Photoinduced processes at surfaces and in nanomaterials

280 Pages·2015·6.382 MB·English

by  Kilin, Dmitri

Photoinduced Processes at
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In Photoinduced Processes at Surfaces and in Nanomaterials; Kilin;
ACS Symposium Series; American Chemical Society: Washington, DC, 2015.
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In Photoinduced Processes at Surfaces and in Nanomaterials; Kilin;
ACS Symposium Series; American Chemical Society: Washington, DC, 2015.
1196
ACS SYMPOSIUM SERIES
Photoinduced Processes at
Surfaces and in Nanomaterials
Dmitri Kilin, Editor
1 North Dakota State University
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AmericanChemicalSociety,Washington,DC
DistributedinprintbyOxfordUniversityPress
In Photoinduced Processes at Surfaces and in Nanomaterials; Kilin;
ACS Symposium Series; American Chemical Society: Washington, DC, 2015.
LibraryofCongressCataloging-in-PublicationData
Photoinducedprocessesatsurfacesandinnanomaterials/DmitriKilin,editor,
NorthDakotaStateUniversity,Fargo,NorthDakota,andUniversityofSouthDakota,
1
0 Vermillion,SouthDakota;sponsoredbytheACSDivisionofComputersinChemistry.
0
w pagescm.-- (ACSsymposiumseries;1196)
96.f Includesbibliographicalreferencesandindex.
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1 ISBN978-0-8412-3094-1(alk.paper)--ISBN978-0-8412-3093-4(alk.paper)
15- 1. Photochemistry.2. Photovoltaicpowergeneration.3. Electrochemistry.4. Surface
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2 chemistry.5. Nanostructuredmaterials. I.Kilin,Dmitri,editor.II.AmericanChemical
k-
b Society.DivisionofComputersinChemistry.
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2 QD708.2.P482015
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0.1 660′.295--dc23
oi: 1 2015036678
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ber ThepaperusedinthispublicationmeetstheminimumrequirementsofAmericanNational
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In Photoinduced Processes at Surfaces and in Nanomaterials; Kilin;
ACS Symposium Series; American Chemical Society: Washington, DC, 2015.
Foreword
The ACS Symposium Series was first published in 1974 to provide a
mechanism for publishing symposia quickly in book form. The purpose of
the series is to publish timely, comprehensive books developed from the ACS
sponsoredsymposiabasedoncurrentscientificresearch. Occasionally,booksare
01 developed from symposia sponsored by other organizations when the topic is of
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In Photoinduced Processes at Surfaces and in Nanomaterials; Kilin;
ACS Symposium Series; American Chemical Society: Washington, DC, 2015.
Preface
ThisACSBookpresentsstudiesofphotoinducedprocessesinnanomaterials
thatfallintothecategoryofbasicresearchcontributingtosolarenergyconversion.
The book focuses on photophysical and photochemical processes at surfaces of
semiconductor nanostructures that are related to photovoltaic and photocatalytic
1 applications with a broader focus on time-resolved spectroscopic monitoring of
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0
pr relatedprocessesinphotoactivematerials. Changesofthecomposition,quantum
6.
9 confinement, size, shape, surface functionalization, doping, and relative spatial
1
1
5- arrangementsofnanocrystals,aswellastheformationofsemiconductor-to-metal
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20 nano-interfaces,tunethetimescalesoftherelevantbasicprocessesandproperties
bk- ofthematerials. Thebookreportsshort,up-to-datereviews,recentexperimental
1/
2 data, and computational results that all contribute to an atomistic description of
0
1
0. electronicdynamicsandchargetransferinducedbyopticalexcitationsandlattice
1
oi: vibrations. Basicprocesses—suchaslightabsorption,formationandevolution
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5 | ofchargetransferexcitations,hotcarrierrelaxation,andreactiondynamics—all
01 areperturbedbytheenvironmentalfactors,suchaslatticevibrationsandsolvent
2
6, polarization,andaretreatedwithdifferentimplementationsofthe"opensystem"
1
er approach. Themergingofexperimentalandcomputationalapproachesallowsfor
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cto aholisticandcoordinatedefforttointerpret,guide,andoptimizetheefficiencyof
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b): photocatalyticandphotovoltaicprocesses.
e Chapters cover the tuning of optoelectronic properties of nanomaterials
W
e ( for energy application via the broad modification of morphological variables.
Dat Properties of nanostructures are tuned by varying their dimensionality from
on zero-dimensional quantum dots (Chapters 5 and 12) and one-dimensional
cati nanorods (Chapter 10) to two-dimensional thin films (Chapters 2, 6, and 7)
Publi and mesoporous materials (Chapter 3). Additional tune-ability is achieved via
sensitization by dyes (Chapters 1, 8, and 12), doping (Chapters 1, 5, 6, and 9),
or deposition of metal clusters on semiconductor surfaces (Chapters 7 and 11).
Althoughthemainfocusofthereportedresearchisbasicscience,severalchapters
report noticeable advances in dye-sensitized solar cells (Chapters 1 and 8),
semiconductor-basedphotovoltaics(Chapters7, 9, and10), sensingapplications
(Chapter 6), pharmaceutical applications (Chapter 12), and conversion of solar
energy to chemical energy in a broad variety of photoelectrochemical cells for
photocatalysis and water splitting (Chapters 3, 4, and 11). The contributions
come from both an experimental community (Chapters 1, 3, 4, and 12) and a
communityofresearchersdealingwithcomputingelectronicstructure(Chapters
2, 5, and 6), nonadiabatic dynamics of excited states (Chapters 7, 8, 9, and 10),
andmodelingchemicalreactiondynamics(Chapter11).
ix
In Photoinduced Processes at Surfaces and in Nanomaterials; Kilin;
ACS Symposium Series; American Chemical Society: Washington, DC, 2015.
1. King, Kern, and Parkinson (Chapter 1, Sensitization of Single Crystal
Substrates) provide a starting point and a “system of coordinates” for
other chapters dealing with the sensitization of single crystal wide-gap
singlecrystalsemiconductorsurfacesbydyes,polymers,quantumdots,
anddoping(Chapters2,3,4,and8).
2. Giorgi and Yamashita (Chapter 2, Electronic and Optical Properties of
Low-Dimensional TiO : From Minority Surfaces to Nanocomposites)
2
focus on the confinement effect for ultra-thin titania films and their
functionalization by graphene, as explored by electronic structure
computationsthatrevealtheexcitonicnatureoftheiropticalspectra.
3. Mahoney, Rasalingam, and Koodali (Chapter 3, Dye-sensitized
and Doped TiO Mesoporous Materials for Visible Light Induced
2
PhotocatalyticHydrogenEvolution)provideanoverviewofthebenefits
1
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0 of doped mesoporous materials for visible light-induced photocatalytic
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6. hydrogen production: Sensitization of wide-gap semiconductors such
9
1
1 as titania with dyes, quantum dots and doping by transition metals
5-
1 extends the response to visible light, while mesoporous morphology
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2
k- provides high surface-to-volume ratio, which collectively contributes
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1/ to the efficiency of photocatalytic processes. This complements other
2
0
1 chapters dealing with the effects of the confinement, morphology, and
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doi: 1 s2e,nasnitdiz4a)tiaonndoofpneannsomaactaelrlifaolsrftohrescoolmarpeunteartigoynaalppmliocdaetiloinngso(Cfhhaypdtreorgse1n,
15 | evolution(Chapter11).
0
6, 2 4. Pillai et al. (Chapter 4, Single Site Metal Ions on the Surface of TiO2
er 1 Nanorods: A Platform for Theoretical and Experimental Investigation)
b summarizethesyntheticprotocolsforcontrolleddepositionoftransition
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Oct metals on the surface of titania nanostructures and outline possible
b): ways to characterize those nanomaterials for solar energy utilization,
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ate ( 5. Proshchenko and Dahnovski (Chapter 5, Transition Metal Doped
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n SemiconductorQuantumDots:TunableEmission)examinethemodeling
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ati of transition metal doping in semiconductor quantum dots, covering
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bli the impact of crystal field splitting and many-electron effects onto the
Pu absorptionandluminescenceofsuchmodels.

6. Inerbaev et al. (Chapter 6, Theoretical Modeling of Oxygen and Water
Adsorptionon Indium Oxide (111) Surface) address the control of the
opticalpropertiesofanindiumoxidethinfilmbythesurfaceadsorption
ofoxygenatdifferentairhumidityforsensorapplications.
7. Micha (Chapter 7, Density Matrix Treatment of Optical Properties in
PhotovoltaicMaterials: PhotoconductivityataSemiconductorSurface)
focuses on metal clusters deposited on silicon surfaces. An overview
ofthepracticalimplementationsofthemethodstodescribethelight-to-
matterinteraction,whicharebasedondensityoperatortechniques,paves
thewaytopredictandinterpretkeyobservablesinsuchnanostructures:
photovoltagespectra,photocurrent,andphotoconductivity. Thischapter
is closely connected to three subsequent chapters (Chapters 8, 9, and
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In Photoinduced Processes at Surfaces and in Nanomaterials; Kilin;
ACS Symposium Series; American Chemical Society: Washington, DC, 2015.
10),whichfocusonperturbationsbylight,solvent,substrate,andlattice
vibrationsontotheevolutionofexcitedstates.
8. Bowman, Chan, and Jakubikova (Chapter 8, Investigating Interfacial
Electron Transfer in Highly Efficient Porphyrin-Sensitized Solar Cells)
explore the way in which electron transfer in dye-sensitized titania
depends on the details of the anchoring group composition, the surface
adsorption, and the binding pattern. This chapter provides an excellent
companion to experimental chapters as well as an overview of one of
thefirstpracticalmethodsfortheatomisticmodelingofelectrontransfer
thatisbasedonthesurvivalprobabilityconcept.
9. Akimov and Prezhdo (Chapter 9, Nonradiative Relaxation of Charge
Carriers in GaN-InN Alloys: Insights from Nonadiabatic Molecular
Dynamics)provideanoverviewofhotcarrierrelaxationinindium-doped
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0 gallium nitride — a promising material for solar energy conversion.
pr
6. The authors review a commonly used method for atomistic modeling
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1 ofrelaxationbasedonTully’ssurface-hoppingalgorithmandon-the-fly
5-
1 coupling along molecular dynamics trajectory. Prezhdo and Akimov
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k- highlighttheimportanceofaccountingforquantumdecoherenceeffects,
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1/ which are responsible for the precision of the computed rates of carrier
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1 relaxation.
0.
doi: 1 10. RKerlyajxeavtsikoin(CinhapNtaerno1p0a,rTtiocwleasr)dfFoicrusst-epsrionnciptlhees Ddeessccrriippttiioonn ooffCcaarrrriieerr
15 | relaxation due to phonon emission in semiconductor nanostructures,
0
6, 2 which is an important process in photo-excited nanostructures and is
er 1 potentiallyrelevanttophotovoltaics. Thechapterdiscussesanalternative
b to the on-the-fly procedure for computing electron–phonon interaction.
o
Oct Here, the electron–phonon interactions are treated perturbatively using
b): the Keldysh technique, or non-equilibrium Green’s function, including
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ate ( couplingsaregivenbyderivativesoftheelectron–ioninteractionalong
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n eachnormalmodeoflatticevibrations.
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ati 11. Meng (Chapter 11, Optical, Electronic and Catalytic Properties of
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bli Metal Nanoclusters by ab initio Molecular Dynamics Simulation: A
Pu Mini Review) covers two classes of photoinduced processes related

to metal nanoparticles: their ability to catalyze chemical reactions
and their influence on excited state relaxation. These two classes of
processesrelatetothedynamicsofinter-atomicdistancesformolecules
adsorbed at metal cluster and to the dynamics of electronic excited
states, respectively. In the first half of the chapter, Meng provides
computational predictions of the efficiency of proton reduction and
hydrogen evolution at the surface of metal and bimetal clusters, thus
makingconnectionstotheexperimentalchapteronhydrogengeneration
(Chapter3). Inthesecondpartofthechapter,Mengaddressesthedetails
of electronic excited state dynamics in metal clusters by combining the
reduceddensityoperatormethod,similartotheonedescribedinChapter
7 by Micha, and the on-the-fly procedure for nonadiabatic coupling,
similar to the one used in Chapter 9 by Prezhdo and Akimov. The
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In Photoinduced Processes at Surfaces and in Nanomaterials; Kilin;
ACS Symposium Series; American Chemical Society: Washington, DC, 2015.
reported methodology paves the way to compute such nonequilibrium
observablesasphotoluminescencespectra.
12. ZenkevichandvonBorczyskowski(Chapter12,SurfacePhotochemistry
of “Quantum Dot – Porphyrin” Nanoassemblies: Exciton Relaxation
Pathways and Singlet Oxygen Generation Generation) provide
experimentaltime-resolveddataonenergytransferandelectrontransfer
at the interface of semiconductor quantum dot and a sensitizing dye
molecule. A range of time-resolved spectoscopical techniques allows
for the coexistence of several pathways of photoexcitation to be
identified: charge transfer, resonant energy transfer, and multi-electron
Auger processes, thus providing new opportunities for the quantitative
comparisonofcomputationalandexperimentalapproaches.
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0 In summary, complementary reviews on a broad variety of physical and
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6. chemical processes in functional nanostructures are presented to recognize
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1 recent achievements and to help explore open problems in order to coordinate
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doi: 1 DDmepiatrrtimKeniltinofChemistry
15 | UniversityofSouthDakota
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In Photoinduced Processes at Surfaces and in Nanomaterials; Kilin;
ACS Symposium Series; American Chemical Society: Washington, DC, 2015.
Editor’s Biography
Dmitri Kilin
Dmitri Kilin is an assistant professor of computational chemistry at USD
(University of South Dakota). Dr. Kilin has over ten years’ experience in
modeling of excited state dynamics in photoactive nanomaterials, including
01 interfacialchargetransferandreactiondynamicsandsurfacereactionsatcatalytic
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ot sites and interfaces of metal and semiconductor nanomaterials for photovoltaic
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19 and photocatalytic solar energy conversion. Dr. Kilin has published over 50
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5- peer-reviewed publications in the area of electron dynamics. Recently, he has
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2 organizedandco-organizedseveralsymposiaattheAmericanChemicalSociety
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02 DmitriKilincompletedhisundergraduate(1994)andmastersdegrees(1996)
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0. inPhysicsfromBelarusStateUniversity(Minsk,Belarus)andreceivedadoctoral
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oi: degree from the Chemnitz University of Technology (Chemnitz, Germany) in
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0 Jeff Cina at the University of Oregon, Prof. Oleg Prezhdo at the University of
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6, Washington, and Prof. David Micha at the University of Florida, he joined the
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er DepartmentofChemistryattheUniversityofSouthDakotaasfaculty. Hiscurrent
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b): of charge transfer, nonradiative charge carrier relaxation, and surface reactions
We at catalytic sites and interfaces of metal and semiconductor nanomaterials for
e ( photovoltaicandphotocatalyticsolarenergyconversion.
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©2015AmericanChemicalSociety
In Photoinduced Processes at Surfaces and in Nanomaterials; Kilin;
ACS Symposium Series; American Chemical Society: Washington, DC, 2015.