹•‡ –•™ƒ”„‡Šƒ˜‹‘”Ž‘‘•†‹•–‹ –Ž›†‹ˆˆ‡”‡–ƒ†‘”‡ Šƒ‘–‹ Ǥ. ͸.

(31) Chapter2:SelfOrganization ‘ˆ”‡Žƒ–‹˜‡Ž›•‹’Ž‡‘‡•Ǥ

(32)  ‘–”ƒ•–ǡ–Š‡–‘’Ǧ†‘™ƒ’’”‘ƒ Š‹’‘•‡•’”‡†‡ˆ‹‡† •–”— –—”‡„›ƒ‰Ž‘„ƒŽ–‡’Žƒ–‡‘”’ŽƒǤ Š‡ Š‡ ‹‰ –Š‡ ’”‡˜‹‘—•Ž› ‡’Ž‘›‡† †‡ˆ‹‹–‹‘ ˆ‘” •‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘ ˆ‘”ƒ’’Ž‹ ƒ„‹Ž‹–›‘–Š‡‘Ž‡ —Žƒ”• ƒŽ‡ǡ•‹‹Žƒ”‹–‹‡•„—–ƒŽ•‘”‡•–”‹ –‹‘•ƒ’’‡ƒ”Ǥ

(33) †‹˜‹†—ƒŽ‘Ž‡ —Ž‡• ƒˆ‘”’ƒ––‡”•‹–Š‡ƒ„•‡ ‡‘ˆ‡š–‡”ƒŽ•–‹—Ž‹Ǥ ‘”–Š‹• ’”‘ ‡•• –‘ ‘ —”ǡ Ž‘ ƒŽ ‹–‡”ƒ –‹‘• ‡‡† –‘ ‰‘˜‡” –Š‡ ‘”†‡”‹‰Ǥ Š‡ „ƒ•‹  Ž‘ ƒŽ ‘•’‡ ‹ˆ‹  ‹–‡”ƒ –‹‘• ƒ– –Š‡ ‘Ž‡ —Žƒ” • ƒŽ‡ ƒ”‡ ƒ––”ƒ –‹‘ǡ ”‡’—Ž•‹‘ ƒ† ‘”‹‡–ƒ–‹‘ǤŠ‡‘•–„ƒ•‹ ƒ––”ƒ –‹˜‡ˆ‘” ‡‹•–Š‡˜ƒ†‡”ƒƒŽ•ˆ‘” ‡ǤŠ‡ƒ—Ž‹ š Ž—•‹‘”‹ ‹’Ž‡’”‡˜‡–•–Š‡‘˜‡”Žƒ’‘ˆ‘Ž‡ —Ž‡•ǡ™Š‹Ž‡‡Ž‡ –”‘•–ƒ–‹ ƒ†‹ ’ƒ”–‹ —Žƒ”†‹’‘Žƒ”ˆ‘” ‡•ǡ‘”‹‡–‘Ž‡ —Ž‡•™‹–Š”‡•’‡ ––‘‡ƒ Š‘–Š‡”ǡ•‡‡ˆ‹‰—”‡ʹǤ.  Figure 2. Molecular selforganization: Š”‡‡ „ƒ•‹  ‘ ‘˜ƒŽ‡– ‹–‡”ƒ –‹‘• ‘ –Š‡ ‘Ž‡ —Žƒ” • ƒŽ‡ –Šƒ– Ž‡ƒ† –‘ ‘Ž‡ —Žƒ” •‡ŽˆǦ ‘”‰ƒ‹œƒ–‹‘Ǥ ƒȌ ƒ †‡” ƒƒŽ• ˆ‘” ‡• ƒ––”ƒ – ‘Ž‡ —Ž‡• –‘ ƒ‘–Š‡”Ǥ „Ȍ Š‡ ƒ—Ž‹ ”‡’—Ž•‹‘ ’”‡˜‡–• ‘Ž‡ —Ž‡• ˆ”‘ ‘˜‡”Žƒ’’‹‰Ǥ Ȍ Ž‡ –”‘•–ƒ–‹  ˆ‘” ‡• ‘”‹‡– ‘Ž‡ —Ž‡• ™‹–Š ”‡•’‡ – –‘ –Š‡‹” Ž‘ ƒŽ ‡˜‹”‘‡–Ǥ Š‡‡ ‡••‹–›ˆ‘”‘Ǧ ‘˜ƒŽ‡–„‘†•‹•‰‹˜‡„›–Š‡Ž‘ ƒŽ Šƒ”ƒ –‡”‘ˆ–Š‡ ‹–‡”ƒ –‹‘•ǡ ™Š‹ Š ”‡“—‹”‡• –Š‡ ’‘••‹„‹Ž‹–› ‘ˆ ”‡ ‘ˆ‹‰—”ƒ–‹‘ –‘ ƒ†ƒ’– –‘ Ž‘ ƒŽ Šƒ‰‡• ‘– ’‘••‹„Ž‡ ™‹–Š ‘˜ƒŽ‡–Ž› „‘†‡† ‘Ž‡ —Žƒ” ‡•Š‡•Ǥ

(34)  –Š‡ ƒ•‡ ‘ˆ •—”ˆƒ ‡ „‘—† •‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘ǡ –Š‡ ’‘••‹„‹Ž‹–› ‘ˆ ƒ –‡’Žƒ–‹‰ ‹ˆŽ—‡ ‡ ‘ˆ –Š‡ •—„•–”ƒ–‡ ƒ‹’‡†‡–Š‡‘”†‡”‹‰’”‘ ‡••ƒ†’”‡†‡–‡”‹‡’‘••‹„Ž‡‘”†‡”‹‰•Ǥ ‘” –Š‡ ‹ˆŽ—‡ ‡ ‘ˆ –Š‡ •—”ˆƒ ‡ ’”‘’‡”–‹‡• ‘ –Š‡ ‘”‰ƒ‹œƒ–‹‘ ’”‘ ‡•• •‡‡ Šƒ’–‡”͹ǤͳǤ †‹•–‹ –Ž›†‹ˆˆ‡”‡–ˆ‘”‘ˆ•‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘ ƒ„‡ˆ‘—†ǡ™Š‡•’‡ ‹ˆ‹  ‡›ǦŽ‘  ‹–‡”ƒ –‹‘• ƒ”‡ ‡’Ž‘›‡†Ǥ ‡”‡ –Š‡ ‹–‡”ƒ –‹‘• ƒ””› ƒ •’‡ ‹ˆ‹  ‹ˆ‘”ƒ–‹‘ ‘’‘‡–ǡ ™Š‹ Š ƒŽŽ‘™• ˆ‘” ƒ ‰”‡ƒ–‡” †‹”‡ –‡† ‡‰‹‡‡”‹‰ ƒ„‹Ž‹–›ȏͶȐǤ Š‡ ƒ††‹–‹‘ƒŽ ‹ˆ‘”ƒ–‹‘ ‘’‘‡– —•—ƒŽŽ› Ž‡ƒ†• –‘ †‹•–‹ –Ž› †‹ˆˆ‡”‡–ƒ••‡„Ž› ‘’‘‡–•™‹–ŠŠ‹‰ŠŽ›‹†‹˜‹†—ƒŽ‹•–‹ ‹–‡”ƒ –‹‘•†‡’‡†‹‰. ͹.

(35) Ph.D.ThesisCarstenRohr ‘ –Š‡ •’‡ ‹ˆ‹ ‹–› ‘ˆ –Š‡ ‹–‡”ƒ –‹‰ ’ƒ”–•Ǥ ‹‘ Š‡‹ ƒŽ ƒ† „‹‘Ž‘‰‹ ƒŽ ‘Ž‡ —Ž‡• ‡’Ž‘›–Š‹•‹†‘ˆ•‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘„‡–™‡‡Š‡–‡”‘‰‡‡‘—•’ƒ”–•Ǥ  ’”‹ƒ”› ‡šƒ’Ž‡ ‘ˆ ‹ˆ‘”ƒ–‹‘ ƒ””›‹‰ „—‹Ž†‹‰ „Ž‘ • ‹• –Š‡ •’‡ ‹ˆ‹ ‹–›‘ˆƒ••‡„Ž›ȏͶͳǡͶʹȐǤŽ›•‡“—‡ ‡•‘ˆ„ƒ•‡•ˆ‹––‹‰–Š‡‹” ‘—–‡” •–”ƒ†„‹†–‘‰‡–Š‡”–‘ˆ‘”ƒ‡••‡–‹ƒŽŽ›‘‡Ǧ†‹‡•‹‘ƒŽ•–”ƒ†•‡‡ˆ‹‰—”‡͵ƒǤ ‡˜‡”–Š‡Ž‡•• –Š‡ ƒ••‡„Ž› ‹–‘ –™‘ ƒ† –Š”‡‡ †‹‡•‹‘ƒŽ •–”— –—”‡• ‹• ƒŽ•‘ ’‘••‹„Ž‡Ǥ

(36)  –Š‡ Š‘Ž‹†ƒ› Œ— –‹‘ ˆ‘” ‡šƒ’Ž‡ǡ ™Š‡”‡ ˆ‘—” ‘Ž› ’ƒ”–‹ƒŽŽ› ˆ‹––‹‰ •–”ƒ†•‘”‰ƒ‹œ‡‹–‘ƒ ”‘••Ž‹‡•Šƒ’‡ǡ•‡‡ˆ‹‰—”‡͵„Ǥ‹–Š–Š‡—•‡‘ˆ•–‹ › ‡†‹‰•–Š‹•‡–™‘” ƒ„‡”‡’‡ƒ–‡†‹–™‘†‹‡•‹‘•ǡ•‡‡ˆ‹‰—”‡͵ Ǥ.  Figure 3. Information and DNA selfassembly:

(37)   ƒ••‡„Ž› ‹ˆ‘”ƒ–‹‘ ‹• ‡ ‘†‡† ‹ –Š‡ „ƒ•‡ •‡“—‡ ‡ ‘ˆ ‹†‹˜‹†—ƒŽ •‡ŽˆǦ ƒ••‡„Ž› „—‹Ž†‹‰ „Ž‘ •Ǥ ƒȌ ”‡’”‘‰”ƒ‡†  •–”ƒ†• ‘Ž› ƒ••‡„Ž‡ ™‹–Š –Š‡‹” ˆ‹––‹‰ ‘—–‡”’ƒ”–Ǥ „Ȍ  ‘Ž‹†ƒ› Œ— –‹‘ ƒ• •‹’Ž‡ ‡šƒ’Ž‡ ‘ˆ –™‘Ǧ†‹‡•‹‘ƒŽ  ‘”‰ƒ‹œƒ–‹‘Ǥ Ȍ –”— –—”‡ ”‡’‡–‹–‹‘—•‹‰•–‹ ›‡†•™‹–Š‹–Š‡•–”— –—”‡Ǥ. ”‡ƒ– •–”‹†‡• Šƒ˜‡ „‡‡ ƒ†‡ ™‹–Š ‹ˆ‘”ƒ–‹‘ ‡ ‘†‡†  •‡ŽˆǦ ƒ••‡„Ž› ‹ –Š‡ ”‡ ‡– ›‡ƒ”•ȏͶ͵Ȑ ƒ† •‹‹Žƒ”‹–‹‡• ƒ† ‘˜‡”Žƒ’ „‡–™‡‡ –Š‡ –™‘ ƒ”‡ƒ•‘ˆ‘Ž‡ —Žƒ”•‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘„‡ ‘‡ƒ’’ƒ”‡–ǤŠ‹•™‘”ˆ‘ —•‡•‘–Š‡ ‘Ǧ•’‡ ‹ˆ‹  ˆ‘” ‘ˆ •‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘ǡ ‹–• ‡‡”‰‡– ’ƒ––‡”• ƒ† –Š‡ ’”‡†‹ –‹‘ –Š‡”‡‘ˆǤ Š‡ †‡–‡ –‹‘ ‘ˆ –Š‡ •‡ŽˆǦ‘”‰ƒ‹œƒ–‹‘ ƒ† –Š‡ ‡‡”‰‹‰ ’ƒ––‡”• ‹Š‡”‡––‘–Š‡•–—†‹‡†•›•–‡•”‡“—‹”‡ƒ–‘‘Ž™‹–Š•—„Ǧ‘Ž‡ —Žƒ””‡•‘Ž—–‹‘ǡƒ• • ƒ‹‰–—‡Ž‹‰‹ ”‘• ‘’› ƒ’”‘˜‹†‡Ǥ . ͺ.

(38) 3. ScanningTunnelingMicroscopy. 3.1 ScanningTunnelingMicroscopy

(39) ͳͻͺͳ• ƒ‹‰–—‡Ž‹‰‹ ”‘• ‘’›ȋȌ™ƒ•‹˜‡–‡†„› Ǥ‹‹‰ —† Ǥ ‘Š”‡”ȏͶͶȐǤ ‹–Š –Š‹• †‡˜‹ ‡ ‹– „‡ ƒ‡ ’‘••‹„Ž‡ –‘ ‹ƒ‰‡ •—”ˆƒ ‡• ™‹–Š ƒ–‘‹ ”‡•‘Ž—–‹‘Ǥ™ƒ•‘–‘Ž›‡’Ž‘›‡†ˆ‘”–Š‡ƒ–‘‹  Šƒ”ƒ –‡”‹œƒ–‹‘‘ˆ ‹—‡”ƒ„Ž‡ •—„•–”ƒ–‡• ƒ† –Š‡‹” ‡Ž‡ –”‘‹  •–ƒ†‹‰ ™ƒ˜‡•ȏͶͷǡ Ͷ͸Ȑǡ „—– ƒŽ•‘ ƒ–‘‹  ƒ† ‘Ž‡ —Žƒ” ƒ†Žƒ›‡”•ȏͶ͹Ȑǡ –Š‡ ‘„•‡”˜ƒ–‹‘ ƒ† ‹†— –‹‘ ‘ˆ Š‡‹ ƒŽ ”‡ƒ –‹‘•ȏͶͺȐǡ •—”ˆƒ ‡ Š‹”ƒŽ‹–›ȏͷȐǡ ‘ˆ‘”ƒ–‹‘ƒŽ •™‹– Š‹‰ȏͶͻǦͷͳȐǡ •’‹ ’‘Žƒ”‹œƒ–‹‘ȏͷʹȐƒ•™‡ŽŽƒ•ƒ–‘‹ ’‘•‹–‹‘‹‰ȏͷ͵ȐǤ  ƒ‹‰ –—‡Ž‹‰ ‹ ”‘• ‘’› ”‡Ž‹‡• ‘ –Š‡ “—ƒ–— ‡ Šƒ‹ ƒŽ –—‡Ž‹‰‡ˆˆ‡ –ǤŠ‡–‹’ƒ†–Š‡•—„•–”ƒ–‡Šƒ˜‡ƒƒ’’Ž‹‡†„‹ƒ•˜‘Ž–ƒ‰‡U‹ƒ•ƒ† ˆ‘” ƒ ‘’‡ ‹” —‹–Ǥ †‡” Žƒ••‹ ƒŽ ‘†‹–‹‘• –Š‹• „ƒ””‹‡” ‘—Ž† ‘– „‡ ‘˜‡” ‘‡ „› –Š‡ ‡Ž‡ –”‘•Ǥ Š‡ ‘•‹†‡”‹‰ “—ƒ–— ‡ Šƒ‹ •ǡ –Š‡‹” ™ƒ˜‡• †‘‘–‡†ƒ„”—’–Ž›ƒ––Š‡„ƒ””‹‡”ǡ„—–†‡ ƒ›‡š’‘‡–‹ƒŽŽ›Ǥ

(40) ˆ–Š‡„ƒ””‹‡”‹•–Š‹ ‡‘—‰Šǡ–Š‡’”‘„ƒ„‹Ž‹–›ˆ— –‹‘‡š–‡†•‹–‘–Š‡”‡‰‹‘„‡›‘†–Š‡„ƒ””‹‡”ƒ† ‡Ž‡ –”‘• ƒ”‡ ƒ„Ž‡ –‘ –—‡Ž –Š”‘—‰Š –Š‡ „ƒ””‹‡”Ǥ Š‡ –—‡Ž‹‰ —””‡– ‹• ‹˜‡”•‡Ž›‡š’‘‡–‹ƒŽ™‹–Š”‡•’‡ ––‘–Š‡–‹’Ȃ•—”ˆƒ ‡†‹•–ƒ ‡ǡ•‡‡ Šƒ’–‡”͵ǤʹǤ Š‹•‹’Ž‹‡•‘–Š‡‘‡Šƒ†–Šƒ––Š‡‹–‡”ƒ –‹‘‹•‡š–”‡‡Ž›•Š‘”–”ƒ‰‡†ʹǡ‘ –Š‡‘–Š‡”Šƒ†‹–ƒŽŽ‘™•–Š‡’”‡ ‹•‡Š‡‹‰Š–†‡–‡ –‹‘‘ˆ–Š‡•—”ˆƒ ‡ǡ‹ˆˆ‘”‡šƒ’Ž‡ –Š‡–‹’‹•Š‡Ž† ‘•–ƒ–ǤŠ‡–—‡Ž‹‰ —””‡–‹•‰‡‡”ƒŽŽ›‹–Š‡‘”†‡”‘ˆͳͲǦͻ–‘ ͳͲǦͳʹǤ ‹‡œ‘Ǧƒ –—ƒ–‘”• ƒŽŽ‘™ –‹’ Ȃ •—„•–”ƒ–‡ ’‘•‹–‹‘‹‰ ™‹–Š •—„Ǧƒ‰•–”‘ ’”‡ ‹•‹‘Ǥ  Š‡‹” ™‘”‹‰ ’”‹ ‹’Ž‡ ”‡Ž‹‡• ‘ ƒ ‡Ž‡ –”‹  ’”‘’‡”–› ‘ˆ ƒ‹•‘–”‘’‹  ”›•–ƒŽ• ƒ† ‡”–ƒ‹ ‡”ƒ‹  ƒ–‡”‹ƒŽ•Ǥ Š‡ †‹‡•‹‘• ‘ˆ –Š‡ ’‹‡œ‘Ǧ‡Ž‡ –”‹  ƒ–‡”‹ƒŽ ™‹ŽŽ Šƒ‰‡ǡ †‡’‡†‹‰ ‘ –Š‡ †‹”‡ –‹‘ ƒ† •–”‡‰–Š ‘ˆ –Š‡ ƒ’’Ž‹‡† . ʹ. Š‡ –—‡Ž‹‰ —””‡– ‹• ”‡†— ‡† –‘ ͳΨ ‘ˆ ‹–• ‘”‹‰‹ƒŽ ˜ƒŽ—‡ ‹ˆ –Š‡ –‹’ •—”ˆƒ ‡ †‹•–ƒ ‡ ‹• ‹ ”‡ƒ•‡†„›ͳƒ‰•–”‘Ǥ. ͻ.

(41) Ph.D.ThesisCarstenRohr ˜‘Ž–ƒ‰‡ ™‹–Š‹ –Š‡ ”ƒ‰‡ ‘ˆ ƒ‘‡–‡”•Ǥ  –Š”‡‡ †‹‡•‹‘ƒŽ ‘˜‡‡– ‹• ƒ Š‹‡˜‡† „› ƒ””ƒ‰‹‰ –Š”‡‡ •— Š ’‹‡œ‘• ’‡”’‡†‹ —Žƒ” –‘ ‡ƒ Š ‘–Š‡”Ǥ

(42)  ‘•– ‘†‡”•‡–—’••‘Ǧ ƒŽŽ‡†•‹‰Ž‡–—„‡Ǧ’‹‡œ‘•ȏͷͶȐƒ”‡‡’Ž‘›‡†ǡ•‡‡ˆ‹‰—”‡ͶǤ.  Figure4.Thescanningtunnelingmicroscope:„‹ƒ•˜‘Ž–ƒ‰‡U‹ƒ• ƒ’’Ž‹‡† „‡–™‡‡ –Š‡ ƒ–‘‹ ƒŽŽ› •Šƒ”’ –‹’ ƒ† –Š‡ •—”ˆƒ ‡ ƒŽŽ‘™• ‡Ž‡ –”‘• –‘ –—‡Ž –Š‡ •ƒŽŽ †‹•–ƒ ‡ǡ ”‡ƒ–‹‰ ƒ ’‹ ‘ ƒ’‡”‡ —””‡– IǤ  ˆ‡‡†„ƒ  Ž‘‘’ ƒ†Œ—•–• –Š‡ ’‘•‹–‹‘ ‘ˆ –Š‡ –‹’ ˜‹ƒ ’‹‡œ‘ ‡Ž‡‡–• –‘ ‡‡’ –Š‡ –—‡Ž‹‰ —””‡– ‘•–ƒ–ǡ ™Š‹Ž‡ –Š‡ ’‹‡œ‘ Šƒ‰‡‹•”‡ ‘”†‡†–‘’”‘†— ‡–Š‡•—”ˆƒ ‡‹ƒ‰‡Ǥ Š‡ –—‡Ž‹‰ —””‡– I ‹• —•‡† ƒ• –Š‡ •‡– ’‘‹– •‹‰ƒŽǡ ™Š‹ Š ƒ ˆ‡‡†„ƒ  Ž‘‘’ –”‹‡• –‘ ‡‡’ ‘•–ƒ–Ǥ

(43)  –Š‹• ‘•–ƒ– —””‡– ‘†‡ –™‘ †ƒ–ƒ•‡–• ƒ”‡ ”‡ ‘”†‡††—”‹‰ƒ• ƒ‹‰’”‘ ‡••Ǥ‡—•‡•–Š‡‘˜‡‡–‘ˆ–Š‡œǦ’‹‡œ‘™Š‹Ž‡ • ƒ‹‰ –Š‡ •—”ˆƒ ‡ǡ ’”‘˜‹†‹‰ –Š‡ ƒ‹ ‹ˆ‘”ƒ–‹‘ ƒ„‘—– –Š‡ •—„•–”ƒ–‡Ǥ Š‡ •‡ ‘††ƒ–ƒ•‡–”‡ ‘”†•–Š‡ƒ –—ƒŽ˜ƒŽ—‡•‘ˆ–Š‡‡ƒ•—”‡†–—‡Ž‹‰ —””‡–ƒ•ƒ ‡””‘” •‹‰ƒŽǤ —‡ –‘ –Š‡ ‹‡”–‹ƒ ‘ˆ –Š‡ ˆ‡‡†„ƒ  ‘–”‘Žǡ –Š‹• •‡– ’‘‹– ˜ƒŽ—‡ •–‹ŽŽ ‘–ƒ‹••‘‡‹ˆ‘”ƒ–‹‘ƒ„‘—––Š‡•—„•–”ƒ–‡Ǥ Š‡ ˆ‡‡†„ƒ  Ž‘‘’ ƒ‹• –‘ ‡‡’ –Š‡ –—‡Ž‹‰ —””‡– I ƒ– ƒ Š‘•‡ •‡– ’‘‹–„› ‘””‡ –‹‰–Š‡œǦ’‘•‹–‹‘‘ˆ–Š‡–‹’Ǥ

(44) ‘•– ƒ•‡•ƒ’”‘’‘”–‹‘ƒŽǦ‹–‡‰”ƒŽǦ †‡”‹˜ƒ–‹˜‡ȋ

(45) Ȍ ‘–”‘Ž ‹” —‹–‹•‡’Ž‘›‡†ƒ†Œ—•–‹‰–Š‡œǦ’‹‡œ‘Š‡‹‰Š––‘‡‡’ –Š‡’”‡•‡– —””‡–•‡–’‘‹–ƒ• ‘•–ƒ–ƒ•’‘••‹„Ž‡ǤŠ‡–Š”‡‡ ‘’‘‡–•‘ˆ–Š‡ ˆ‡‡†„ƒ  ’”‘’‘”–‹‘ƒŽǡ ‹–‡‰”ƒŽ ƒ† †‡”‹˜ƒ–‹˜‡ ƒ „‡ ƒ†Œ—•–‡† „› Šƒ‰‹‰ –Š‡ ˜ƒŽ—‡•ˆ‘”–Š‡–Š”‡‡’ƒ”ƒ‡–‡”•KPǡKIƒ†KD‹†‹˜‹†—ƒŽŽ›ǡ•‡‡ˆ‹‰—”‡ͷǤ. ͳͲ.

(46) Chapter3:ScanningTunnelingMicroscopy.  Figure 5. The feedback loop (PID): Š‡ –—‡Ž‹‰ —””‡– •Š‘—Ž† „‡ ‡’– –‘ ƒ •’‡ ‹ˆ‹  •‡– ’‘‹–Ǥ Š‡ ’”‘’‘”–‹‘ƒŽ ‰ƒ‹ P ”‡ƒ –• ’”‘’‘”–‹‘ƒŽ –‘ –Š‡ †‹ˆˆ‡”‡ ‡ „‡–™‡‡ •‡– ’‘‹– ƒ† –—‡Ž‹‰ —””‡–ǤŠ‡‹–‡‰”ƒŽ‰ƒ‹I‹–‡‰”ƒ–‡•–Š‡’ƒ•–†‡˜‹ƒ ‡•ˆ”‘–Š‡•‡– ’‘‹–ǡ™Š‹Ž‡–Š‡†‡”‹˜ƒ–‹˜‡‰ƒ‹D—•‡•–Š‡•Ž‘’‡‘ˆ–Š‡ —””‡– —”˜‡ ™‹–Š”‡•’‡ ––‘–Š‡•‡–’‘‹–Ǥ Š‡’”‘’‘”–‹‘ƒŽ‰ƒ‹—Ž–‹’Ž‹‡•–Š‡ˆƒ –‘”KP–‘–Š‡†‹ˆˆ‡”‡ ‡‘ˆ•‡–’‘‹– ƒ†–Š‡‡ƒ•—”‡†–—‡Ž‹‰ —””‡–ǡ–Š‡‡””‘”•‹‰ƒŽe(t)ǤŠ‡”‡•—Ž–‹‰„‹ƒ•u(t) ‹• ƒ’’Ž‹‡† –‘ –Š‡ œǦ ‘’‘‡– ‘ˆ –Š‡ ’‹‡œ‘Ǧ–—„‡ –‘ ‘—–‡” –Š‡ †‹”‡ –‹‘ ‘ˆ –Š‡ ‡””‘”•‹‰ƒŽǤ ‫ݑ‬ሺ‫ݐ‬ሻ ൌ ‫ܭ‬௉ ή ݁ሺ‫ݐ‬ሻ Š‡‹–‡‰”ƒŽ‰ƒ‹‹–‡‰”ƒ–‡•‘˜‡”’ƒ•–˜ƒŽ—‡•‘ˆ–Š‡‡””‘”•‹‰ƒŽ—Ž–‹’Ž‹‡† „› –Š‡ ˆƒ –‘” KI ”‡•—Ž–‹‰ ‹ ƒ „‹ƒ• ˜‘Ž–ƒ‰‡ǡ ™Š‹ Š ‹• –Š‡ ƒ’’Ž‹‡† –‘ –Š‡ œǦ’‹‡œ‘Ǥ Š‡‹–‡‰”ƒŽ‰ƒ‹”‡†— ‡•‘• ‹ŽŽƒ–‹‘•‘ˆƒ‘˜‡”•Š‘‘–‹‰ˆ‡‡†„ƒ Ǥ ௧. ‫ݑ‬ሺ‫ݐ‬ሻ ൌ ‫ܭ‬ூ න ݁ሺ߬ሻ݀߬ ଴. Š‡ †‡”‹˜ƒ–‹˜‡ ‰ƒ‹ ‹• —•‡† Ž‡•• ‘ˆ–‡ –‘ ‹‹‹œ‡ –Š‡ ‘˜‡”•Š‘‘– ‘ˆ –Š‡ ˆ‡‡†„ƒ  ”‡•’‘•‡Ǥ ‡”‡ǡ –Š‡ ˆƒ –‘” KD ‹• —Ž–‹’Ž‹‡† –‘ –Š‡ †‡”‹˜ƒ–‡ ‘ˆ –Š‡ ‡””‘” •‹‰ƒŽǤ ݀ ‫ݑ‬ሺ‫ݐ‬ሻ ൌ ‫ܭ‬஽ ݁ሺ‫ݐ‬ሻ ݀‫ݐ‬ —”‹‰ ‘ˆˆ –Š‡ ˆ‡‡†„ƒ  Ž‘‘’ ™‹ŽŽ •™‹– Š –Š‡ ‹ ”‘• ‘’‡ –‘ ‘•–ƒ– Š‡‹‰Š–‘†‡Ǥ

(47) –Š‹•‘†‡–Š‡ˆ—ŽŽ‹ˆ‘”ƒ–‹‘‘ˆ–Š‡•—”ˆƒ ‡ ‘””—‰ƒ–‹‘‹•ˆ‘—† ‹–Š‡–—‡Ž‹‰ —””‡–Ǥ

(48) –•—•‡‹•‘Ž›ƒ†˜‹•ƒ„Ž‡‘ˆŽƒ–‘–‹Ž–‡†•—”ˆƒ ‡•Ǥ. ͳͳ.

(49) Ph.D.ThesisCarstenRohr.  Figure6.Scanningmovement:Š‡–‹’—•‡•ƒ”ƒ•–‡”‘˜‡‡––‘ •ƒ’Ž‡–Š‡•—”ˆƒ ‡‘ˆ–Š‡•—„•–”ƒ–‡ǤŠ‹•‘–‹‘”‡•—Ž–•‹ƒˆƒ•–• ƒ †‹”‡ –‹‘ƒŽ‘‰–Š‡šǦƒš‹•ƒ†ƒ•Ž‘™• ƒƒŽ‘‰–Š‡›Ǧƒš‹•Ǥ –›’‹ ƒŽ• ƒ‹‰‘˜‡‡–ˆ‘”ƒˆ‘”™ƒ”†• ƒ‹•‹ŽŽ—•–”ƒ–‡†‹ˆ‹‰—”‡͸Ǥ –‹–‡”˜ƒŽ•‘ˆ‡“—ƒŽ†‹•–ƒ ‡‡ƒ•—”‡‡–˜ƒŽ—‡•ƒ”‡–ƒ‡ǤŠ‡‘˜‡‡––Šƒ– ”‡•—Ž–• ƒŽ‘‰ –Š‡ šǦƒš‹• ‹• ƒŽŽ‡† –Š‡ ˆƒ•– • ƒ †‹”‡ –‹‘ǡ ™Š‡”‡ƒ• –Š‡ ‘˜‡‡– ƒŽ‘‰–Š‡›Ǧƒš‹•‹•–Š‡•Ž‘™• ƒ†‹”‡ –‹‘Ǥ Š‡–‹’”‡ ‘”†•ƒ‹š–—”‡‘ˆ–Š‡•—”ˆƒ ‡‡Ž‡˜ƒ–‹‘ǡ–Š‡‡Ž‡ –”‘‹ Ž‘ ƒŽ †‡•‹–› ‘ˆ •–ƒ–‡• ȋȌ ‡ƒ” –Š‡ ‡”‹ Ž‡˜‡ŽȏͷͷȐǤ

(50) ˆ ‘Ž‡ —Žƒ” ƒ†Žƒ›‡”• ƒ”‡ ‹ƒ‰‡†ǡ ‹– ‹• ‡š’‡ –‡† –Šƒ– ‡Ž‡ –”‘• ƒ –—‡Ž ˆ”‘ –Š‡ Š‹‰Š‡•– ‘ —’‹‡† ‘Ž‡ —Žƒ”‘”„‹–ƒŽ•ȋ •Ȍ‹–‘Ž‘™‡•–—‘ —’‹‡†‘Ž‡ —Žƒ”‘”„‹–ƒŽȋȌ‘ˆ –Š‡ –‹’ǡ ‘” ˜‹ ‡ ˜‡”•ƒ †‡’‡†‹‰ ‘ –Š‡ •‹‰ ‘ˆ –Š‡ ƒ’’Ž‹‡† ˜‘Ž–ƒ‰‡Ǥ Š‡ ‘”„‹–ƒŽ• ‘–”‹„—–‹‰ –‘ –Š‹• ’”‘ ‡•• †‡’‡† ‘ –Š‡ •–”‡‰–Š ‘ˆ –Š‡ ƒ’’Ž‹‡† „‹ƒ• ƒ† ‹–‡‰”ƒ–‡ ƒŽŽ ‘”„‹–ƒŽ• ˆ”‘ –Š‡ ‡”‹ ‡‡”‰› —’ –‘ –Š‡ ƒ’’Ž‹‡† „‹ƒ•ǡ •‡‡ Šƒ’–‡” ͵Ǥ͵Ǥ Š‡‡š–‡†‡†‰‡‘‡–”›‘ˆ–Š‡–‹’‹•ƒŽ™ƒ›• ‘˜‘Ž—–‡†™‹–Š–Š‡‡ƒ•—”‡† •—”ˆƒ ‡ •–”— –—”‡• ”‡•—Ž–‹‰ ‹ „”‘ƒ†‡”  ˆ‡ƒ–—”‡• ™‹–Š‹ ƒ ‡ƒ•—”‡‡– ƒ• –Š‡–‹’’ƒ••‡•ƒ„‘˜‡ƒ ‘””—‰ƒ–‡†•—”ˆƒ ‡ǤŠ‹•‡‡†•–‘„‡‡’–‹‹†ˆ‘”–Š‡ •‹—Žƒ–‹‘‘ˆ‡ƒ•—”‡‡–•ǡ•‡‡ Šƒ’–‡”͸ǤʹǤ ‘˜‹‰ –Š‡ –‹’ –‘ ƒ †‹ˆˆ‡”‡– Ž‘ ƒ–‹‘ ‘ –Š‡ •—„•–”ƒ–‡ ƒŽ•‘ ƒ› ”‡•—Ž– ‹ •‘‡ †‹•–‘”–‹‘ †—”‹‰ –Š‡ ˆ‹”•– ˆ‡™ Ž‹‡• ‘ˆ –Š‡ ‡ƒ•—”‡‡–Ǥ Š‹• ‡ˆˆ‡ – ‹• ”‡ˆ‡””‡†–‘ƒ•’‹‡œ‘ ”‡‡’ǤŠ‡’‹‡œ‘Ǧ‡Ž‡ –”‹ ƒ–‡”‹ƒŽ‡‡†••‘‡–‹‡–‘ƒ†Œ—•– ‹–• †‹‡•‹‘• –‘ ƒ„”—’– Šƒ‰‡• ‹ –Š‡ ƒ’’Ž‹‡† ˜‘Ž–ƒ‰‡Ǥ Š‡ •–”‘‰ ‹Š‘‘‰‡‡‘—• ‡Ž‡ –”‹  ˆ‹‡Ž† „‡–™‡‡ –‹’ ƒ† •—„•–”ƒ–‡ ƒ „‡ —•‡† –‘ ƒ‹’—Žƒ–‡–Š‡•—„•–”ƒ–‡•–”— –—”‡ȏͷ͸ȐǤ ͳʹ.

(51) Chapter3:ScanningTunnelingMicroscopy Š‡ ‡ƒ•—”‡‡–• ‹ –Š‹• –Š‡•‹• ™‡”‡ ƒ†‡ ™‹–Š ƒ ƒ‘• ‘’‡

(52)

(53)

(54)  ‡’Ž‘›‡† ™‹–Š Ž‘™ —””‡– ‘˜‡”–‡”Ǥ Š‡ ‹ƒ‰‡• ™‡”‡ –ƒ‡ ƒ– ƒ„‹‡– ‘†‹–‹‘•Ǥ. 3.2 TunnelTheory ™‘ †‹ˆˆ‡”‡– ‡ˆˆ‡ –• ƒ”‡ ‹’‘”–ƒ– –‘ ’”‘˜‹†‡ ƒ ”‡Ž‹ƒ„Ž‡ –Š‡‘”› ‘ˆ –Š‡ –—‡Ž‹‰ǣ ‹”•–Ž› –Š‡ ‡‡”‰‡ ‡ ‘ˆ ƒ Ž‘ ƒŽ ˜ƒǦ†‡”ǦƒƒŽ• ˆ‘” ‡ǡ •‡ ‘†Ž› –Š‡ ‡š Šƒ‰‡ ‹–‡”ƒ –‹‘ ‹–•‡ŽˆǤ  Š‡ Ž‘•‡ ’”‘š‹‹–› ‘ˆ –‹’ ƒ† •—„•–”ƒ–‡ Ž‡ƒ†• –‘ ƒ †‹•–‘”–‹‘ ‘ˆ –Š‡ —†‹•–—”„‡† ‡Ž‡ –”‘ ™ƒ˜‡ ˆ— –‹‘• ‘ˆ „‘–Š –‹’ ƒ† •—„•–”ƒ–‡Ǥ Š‹• †‹•–‘”–‹‘ ‰‹˜‡• ”‹•‡ –‘ –Š‡ ˜ƒǦ†‡” ƒƒŽ• ˆ‘” ‡Ǥ Š‹• ‘†‹ˆ‹ ƒ–‹‘ ‘ˆ –Š‡ —†‹•–—”„‡† ™ƒ˜‡ ˆ— –‹‘• ™‹ŽŽ „‡ –”‡ƒ–‡† „› ƒ •–ƒ–‹‘ƒ”›Ǧ•–ƒ–‡ ’‡”–—”„ƒ–‹‘ ƒŽ —Žƒ–‹‘ǤŠ‡’”‘ ‡••‘ˆ“—ƒ–—–”ƒ•‹••‹‘‹–Š‡–—‡Ž‹‰’”‘ ‡••‹–•‡Žˆ ƒ „‡ –”‡ƒ–‡† „› –‹‡Ǧ†‡’‡†‡– ’‡”–—”„ƒ–‹‘ –Š‡‘”› ƒˆ–‡” –Š‡ ƒ’’”‘ƒ Š ‘ˆ ƒ”†‡‡ ƒ† ’’‡Š‡‹‡”ȏͷ͹ȐǤ Š‡”‡ ƒ”‡ ‘”‡ •‘’Š‹•–‹ ƒ–‡† ‘†‡Ž‹‰ ƒ’’”‘ƒ Š‡• ƒ˜ƒ‹Žƒ„Ž‡ȏͷͺȐ ȏͷͻȐǡ ™Š‹ Š ‡š’Žƒ‹ ‘”‡ ‘ˆ –Š‡ ‹–”‹ ƒ–‡ ‡ˆˆ‡ –•ȏ͸ͲȐ •‡‡‹‡ƒ•—”‡‡–•‘˜‡”–Š‡›‡ƒ”•Ǥ ‡”•‘ˆˆ ƒ† ƒƒ —•‡† ƒ •‹’Ž‹ˆ‹‡† –‹’ ‰‡‘‡–”› –‘ †‡‘•–”ƒ–‡ –Š‡ ƒ„‹Ž‹–› ‘ˆ –Š‡  –‘ ‡ƒ•—”‡ ƒ •—”ˆƒ ‡ ‘ˆ ‘•–ƒ– †‡•‹–› ‘ˆ •–ƒ–‡• ‡ƒ” –Š‡ ‡”‹Ž‡˜‡Žȏ͸ͳȐǤ ‘™‡˜‡”ˆ‘”ƒƒ†‡“—ƒ–‡‡š’Žƒƒ–‹‘‘ˆ–Š‡ƒ–‘‹ ”‡•‘Ž—–‹‘‘ˆ –Š‡ ǡ –Š‡ †‡• ”‹’–‹‘ ‘ˆ –Š‡ –‹’ ‰‡‘‡–”› Šƒ• –‘ „‡ ‡š’ƒ†‡† –‘ ‹ Ž—†‡ •‘Ǧ ƒŽŽ‡† †ƒ‰Ž‹‰ „‘† •–ƒ–‡• ƒ• Šƒ• „‡‡ •Š‘™ „› Ǥ Ǥ Š‡ȏ͸ʹȐǤ Š‡ ˆ‘ŽŽ‘™‹‰ Šƒ’–‡”• ‘™ ‰‹˜‡ ƒ •–‡’Ǧ„›Ǧ•–‡’ †‡”‹˜ƒ–‹‘ ˆ‘” –Š‡ –—‡Ž‹‰ —””‡– ˆ‘ŽŽ‘™‹‰ –Š‡‡–Š‘†‘ˆ–Š‡‘†‹ˆ‹‡†ƒ”†‡‡’’”‘ƒ ŠǤ ‘ †‡• ”‹„‡ –Š‡ ˜ƒǦ†‡”ǦƒƒŽ• ˆ‘” ‡ ™‹–Š ’‡”–—”„ƒ–‹‘ ƒŽ —Žƒ–‹‘•ǡ ƒ •‡’ƒ”ƒ–‹‘ •—”ˆƒ ‡ ‹• †”ƒ™ „‡–™‡‡ –‹’ ƒ† •—„•–”ƒ–‡ǡ •‡‡ ˆ‹‰—”‡ ͹ƒǤ Š‡ ’‘–‡–‹ƒŽ•†‡• ”‹„‹‰–Š‡–™‘•—„•›•–‡•USƒ†UT,ˆ‘”–Š‡•—„•–”ƒ–‡ȋSȌƒ†–‹’ ȋTȌ”‡•’‡ –‹˜‡Ž›ǡƒ”‡†‡ˆ‹‡†–‘•ƒ–‹•ˆ›–™‘ ‘†‹–‹‘•Ǥ ܷௌ  ൅  ்ܷ  ൌ ܷƒ†ܷௌ ή ்ܷ  ൌ Ͳ Š‡’”‘†— –‘ˆ–Š‡–™‘’‘–‡–‹ƒŽ•‘ˆ–Š‡–™‘•—„•›•–‡•‡“—ƒŽ•œ‡”‘‹–Š‡ ‡–‹”‡•’ƒ ‡ǤŽ›‹–Š‡‹–‡”ƒ –‹‘”‡‰‹‘ǡ‹ Ž‘•‡’”‘š‹‹–›–‘–Š‡ƒ’‡š‘ˆ–Š‡ –‹’ǡ–Š‡’‘–‡–‹ƒŽ„ƒ””‹‡”‹••—„•–ƒ–‹ƒŽŽ›Ž‘™‡”‡†Ǥ—–•‹†‡‘ˆ–Š‹•”‡‰‹‘Š‘™‡˜‡”ǡ –Š‡’‘–‡–‹ƒŽ‡“—ƒŽ•–Š‡”‡ˆ‡”‡ ‡’‘‹–‘ˆ‡‡”‰›ǡ–Š‡˜ƒ ——Ž‡˜‡ŽUǤ Š‡ˆ”‡‡ƒ††‹•–—”„‡†’‘–‡–‹ƒŽ•‘ˆ–Š‡•—„•–”ƒ–‡ǡUS0ƒ†USƒ”‡•Š‘™‹ ˆ‹‰—”‡͹„Ǥ

(55) ˆ–Š‡’‡”–—”„ƒ–‹‘’‘–‡–‹ƒŽVS=US0–US‹•‘™ǡ–‹‡Ǧ‹†‡’‡†‡– ’‡”–—”„ƒ–‹‘–Š‡‘”› ƒ„‡ƒ’’Ž‹‡†–‘†‡”‹˜‡–Š‡’‡”–—”„‡†™ƒ˜‡ˆ— –‹‘•\PǤ

(56)  ’”‹ ‹’Ž‡–Š‘—‰Šǡ–Š‡™ƒ˜‡ˆ— –‹‘•ƒ”‡•‘Ž—–‹‘•‘ˆ–Š‡ Š”Ú†‹‰‡”‡“—ƒ–‹‘ ͳ͵.

(57) Ph.D.ThesisCarstenRohr.  Figure7.Perturbationtheoryatthetipsamplegap:ƒȌ–‘•ƒ– –Š‡ –‹’ ƒ† –Š‡ •ƒ’Ž‡ ‹–‡”ˆƒ ‡Ǥ „Ȍ  ‡‡”‰› • Š‡‡ ‘ˆ –Š‡ –‹’Ǧ •—„•–”ƒ–‡•›•–‡‹••Š‘™Ǥȋ„ȌŠ‡’‘–‡–‹ƒŽ•—”ˆƒ ‡‘ˆ–Š‡ ‘’Ž‡–‡ •›•–‡ǤEFSƒ†EFT”‡ˆ‡”–‘–Š‡ ‡”‹Ž‡˜‡ŽǡEPƒ†EQ–‘–Š‡‡‡”‰› Ž‡˜‡Ž• ‘ˆ •—„•–”ƒ–‡ ƒ† –‹’ǡ ”‡•’‡ –‹˜‡Ž›Ǥ  †‡‘–‡• –Š‡ ’‘–‡–‹ƒŽ ‘ˆ –Š‡ ‘’Ž‡–‡ •›•–‡Ǥ Ǧ†Ȍ †‹•–—”„‡† ƒ† —†‹•–—”„‡† ’‘–‡–‹ƒŽ ‘ˆ •—„•–”ƒ–‡ƒ†–‹’”‡•’‡ –‹˜‡Ž›Ǥ ሺܶ ൅ ܷௌ ሻ߰ఓ ൌ ‫ܧ‬ఓ ߰ఓ. Š‡•ƒ‡‹•–”—‡ˆ‘”–Š‡–‹’Ǥ ሺܶ ൅ ்ܷ ሻ߯ఔ ൌ ‫ܧ‬ఔ ߯ఔ. ‘™‹‰–Š‡‘†‹ˆ‹‡†™ƒ˜‡ˆ— –‹‘• \Pƒ† FQǡ–Š‡–™‘•—„•›•–‡• ƒ ‘ ‡ ƒ‰ƒ‹ „‡ ‘„‹‡† ƒ† –Š‡ –‹‡Ǧ†‡’‡†‡– ‡˜‘Ž—–‹‘ ‘ˆ –Š‡ ‘’Ž‡–‡ •›•–‡„‡‡šƒ‹‡†Ǥ. ͳͶ.

(58) Chapter3:ScanningTunnelingMicroscopy Š‡ –‹‡Ǧ†‡’‡†‡–  Š”Ú†‹‰‡” ‡“—ƒ–‹‘ ‰‹˜‡• –Š‡ ™ƒ˜‡ ˆ— –‹‘ ‘ˆ –Š‡ ‘’Ž‡–‡ •›•–‡Ǥ •‹‰ –‹‡Ǧ†‡’‡†‡– ’‡”–—”„ƒ–‹‘ –Š‡‘”› –Š‡ –”ƒ•‹–‹‘ ’”‘„ƒ„‹Ž‹–› ƒ •—„•‡“—‡–Ž› „‡ †‡–‡”‹‡† ˆ”‘ –Š‡ ‡š’ƒ•‹‘ ‘‡ˆˆ‹ ‹‡–•Ǥ

(59)  ˆ‹”•–Ǧ‘”†‡” ’‡”–—”„ƒ–‹‘ –Š‡‘”› –Š‹• –”ƒ•‹–‹‘ ’”‘„ƒ„‹Ž‹–› ‹• ƒŽ•‘ ‘™ ƒ• ‡”‹ǯ• ‘Ž†‡—Ž‡Ǥ – –Š‡ „‡‰‹‹‰ ‘ˆ –Š‡ ƒŽ —Žƒ–‹‘ ‡ƒ Š •—„•›•–‡ ‹• ‹ ‹–• †‹•–—”„‡† „—– •–ƒ–‹‘ƒ”›•–ƒ–‡ǡƒ•†‡• ”‹„‡†ƒ„‘˜‡Ǥ––Š‡–‹‡tεͲ–Š‡’‡”–—”„ƒ–‹‘’‘–‡–‹ƒŽ ‘ˆ–Š‡–‹’UT‹••™‹– Š‡†‘ƒ†–Š‡•›•–‡ƒ•ƒ™Š‘Ž‡•–ƒ”–•–‘‡˜‘Ž˜‡ˆ‘ŽŽ‘™‹‰ –Š‡–‹‡Ǧ†‡’‡†‡– Š”Ú†‹‰‡”‡“—ƒ–‹‘ ݅԰. ߲Ȳ ൌ ሺܶ ൅ ܷௌ ൅ ்ܷ ሻȲ ߲–. š’ƒ†‹‰–Š‡–‹‡Ǧ†‡’‡†‡–™ƒ˜‡ˆ— –‹‘<‹–‘FQ ௜ாഌ ௧ ԰ . Ȳ ൌ ෍ ܽఔ ሺ‫ݐ‬ሻ߯ఔ ݁ ି ఔ. –tαͲǡ–Š‡•–ƒ–‡‘ˆ–Š‡•›•–‡•–‹ŽŽ•Š‘—Ž†„‡ \Pǡ–Š—•–Š‡‡š’ƒ•‹‘ ‘‡ˆˆ‹ ‹‡–• ™‹ŽŽŠƒ˜‡–‘„‡ ௜ሺாഋ ିாഌ ሻ௧ ԰. ܽఔ ሺ‫ݐ‬ሻ ൌ ൻ߯ఔ ห߰ఓ ൿ݁ ି. ൅ ܿఔ ሺ‫ݐ‬ሻ. —•‹‰ QȋͲȌαͲǤ—„•–‹–—–‹‰aŽ‡ƒ†•–‘–Š‡ˆ‘ŽŽ‘™‹‰ˆ‘”‘ˆ–Š‡™ƒ˜‡ˆ— –‹‘ < ‘ˆ–Š‡ ‘„‹‡†•›•–‡ǣ ௜ாഋ ௧ ԰. Ȳ ൌ ߰ఓ ݁ ି. ௜ாഌ ௧ ԰ . ൅ ෍ ܿఔ ሺ‫ݐ‬ሻ߯ఔ ݁ ି ఔ. Š‡ˆ‹”•––‡”†‡• ”‹„‡•Š‘™ <™‘—Ž†‡˜‘Ž˜‡‹ˆUT™‘—Ž†‘–Šƒ˜‡„‡‡•™‹– Š‡† ‘ǡ–Š‡•‡ ‘†–‡”†‡• ”‹„‡•–Š‡’‡”–—”„ƒ–‹‘‹†— ‡†„›UTǤ •‹‰–Š‹•™ƒ˜‡ˆ— –‹‘ƒ†‡š’ƒ†‹‰„›δFQȁ‰‹˜‡•–Š‡ ‘†‹–‹‘ˆ‘”–Š‡ Qȋ–Ȍǣ ௜ሺாഋ ିாഌ ሻ௧ ԰. ݅԰ܿሶఔ ሺ‫ݐ‬ሻ ൌ ൻ߯ఔ ห்ܷ ห߰ఓ ൿ݁ ି. ௜ሺாഊ ିாഌ ሻ௧ ԰ . ൅ ෍‫߯ۦ‬ఔ ȁܷௌ ȁ߯ఒ ۧܿఒ ሺ‫ݐ‬ሻ݁ ି ఒ. Š‡–”ƒ•‹–‹‘’”‘„ƒ„‹Ž‹–›ˆ”‘ƒ•–ƒ–‡ \P‘ˆ–Š‡•—„•–”ƒ–‡–‘ƒ•–ƒ–‡ FQ‘ˆ–Š‡–‹’ǡ PPQǡ ƒ‘™„‡†‡”‹˜‡†ˆ”‘–Š‡‡š’ƒ•‹‘ ‘‡ˆˆ‹ ‹‡–•cQ(t)ǣ ଶ. ௧. ܲటഋ՜ఞഌ ൌ ܲఓఔ ൌ ቤන ܿሶఔ ሺ‫ݐ‬ሻ݀‫ݐ‬ቤ  ଴. Š‡–”ƒ•‹–‹‘”ƒ–‡ ZPQ‹ˆ‹”•–‘”†‡”’‡”–—”„ƒ–‹‘–Š‡‘”›‹•‰‹˜‡„›ȀWƒ†‹–• ƒŽ —Žƒ–‹‘Ž‡ƒ†•–‘ ‡”‹ǯ• ‘Ž†‡—Ž‡ ሺଵሻ. ߱ߤߥ ൌ ™‹–Š–Š‡–—‡Ž‹‰ƒ–”‹š‡Ž‡‡–. ʹߨ ԰. ห‫ ߥߤܯ‬ห;. ݀ܰ  ݀‫ܧ‬. ͳͷ.

(60) Ph.D.ThesisCarstenRohr ‫ ߥߤܯ‬ൌ ർ߯ߥ ቚܷܶ ቚ߰ߤ ඀ ൌ න ߯‫ ݌ܸ݅ܶ݀ ߤ߰ ܷܶ ߥכ‬ ܸܶ݅‫݌‬. ‘ ƒŽ —Žƒ–‡ –Š‡ –—‡Ž‹‰ —””‡– I ƒŽŽ –Š‡ •–ƒ–‡• ™‹–Š‹ –Š‡ –‹’ ƒ† –Š‡ •—„•–”ƒ–‡ ƒ† –Š‡‹” ‘ —’ƒ–‹‘ ’”‘„ƒ„‹Ž‹–‹‡• Šƒ˜‡ –‘ „‡ —•‡†ǡ ƒ• ™‡ŽŽ ƒ• –Š‡ ‹–‡”’Žƒ›‘ˆ–Š‡•‡•–ƒ–‡•†‡• ”‹„‡†„›–Š‡ƒ–”‹š‡Ž‡‡–MPQǤ ‘”ƒƒ”„‹–”ƒ”›‡‡”‰›Ž‡˜‡Ž Hȋ•‡‡ˆ‹‰—”‡͹Ȍ–Š‡ ‘–”‹„—–‹‘‘ˆ–Š‡•–ƒ–‡• ‘ˆ•—„•–”ƒ–‡ȋȌƒ†–‹’ȋȌ–‘–Š‡–—‡Ž‹‰ —””‡– ‘””‡•’‘†•–‘–Š‡†‡•‹–›‘ˆ •–ƒ–‡• ȋȌ Uǡ ”‡•—Ž–‹‰ ‹ –Š‡ ˆ‘ŽŽ‘™‹‰ ˆƒ –‘”• ߩௌ ሺ‫ܧ‬ிௌ െ ܷ݁ ൅ ߝሻ ƒ† ߩ் ሺ‫ܧ‬ி் ൅ ߝ ሻ™Š‡”‡EFSƒ†EFT†‡‘–‡–Š‡ ‡”‹Ž‡˜‡ŽEF‘ˆ–Š‡•—„•–”ƒ–‡ƒ†–‹’ǡ ”‡•’‡ –‹˜‡Ž›Ǥ‘ˆ‹†ƒ‡š’”‡••‹‘ˆ‘”–Š‡‘ —’ƒ–‹‘’”‘„ƒ„‹Ž‹–‹‡•ǡ–Š‡–—‡Ž‹‰ —””‡– ‹• †‹˜‹†‡† ‹–‘ –™‘ ’ƒ”–•ǣ ȋ‹Ȍ –”ƒ•‹–‹‘ ˆ”‘ ƒ ‘ —’‹‡† •–ƒ–‡ ‘ˆ –Š‡ •—”ˆƒ ‡–‘ƒ—‘ —’‹‡†•–ƒ–‡‘ˆ–Š‡–‹’ƒ†ȋ‹‹Ȍ–”ƒ•‹–‹‘ˆ”‘ƒ‘ —’‹‡†•–ƒ–‡ ‘ˆ–Š‡–‹’–‘ƒ—‘ —’‹‡†•–ƒ–‡‘ˆ–Š‡•—”ˆƒ ‡ǡƒ••Š‘™‹ˆ‹‰—”‡ͺǤ.  Figure8.Thetunnelingcurrent:Š‡ ‡”‹Ž‡˜‡Ž†‹ˆˆ‡”‡ ‡‘ˆ–‹’ ƒ† •ƒ’Ž‡ ’Ž—• –Š‡ ƒ’’Ž‹‡† „‹ƒ• ˜‘Ž–ƒ‰‡ ”‡•—Ž–• ‹ –Š‡ ’‘••‹„Ž‡ –—‡Ž‹‰ —””‡–ǤŠ‡‡‡”‰›‘ˆƒ•–ƒ–‡‹•‡ƒ•—”‡†‹”‡ˆ‡”‡ ‡–‘ –Š‡ ‡”‹Ž‡˜‡ŽEF‘ˆ•—„•–”ƒ–‡ȋȌƒ†–‹’ȋȌǤ–ƒƒ”„‹–”ƒ”›‡‡”‰› Hǡ ‡Ž‡ –”‘• ƒ –—‡Ž ˆ”‘ ƒ ‘ —’‹‡† •–ƒ–‡ ‘ˆ –Š‡ •—„•–”ƒ–‡ ‹–‘ ƒ—‘ —’‹‡†•–ƒ–‡‘ˆ–Š‡–‹’Ǥ‹•–Š‡™‘”ˆ— –‹‘‘ˆ–Š‡•—”ˆƒ ‡Ǥ •‹‰–Š‡ ‡”‹Ǧ‡”‰›ƒ•–Š‡”‡ˆ‡”‡ ‡Ž‡˜‡Žǡ–Š‡‘ —’ƒ–‹‘’”‘„ƒ„‹Ž‹–‹‡•Fˆ‘” ƒ•‡ȋ‹Ȍƒ”‡–Š‡‰‹˜‡„›ǣ ‫ܨ‬՜ ൌ ݂ௌ ሺߝ െ ܷ݁ሻሾͳ െ ்݂ ሺߝሻሿ —•‹‰–Š‡ ‡”‹Ǧ‹”ƒ †‹•–”‹„—–‹‘ ͳ ݂ሺ‫ ܧ‬ሻ ൌ ாିாಷ  ͳ ൅ ݁ ௞் ‘”–Š‡–”ƒ•‹–‹‘‹–Š‡”‡˜‡”•‡†‹”‡ –‹‘–Š‡‘ —’ƒ–‹‘’”‘„ƒ„‹Ž‹–‹‡•ƒ”‡ǣ ‫ܨ‬՚ ൌ ்݂ ሺߝሻሾͳ െ ݂ௌ ሺߝ െ ܷ݁ሻሿ Š‡”‡ˆ‘”‡ǡ ‘„‹‹‰„‘–Š‘ —’ƒ–‹‘’”‘„ƒ„‹Ž‹–‹‡•ǣ ͳ͸.

(61) Chapter3:ScanningTunnelingMicroscopy ‫ܨ‬՜ െ ‫ܨ‬՚ ൌ ݂ௌ ሺߝ െ ܷ݁ሻ െ ்݂ ሺߝሻ Š‹•”‡•—Ž–•‹–Š‡‡š’”‡••‹‘ˆ‘”–Š‡–‘–ƒŽ–—‡Ž‹‰ —””‡–ǣ Ͷߨ݁ ஶ ‫ܫ‬ൌ න ሾ݂ ሺ‫ ܧ‬െ ܷ݁ ൅ ߝ ሻ െ ்݂ ሺ‫ܧ‬ிௌ ൅ ߝ ሻሿ ԰ ିஶ ௌ ிௌ ‫ߩ ڄ‬ௌ ሺ‫ܧ‬ிௌ െ ܷ݁ ൅ ߝ ሻߩ் ሺ‫ܧ‬ிௌ ൅ ߝ ሻȁ‫ܯ‬ȁଶ ݀ߝ Š‡ƒ–”‹š‡Ž‡‡–M†‡’‡†•‡š’‘‡–‹ƒŽŽ›‘–Š‡–‹’Ǧ•—„•–”ƒ–‡†‹•–ƒ ‡Ǥ Š‹• ˆƒ – ‹• ”‡•’‘•‹„Ž‡ ˆ‘” –Š‡ ƒ–‘‹  ”‡•‘Ž—–‹‘ ‘ˆ –Š‡ Ǥ ‹ ‡ ‘Ž› –Š‡ ‘—–‡”‘•– ƒ–‘ ƒ– –Š‡ ƒ’‡š ‘ˆ –Š‡ –‹’ ‘–”‹„—–‡• •‹‰‹ˆ‹ ƒ–Ž› –‘ –Š‡ –—‡Ž‹‰ —””‡–ǡ–Š‡ƒ†Œƒ ‡–ƒ–‘•Ʋ ‘–”‹„—–‹‘‹•‡‰Ž‹‰‹„Ž‡Ǥ Š‡ –—‡Ž‹‰ —””‡– ™‹–Š ƒ •‹’Ž‹ˆ‹‡† –‹’ ‰‡‘‡–”› ȋ•Ǧ™ƒ˜‡ ˆ— –‹‘Ȍ ™ƒ••Š‘™„›‡”•‘ˆˆƒ† ƒƒ‹ͳͻͺ͵ƒ†”‡’”‘†— ‡•ƒ–›’‹ ƒŽ‹ƒ‰‡ ‘ˆ ƒ  ‰‘Ž† •—„•–”ƒ–‡ ƒ’’‹‰ ƒ •—”ˆƒ ‡ ‘ˆ ‘•–ƒ– †‡•‹–› ‘ˆ •–ƒ–‡•ȏ͸ͳȐ. Š‡ •Ǧ ™ƒ˜‡ ƒ’’”‘š‹ƒ–‹‘ ‹• ƒ ‘‘ ‡–Š‘† —•‡† ˆ‘” •‹—Žƒ–‹‘• ‹ƒ‰‡• ‘ˆ • ƒ‹‰–—‡Ž‹‰‹ ”‘• ‘’›ǡ•‡‡ Šƒ’–‡”͸ǤʹǤ‘‡š’Žƒ‹–Š‡ƒ–‘‹ ”‡•‘Ž—–‹‘ ‘ˆ ƒ  ‹ƒ‰‡ ‘‡ ”‡“—‹”‡• ‘”‡ •–ƒ–‡• ‘ˆ –Š‡ –‹’ •—”ˆƒ ‡ –‘ „‡ –ƒ‡ ‹–‘ ƒ ‘—–Ǥ •‹‰ Ž‘ ƒŽ‹œ‡† pœ ƒ† dœ;Ǧ†ƒ‰Ž‹‰ „‘†• Ǥ Ǥ Š‡ †‡”‹˜‡† ƒ ‡š’”‡••‹‘ ˆ‘” –Š‡ –—‡Ž‹‰ —””‡– ‡š’Žƒ‹‹‰ –Š‡ ƒ–‘‹  ”‡•‘Ž—–‹‘ ‘ˆ ƒ ȏ͸ʹȐǤ. 3.3 Tunnelingthroughmolecularadlayers •‹‰ –Š‡ †‡”‹˜‡† ˆ‘”—Žƒ ˆ‘” –Š‡ –—‡Ž‹‰ —””‡– ™‹–Š •‘‡ ƒ••—’–‹‘• ƒ Žƒ”‹ˆ› –Š‡ –—‡Ž‹‰ –Š”‘—‰Š ƒ ‘Ž‡ —Žƒ” ƒ†Žƒ›‡”Ǥ

(62) ‹–‹ƒŽŽ› ƒ••—‹‰ ƒ ‘Ǧ• ƒ‹‰ –‹’ ƒ– ƒ ‡”–ƒ‹ ’‘‹– ƒ„‘˜‡ –Š‡ •—„•–”ƒ–‡ ƒ† —•‹‰ ‡”•‘ˆˆƒ† ƒƒ•ƒ’’”‘š‹ƒ–‹‘ȏ͸ͳȐ‘ˆ–Š‡–—‡Ž‹‰ƒ–”‹š‡Ž‡‡–•„› ʹ݉߶ ȁ‫ܯ‬ȁ; ‫ି ݁ ן‬ଶ఑ௗ ߢ ൌ ඨ  ԰ ™Š‡”‡d‹•–Š‡†‹•–ƒ ‡„‡–™‡‡–‹’ƒ†•ƒ’Ž‡ǡm‹•–Š‡‡Ž‡ –”‘ƒ••ƒ†  –Š‡ ™‘” ˆ— –‹‘ ‘ˆ –‹’ ƒ† •ƒ’Ž‡Ǥ Š‡ ƒ††‹–‹‘ƒŽŽ› ƒ’’”‘š‹ƒ–‹‰ –Š‡ †‡•‹–› ‘ˆ •–ƒ–‡• ‘ˆ –‹’ ƒ† •—„•–”ƒ–‡ „› Š‘‘‰‡‘—•Ž› ˆ‹ŽŽ‡† „ƒ†• —’ –‘ –Š‡ ‡”‹ǦŽ‡˜‡Žǡ–Š‡›„‘–Š ‘–”‹„—–‡‘Ž›ƒˆƒ –‘”–‘–Š‡ —””‡–Ǥ

(63) ˆ‘™ƒ‘Ž‡ —Ž‡‹• ‹–”‘†— ‡† ‹–‘ –Š‡ –—‡Ž‹‰ ‰ƒ’ –Šƒ– Šƒ• ƒ •ƒŽŽ ‹–‡”ƒ –‹‘ ™‹–Š –Š‡ •—”ˆƒ ‡ ƒ† –Š‡ –‹’ǡ ‹–• ‡‡”‰› Ž‡˜‡Ž ™‹ŽŽ ‘™ ‘’‡ —’ ƒ ‡™ –—‡Ž‹‰ Šƒ‡Ž ˆ‘” –Š‡ –—‡Ž‹‰ —””‡–Ǥ ‘”–Š‹• Šƒ‡Ž–Š‡ —””‡–„‡ ‘‡• ߛௌ ߛ் ሾ݂ ሺ‫ ܧ‬െ ܷ݁ ൅ ߝ௜ ሻ െ ்݂ ሺ‫ܧ‬ிௌ ൅ ߝ௜ ሻሿ ‫ି ݁ ן ܫ‬ଶ఑ௗ ෍ ߛௌ ൅ ߛ் ௌ ிௌ ఌ೔. ͳ͹.

(64) Ph.D.ThesisCarstenRohr ™‹–Š†‡‘–‹‰–Š‡ ‘—’Ž‹‰ ‘•–ƒ–•„‡–™‡‡–Š‡–‹’ƒ†–Š‡‘Ž‡ —Žƒ” ‡‡”‰› Ž‡˜‡Ž ƒ† –Š‡ •—„•–”ƒ–‡ ƒ† –Š‡ ‘Ž‡ —Žƒ” ‡‡”‰› Ž‡˜‡ŽǤ ‘” ƒ ‘Ž‡ —Ž‡ ‹–”‘†— ‡† ‹–‘ –Š‡ –—‡Ž‹‰ ‰ƒ’ –Š‡ ‡ˆˆ‡ –‹˜‡ –—‡Ž‹‰ †‹•–ƒ ‡ † ‹• ”‡†— ‡†ǡ ‡Šƒ ‹‰ ‘–”‹„—–‹‘‘ˆ–Š‹• Šƒ‡Žƒ†’‘••‹„Ž›†‘‹ƒ–‹‰–Š‡ —””‡–Ǥ.  Figure 9. Tunneling through molecules: ƒȌ —‡Ž‹‰ ˆ”‘ –Š‡ •—„•–”ƒ–‡ –Š”‘—‰Š ‘‡ ‘”„‹–ƒŽ ȋ‡Ǥ‰Ǥ Ȍ ‘ˆ ƒǡ ˆ”‘ –Š‡ •—”ˆƒ ‡ †‡ ‘—’Ž‡†‘Ž‡ —Ž‡‹–‘–Š‡–‹’™‹–Šƒ’’Ž‹‡†„‹ƒ•˜‘Ž–ƒ‰‡Ǥ„Ȍ–”‘‰ ‘Ž‡ —Ž‡Ǧ•—„•–”ƒ–‡ ‹–‡”ƒ –‹‘• Ž‡ƒ† –‘ ƒ •‡ƒ”‡† ‘—– †‡•‹–› ‘ˆ •–ƒ–‡•ˆ‘”–Š‡–—‡Ž‹‰Ǥ 

(65)  –Š‡ •‹’Ž‡•– ƒ•‡ ‘Ž› ‘‡ ‡‡”‰› Ž‡˜‡Ž ‘ˆ –Š‡ ‘Ž‡ —Ž‡ǡ ‡‹–Š‡” ‹–• Š‹‰Š‡•– ‘ —’‹‡† ‘Ž‡ —Žƒ” ‘”„‹–ƒŽ ȋ Ȍ ‘” ‹–• Ž‘™‡•– —‘ —’‹‡† ‘Ž‡ —Žƒ” ‘”„‹–ƒŽȋȌǡ†‡’‡†‹‰‘–Š‡„‹ƒ•‹•—•‡†ˆ‘”–Š‡–—‡Ž‹‰ǡ•‡‡ˆ‹‰—”‡ͻƒǤŠ‡ ‘”„‹–ƒŽ‡‡†•–‘Ž‹‡„‡–™‡‡–Š‡‡‡”‰›‘ˆ–Š‡–‹’ƒ†–Š‡•—„•–”ƒ–‡ǡ™Š‡ƒ„‹ƒ•‹• ƒ’’Ž‹‡†–‘„‡—•‡†ˆ‘”–—‡Ž‹‰Ǥ

(66) ˆ—Ž–‹’Ž‡‘Ž‡ —Žƒ”‘”„‹–ƒŽ•ˆƒŽŽ‹–‘–Š‹•”‡‰‹‘ ƒŽŽ ‘ˆ –Š‡ ‘–”‹„—–‡ –‘ –Š‡ —””‡–Ǥ

(67)  –Š‡ ƒ•‡ ‘ˆ ƒ •–”‘‰ ‘—’Ž‹‰ „‡–™‡‡ ‘Ž‡ —Ž‡ ƒ† •—„•–”ƒ–‡ǡ ‘ˆ–‡ –Š‡ ƒ•‡ ˆ‘” ‡–ƒŽ •—„•–”ƒ–‡•ǡ –Š‡ ‡‡”‰› Ž‡˜‡Ž• ˆ‘”ƒ‘”‡†‹•–”‹„—–‡† ‘„‹‡††‡•‹–›‘ˆ•–ƒ–‡•‹•–‡ƒ†‘ˆ†‹•–‹ –‘Ž‡ —Žƒ” ‘”„‹–ƒŽ•ǡ •‡‡ ˆ‹‰—”‡ ͻ„Ǥ — Š ƒ †‡ ‘—’Ž‹‰ ƒ „‡ ‡š’‡”‹‡–ƒŽŽ› ƒ Š‹‡˜‡† „› ‡’Ž‘›‹‰ƒ–Š‹‹•—Žƒ–‹‰ƒŽŽƒ›‡”ȏ͸͵Ȑ ‘’ƒ”‡†–‘–Š‡—•‡‘ˆ–Š‡’—”‡‡–ƒŽ •—”ˆƒ ‡ȏ͸ͶȐǤ ‘” ƒ •‹—Žƒ–‹‘ ‘ˆ  ‹ƒ‰‡• –Š‡ –—‡Ž‹‰ —””‡– –Š”‘—‰Š –Š‡ ‡Ž‡ –”‘‹  •–”— –—”‡ ‘ˆ –Š‡ ƒ†•‘”„ƒ–‡Ǧ•—„•–”ƒ–‡ ƒ „‡ ƒŽ —Žƒ–‡†Ǥ Š‡ ˜ƒ”‹‘—• –‡ Š‹“—‡• —•‡ ò ‡Ž ƒ’’”‘š‹ƒ–‹‘• ƒ† ˆ‹”•–Ǧ’”‹ ‹’Ž‡ •‡ŽˆǦ ‘•‹•–‡– ‡–Š‘†•ǡƒ‹Ž›†‡•‹–›ˆ— –‹‘ƒŽ–Š‡‘”›ȋ Ȍȏ͸ͷȐǤ ͳͺ.

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Outline

Size Matters in Ostwald´s Rule of Stages: Multiphase Transformations Caused by Structural Complexity Molecular Jigsaw: Pattern Diversity Encoded by Elementary Geometrical Features Multi-hierarchical assembly via molecular flexibility** Surface control of chirality, orientation and hierarchical assembly of self- self-organized monolayers** A Versatile Fréchet-Dendron Compound Unifi es Host-Guest and Templated Heterogeneous Self-Assembly Wechselwirkungen unter gleichen Bausteinen Wechselwirkungen unter unterschiedlichen programmierten Bausteinen Organic superconductors revisited

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