Non-Linear Optical Properties of Matter: From Molecules to Condensed Phases

680 Pages·2006·8 MB·English

by  Patrick Norman

Non-Linear Optical Properties of Matter
CHALLENGES AND ADVANCES IN
COMPUTATIONAL CHEMISTRY AND PHYSICS
Volume 1
SeriesEditor:
JERZY LESZCZYNSKI
DepartmentofChemistry,JacksonStateUniversity,U.S.A.
Non-Linear Optical
Properties of Matter
From Molecules to Condensed Phases
Edited by
Manthos G. Papadopoulos
NationalHellenicResearchFoundation,Greece
Andrzej J. Sadlej
NicolausCopernicusUniversity,Poland
and
Jerzy Leszczynski
JacksonStateUniversity,USA
AC.I.P.CataloguerecordforthisbookisavailablefromtheLibraryofCongress.
ISBN-101-4020-4849-1(HB)
ISBN-13978-1-4020-4849-4(HB)
ISBN-101-4020-4850-5(e-book)
ISBN-13978-1-4020-4851-3(e-book)
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CONTENTS
Preface ix
Manthos G. Papadopoulos, Jerzy Leszczynski and Andrzej J. Sadlej
Introduction xv
Mark A. Ratner
1. Microscopic Theory of Nonlinear Optics 1
Patrick Norman and Kenneth Ruud
2. Accurate Nonlinear Optical Properties for Small Molecules 51
Ove Christiansen, Sonia Coriani, Jürgen Gauss, Christof Hättig,
Poul Jørgensen, Filip Pawłowski, and Antonio Rizzo
3. Determination of Vibrational Contributions to Linear
and Nonlinear Optical Properties 101
B. Kirtman and J.M. Luis
4. SOS Methods in Calculations of Electronic NLO Properties 129
Wojciech Bartkowiak and Robert Zales´ny
5. Kohn–Sham Time-Dependent Density Functional Theory with
Applications to Linear and Nonlinear Properties 151
Dan Jonsson, Olav Vahtras, Branislav Jansik, Zilvinas Rinkevicius,
Paweł Sałek, and Hans Ågren
6. Non-Linear Pulse Propagation in Many-Photon Active
Isotropic Media 211
A. Baev, S. Polyutov, I. Minkov, F. Gel’mukhanov and H. Ågren
7. Collective and Cooperative Phenomena in Molecular Functional
Materials 251
Anna Painelli and Francesca Terenziani
8. Multiconfigurational Self-Consistent Field-Molecular Mechanics
Response Methods 283
Kurt V. Mikkelsen
v
vi Contents
9. Solvatochromism and Nonlinear Optical Properties of
Donor-Acceptor (cid:2)-Conjugated Molecules 299
Wojciech Bartkowiak
10. Symmetry Based Approach to the Evaluation of Second Order
NLO Properties of Carbon Nanotubes 319
L. De Dominicis and R. Fantoni
11. Atomistic Molecular Modeling of Electric Field Poling
of Nonlinear Optical Polymers 337
Megan R. Leahy-Hoppa, Joseph A. French, Paul D. Cunningham,
and L. Michael Hayden
12. Nonlinear Optical Properties of Chiral Liquids 359
Peer Fischer and Benoît Champagne
13. Recent Progress in Molecular Design of Ionic Second-order
Nonlinear Optical Materials 383
Paresh Chandra Ray
14. Characterization Techniques of Nonlinear Optical Materials 419
Inge Asselberghs, Javier Pérez-Moreno and Koen Clays
15. Third-Order Nonlinear Optical Response of Metal Nanoparticles 461
Bruno Palpant
16. From Dipolar to Octupolar Phthalocyanine Derivatives:
The Example of Subphthalocyanines 509
Christian G. Claessens, Gema de la Torre and Tomás Torres
17. NLO Properties of Metal Alkynyl and Related Complexes 537
Joseph P.L. Morrall, Mark G. Humphrey, Gulliver T. Dalton,
Marie P. Cifuentes and Marek Samoc
18. Ruthenium Complexes as Versatile Chromophores with Large,
Switchable Hyperpolarizabilities 571
Benjamin J. Coe
19. Linear and Nonlinear Optical Properties of Selected
Rotaxanes and Catenanes 609
Jacek Niziol, Kamila Nowicka and Francois Kajzar
Contents vii
20. Second Harmonic Generation from Gold and Silver Nanoparticles
in Liquid Suspensions 645
Jérôme Nappa, Guillaume Revillod, Gaelle Martin, Isabelle
Russier-Antoine, Emmanuel Benichou, Christian Jonin
and Pierre-François Brevet
Index 671
PREFACE
Manyareasofscienceandtechnologyhavebenefitedfromthetremendousadvance
in computational techniques over the last two decades. In a number of cases theo-
reticalpredictionshavedirectlyimpactedthedesignofnewandimprovedmaterials
withuniquecharacteristics.Anunderstandingofthedetailsofmolecularstructures
andtheirrelationshipwiththedesiredpropertiesofsuchmaterialshasalwaysbeen
a key factor for successful interplay between theory and experiment. Among such
important characteristics are the non-linear optical (NLO) properties of matter.
ThereiscurrentlyanimmenseinterestinNLOpropertiesofmaterials,sincethey
provide valuable information about important aspects of matter. For example, they
are related to electronic and vibrational structures as well as to intra- and inter-
molecular interactions. On the other hand, NLO properties are of great practical
importance for the design of materials and devices, which have numerous and
important applications (e.g. optical devices for the transfer and storage of data).
Taking into account the widespread interest in the NLO properties/materials and
the rapid progress of both the scientific and technological aspects of this field, we
believe that it is timely and useful to select some topics of particular interest (this
issubjective,ofcourse)andinviteleadingexpertstoreviewcurrentprogress.This
idea underlies the composition of the present volume. Obviously, the selection of
topics was strongly influenced by our research interests. They may not cover all
important areas of chemistry and physics of the NLO systems. However, in spite
of the possible deficiencies, we believe that the reviews presented here cover a
relativelywideclassofproblemsandwillbeofinterestforresearchersandstudents
in this area. Particular care was taken to impartially address both theoreticians and
experimentalists to increase the extent of the mutual interaction between them.
ThisbookstartswithanintroductionwrittenbyM.A.Ratnerandthenthereisan
openingchapterthatintroducesreaderstothetheoryoflinearandNLOproperties.
Norman and Ruud review the basic physical processes and their connection with
theformulasderivedfromtime-dependentperturbationtheory.Theybrieflydiscuss
the vibrational properties as well as the connection between the microscopic and
macroscopic NLO properties.
Christiansen et al. review the coupled cluster (CC) response methods for the
calculation of the electronic contributions to first and second hyperpolarizabilities
and some magneto-optic NLO properties. The latter include the magneto-optical
activity (Faraday effect, magneto-circular dichroism), Buckingham and Cotton–
MoutoneffectsaswellasJonesandmagneto-electricbirefringence.Theydiscussed
thebasissetconvergenceforthepropertiesofinterestaswellastheconvergenceof
thepropertieswiththewavefunctionmodel.Christiansenetal.comparetheoretical
ix
x Preface
with experimental results and show that the CC approaches, connected with the
hierarchy of correlation-consistent basis sets, can lead to very accurate results for
smallmolecules.Theyalsopointoutsomeofthepresentchallengesfortheaccurate
calculationofthepropertiesofinterest(e.g.computationofNLOpropertiesofopen
shell molecules).
Kirtman and Luis review some of the theoretical/computational methods which
have been proposed over the past fifteen years for the calculation of vibrational
contributionstothelinearandNLOproperties.Theydiscuss:(i)thetime-dependent
sum-over-statesperturbationtheoryandthealternativenuclearrelaxation/curvature
approach, (ii) the static field-induced vibrational coordinates which reduce the
number of nth-order derivatives to be evaluated, (iii) the convergence behavior of
the perturbation series, (iv) an approach to treat large amplitude (low frequency)
vibrations, (v) the effect of the basis set and electron correlation on the vibrational
properties,and(vi)techniquestocomputethelinearandNLOpropertiesofinfinite
polymers.
BartkowiakandZales´nydiscussthesum-over-states(SOS)methodwhichisused
for the calculation of NLO properties (electronic contribution) and multi-photon
absorption. They comment on the various approximations, including the widely
usedfew-statesmodels,andtheexactsum-over-statesformulas.Theyshowthatone
of the main advantages of the many variants of this approach is the interpretation
oftheNLOpropertiesintermsofcontributionsfromexcitedstates.Theycomment
on the limited utility of the SOS technique for small molecules, aggregates and
clusters, but they point out, that it is still a very attractive tool for large molecules.
Jonsson et al. review the Kohn-Sham density functional theory (DFT) for time-
dependent (TD) response functions. They describe the derivation of the working
expressions.TheyalsoreviewrecentprogressintheapplicationofTD-DFTtoopen
shell systems. They reported results on several properties: (i) hyperpolarizabilities
(e.g. para-nitroaniline, benzene, C fullerene), (ii) excited state polarizabilities
60
(e.g. pyrimidine), (iii) three-photon absorption and (iv) EPR spin Hamiltonian
parameters.
Baev et al. review a theoretical framework which can be useful for simulations,
design and characterization of multi-photon absorption-based materials which are
usefulforopticalapplications.Thismethodologyinvolvesquantumchemistrytech-
niques, for the computation of electronic properties and cross-sections, as well
as classical Maxwell’s theory in order to study the interaction of electromagnetic
fields with matter and the related properties. The authors note that their dynamical
method, which is based on the density matrix formalism, can be useful for both
fundamental and applied problems of non-linear optics (e.g. self-focusing, white
light generation etc).
Painelli and Terenziani discuss the cooperative and collective behavior resulting
from classical electrostatic intermolecular interactions in molecular materials with
negligible intermolecular overlap. The simple model they employ for clusters of
push-pullchromophoresneglectsintermolecularoverlapanddescribesthemusinga
two-state model. They comment on the excitonic approximation which is expected
Preface xi
to work well for clusters of molecules with low polarizability. These authors
reviewed the mean-field approximation, which has been introduced for the calcu-
lation of the polarizability of molecular crystals and films. Painelli and Terenziani
describe: (i) the optical susceptibilities of some representative clusters and (ii) the
excited states in a cluster of polar and polarizable molecules.
Mikkelsen reviews recent advances of the MCSCF/MM method. This approach
hasbeendevelopedinordertoobtainfrequency-dependentmolecularpropertiesfor
a solute perturbed by solvent interactions. He defines the Hamiltonian for the total
system. It involves three components: the first describes the quantum mechanical
(QM)system,thesecond,theclassical(MM)systemandthethirdtheirinteraction.
He describes the energy functional, the MCSCF wave function and the linear and
quadratic response functions.
Bartkowiak reviewed the connection between the NLO response and solva-
tochromic behavior of donor-acceptor (cid:2)-conjugated molecules. The marked NLO
propertiesofthesemoleculesareassociatedwithanintra-molecularcharge-transfer
excited state. This author points out that the environmental interactions may have
a very significant effect on the hyperpolarizabilities (they may even lead to a
change of sign). Bartkowiak shows that a simple two-state model combined with
the solvatochromic methods may allow the prediction of changes of in molecular
hyperpolarizabilities as a function of the solvent polarity.
Dominicis and Fantoni present a method for the computation of the electronic
first hyperpolarizability of chiral carbon nano-tubes (CNTs). The CNT eigenstates
are computed by an algorithm reported by Damnjanovic et al. They discuss the
symmetry properties of CNTs and selection rules for electronic transitions and
demonstrate that the use of symmetry reveals the state-to-state transitions, which
contributetothefirsthyperpolarizabilityofCNTs.Thelatterisrelatedtoparticular
state-to-state transitions. The principles for predicting the magnitude of the first
hyperpolarizability and its relation to the topology of CNTs are also discussed.
Leahy-Hoppaetal.reviewtheresultsforanelectricfield-poledguest-hostNLO
polymersystem,computedbyusingMonteCarloandatomisticmoleculardynamics
simulations.Theydiscusstheworkofthegroupsinvestigatingthistopic.TheMonte
Carlostudiesprovideresultsingoodagreementwithexperimentaldataandvaluable
information concerning the optimal loading concentration for a chromophore of
a given shape and dipole moment. The findings of the teams, which have used
molecular dynamics are also described. The alignment of dopants is studied by
employing<cos(cid:3)>and<cos3(cid:3)>.Leahy-Hoppaetal.notedthattheorientational
order in the system is strongly dependent on the strength of the poling field.
Fischer and Champagne present an overview of linear and nonlinear optical
properties of chiral molecules in isotropic media. The authors state the general
symmetry requirements of chiroptical processes, and show that nonlinear
chiralspectroscopiescanarisewithintheelectricdipoleapproximation.Theauthors
describe sum-frequency–generation experiments at second order and demonstrate
how nonlinear optics can be used to determine the absolute conformation of a
chiralmoleculeinsolution.Thisisdiscussedwithrecoursetoelectric-fieldinduced