Density-Functional Methods for Excited States

487 Pages·2016·8.943 MB·English

by  Nicolas Ferré, Michael Filatov, Miquel Huix-Rotllant (eds.)

Topics in Current Chemistry 368
Nicolas Ferré
Michael Filatov
Miquel Huix-Rotllant Editors
Density-
Functional
Methods for
Excited States
368
Topics in Current Chemistry
Editorial Board
H. Bayley, Oxford, UK
K.N. Houk, Los Angeles, CA, USA
G. Hughes, CA, USA
C.A. Hunter, Sheffield, UK
K. Ishihara, Chikusa, Japan
M.J. Krische, Austin, TX, USA
J.-M. Lehn, Strasbourg Cedex, France
R. Luque, C(cid:2)ordoba, Spain
M. Olivucci, Siena, Italy
J.S. Siegel, Tianjin, China
J. Thiem, Hamburg, Germany
M. Venturi, Bologna, Italy
C.-H. Wong, Taipei, Taiwan
H.N.C. Wong, Shatin, Hong Kong
V.W.-W. Yam, Hong Kong, China
S.-L. You, Shanghai, China
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Nicolas Ferre´ • Michael Filatov •
Miquel Huix-Rotllant
Editors
Density-Functional Methods
for Excited States
With contributions by
C. Adamo (cid:2) M. Barbatti (cid:2) K. Bennett (cid:2) M.E. Casida (cid:2)
R. Crespo-Otero (cid:2) C. Daniel (cid:2) M. Filatov (cid:2) K.J.H. Giesbertz (cid:2)
U.DeGiovannini(cid:2)W.Hua(cid:2)M.Huix-Rotllant(cid:2)D.Jacquemin(cid:2)
M. Krykunov (cid:2) A.H. Larsen (cid:2) S. Mukamel (cid:2) A. Nikiforov (cid:2)
Y.C. Park (cid:2) K. Pernal (cid:2) A. Rubio (cid:2) I. Seidu (cid:2) W. Thiel (cid:2)
C.A. Ullrich (cid:2) Z.-h. Yang (cid:2) Y. Zhang (cid:2) T. Ziegler
Editors
NicolasFerre´ MichaelFilatov
InstitutdeChimieRadicalaire Inst.fu¨rPhysikalischeundTheoretischeChemie
Universite´d’Aix-Marseille Universita¨tBonn
Marseille,France Bonn,Germany
MiquelHuix-Rotllant
Institutfu¨rPhysikalischeundTheoretischeChemie
Goethe-Universita¨tFrankfurtamMain
Frankfurt,Germany
ISSN0340-1022 ISSN1436-5049 (electronic)
TopicsinCurrentChemistry
ISBN978-3-319-22080-2 ISBN978-3-319-22081-9 (eBook)
DOI10.1007/978-3-319-22081-9
LibraryofCongressControlNumber:2015947367
SpringerChamHeidelbergNewYorkDordrechtLondon
©SpringerInternationalPublishingSwitzerland2016
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Obituary
It is with great sadness and sorrow that we have learnt about the sudden and
untimelydeathofourcolleague,Prof.Dr.TomZiegler.Tomwasabrightscientist
andoneofthefoundersandpioneersofdensityfunctionaltheory.Tomhasalways
supported and encouraged new developments and always took an active part in
advancing and promoting them. Tom’s recent research on constricted variational
density functional theory holds considerable promise for the field of quantum
theoretical modeling ofexcited electronicstates, andoneof thelatest accountsof
these developments is published in this book. Tom will be sorely missed by his
colleaguesandtheentirecommunityofquantumtheoreticalchemists.
ThiSisaFMBlankPage
Preface
The rapidly expanding use of ultrafast laser spectroscopic methods to study the
photodynamicsofchemicalbondsunderlinestheimportanceofaccuratetheoretical
interpretationandmodelingofexperimentalobservations.Tomatchthisneedthere
wasrecentprogressinthedevelopmentandapplicationofcomputationalmethods
based on density functional theory (DFT) designed to describe the excited elec-
tronicstatesandtherelatedpotentialenergysurfaces(PESs).Thesedevelopments
are especially valuable as DFT methods enable one to study the properties of
excited states and to obtain on-the-fly the relevant dynamical parameters of large
molecular and condensed phase species occurring in natural as well as artificial
photoactive systems. As Kohn–Sham DFT is strictly formulated for ground elec-
tronicstatesonly[1,2],excitedelectronicstatesaretypicallyaccessedthroughthe
use of linear response formalism implemented in time-dependent DFT (TD-DFT)
methodology [3, 4], which currently enjoys a wide popularity among theoretical
photochemists and photophysicists. The widespread use of TD-DFT, however,
revealed certain drawbacks and limitations of the methodology, which are being
constantly addressed through the development of improved computational pro-
tocols, new exchange-correlation density functionals, and conceptually new com-
putational approaches. Besides methodological developments in the domain of
linear response TD-DFT, there is growing activity in the field of development of
alternative time-independent DFT methods as well as the methods going beyond
theparadigmofelectronicdensityandexploringtheworldof(one-electron)density
matrixfunctionals.AlthoughanumberofexcellentreviewsofTD-DFTformalism
canbefoundintheliterature[5–9],therateofnewdevelopmentsseemstooutpace
the rate of review publishing. This book attempts to fill the gap by providing a
collectionofchaptersaddressingthemostrecentdevelopmentsintherealmofDFT
methodologyfortheexcitedelectronicstateswrittenbyleadingexpertsinthefield.
The opening chapter (p. 1) of the book gives a broad perspective on linear
response TD-DFT and its formal connection to many-body theory. By exploring
the latter, the authors expand on the possibilities to ameliorate some well-known
deficienciesofcurrentlyavailableTD-DFTmethodology,especiallywithregardto
treatmentofdouble(and,ingeneral,multiple)excitationsandproperdescriptionof
viii Preface
chemical bond dissociation. The dressed TD-DFT approach and its current and
potential capabilities are discussed in detail. An entirely different approach to
describing excited states in the context of DFT is taken in the following two
chapters, which expand on the use of time-independent methodologies. The
constricted-variational DFT method, presented in the second chapter (p. 61), has
the potential to outperform the currently available linear response TD-DFT when
describing excitations in large conjugated systems or charge transfer excitations,
both of which are notoriously difficult for the standard linear response TD-DFT
formalism. A practically accessible implementation of ensemble DFT formalism,
presentedinthenextchapter(p.97),holdsgreatpromisefortheoreticalmodeling
of non-adiabatic relaxationprocesses of excited electronic states, relevant to pho-
tochemistryandphotovoltaics,andprovidesproperdescriptionofrealandavoided
crossings between the ground and excited electronic states of large molecular
species.Tocomplementthesenewdevelopments,thefourthchapter(p.125)gives
a wide perspective on the general background and practical aspects of a novel
quantumtheoreticalapproachtothegroundandexcitedstatesofelectronicsystems
–densitymatrixfunctionaltheory(DMFT).Althoughayoungermethodologythan
DFT,DMFThasthepotentialtoovertakeitscounterpartoncepracticallyaffordable
functionalsoftheone-bodydensitymatrixbecomeavailable.
Methodologicalaspectsofthetheoreticaldescriptionofexcitedelectronicstates
inthecondensedphaseandopenquantumsystemsintheframeworkofTD-DFTare
amply discussed inthefifthandsixthchaptersofthebook.On p.185Ullrichand
Yang give a comprehensive survey of currently available exchange-correlation
kernelsofTD-DFT,analyzetheirshortcomings,andoutlinepossibleremediesfor
the description of excitonic states in condensed phase systems. A comprehensive
and pedagogical review of theoretical approaches, such as complex scaling and
open boundary conditions, for the description of time-dependent phenomena in
open quantum systems, especially with regard to resonance states photoemission
spectroscopy,isgiveninthechapterbyRubioetal.onp.219.Acontemporaryand
encyclopedic presentation of various approaches for theoretical modeling of
nonlinear core and valence X-ray spectra is presented by Mukamel et al. on
p.273intheseventhchapterofthebook.InthischaptertheuseofDFT/TD-DFT
methodstoaddressthedemandsofnonlinearX-rayspectroscopymeasurementsare
analyzedindepthandtheprospectoftheiruseareoutlined.
Practical aspects of using TD-DFT for computational description of molecular
electronic spectroscopy are reviewed in the chapter by Jacquemin and Adamo on
p. 347. Special emphasis was put on going beyond the vertical excitation approx-
imation in TD-DFT and including vibronic effects for realistic description of 0–0
transitionenergiesinreal-lifemolecularsystems.TheuseofTD-DFTforcompu-
tational modeling of absorption spectroscopy, emission properties, and ultrafast
intersystemcrossingprocessesintransitionmetalcomplexesissurveyedbyDaniel
(p.377)inChap.8,wherespecialattentionispaidtotheinclusionofspin-orbitand
vibroniceffectsinTD-DFTcomputations.TheabilityoftheDFT/TD-DFTframe-
worktoprovideaproperdescriptionofdynamicaleffectsonthespectroscopicand
photochemical properties of molecular species is analyzed in the chapters by
Preface ix
BarbattiandCrespo-OteroandHuix-Rotllantetal.Acomprehensivesurveyofthe
useofDFTandTD-DFTmethodsinthecontextofquasi-classicalsurfacehopping
non-adiabatic molecular dynamics simulations is given in Chap. 10 on p. 415,
wheretheinabilityofthecurrentlinearresponseTD-DFTintheadiabaticapprox-
imation to describe properly the real crossings between the ground and excited
electronic sates, the so-called conical intersections, was identified as the major
causeofspuriouspredictionsforthephotodynamicsofexcitedstates.Thisinability
ofthestandardTD-DFTtodescribetheconicalintersectionswasanalyzedfurther
in the following chapter (p. 445), where approaches represented by the spin-flip
TD-DFTandensembleDFTmethodologieswereproposedasviablealternativeto
theconventionalTD-DFTcalculations.
It is our sincere belief that these chapters, written by renowned experts in
quantum molecular and condensed phase theory and computational spectroscopy,
presentthemostcontemporarystateofaffairsinthefieldofapplicationofdensity
functional theory to the description of excited electronic states and lay down
guidelines for future developments, thus assisting the widespread community of
computational quantum scientists in extending the range of applicability and
improvingthequalityofpredictionsofthisexcitingtheoreticalmethodology.
NicolasFerre´
MichaelFilatov
MiquelHuix-Rotllant
References
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