ELSEVIER Synth&M&ls84(1997)945-946

Third-order Nonlinear Optical Properties of Conjugated Molecules by Coherent Raman Scattering

K.J.Atherton, G.P.Keogh,andG.Rumbles.
Departmentof Chemistry,ImperialCollegeof Science,TechnologyandMedicine, Exhibition Road,
London,SW72AY, UK

Abstract

We have studiedCoherentAnti-Stokes RamanSpectra(CARS) of trans.-B-carotene in chloroformsolutionat variousconcentrations.

We have determinedthe nonresonantmolecularthird-ordernonlinearoptical responseof this conjugatedmoleculein chloroformto be
~(-59lnm,65Omn,-721.4nm,65Onm)= (13W)x10”3esu.

Keywords:Nonlinearopticalmethods;Conjugatedmolecules;CoherentRamanscattering

1. Introduction 3. Results and Analysis

Conjugatedmolecules and polymers exhibit large third- CARS spectraof &ins-~-carotenein chloroform at three
order nonlinearoptical propertiesdue to their delocalizedx- different concentrationsare shown in figure 1. The pump
electron backbone. In order to use synthesis to develop wavelengthwas650~1 andthe 1524cm-’Ramanbandhasbeen
molecular third-order materials with sufficiently high studied. The absorption maximum for trans-p-carotenein
responses for deviceapplicationsit is necessaryto have a clear chloroformis at 46Onmwith the O-Otransitionat 487nm.
understandingof the microscopicorigin of the nonlinearity and The coherent Raman data has been analysedusing the
thereforethe structure-propertyrelationship. following expressionfor CARS spectrallineshape5,6
Coherent Anti-Stokes Raman Spectroscopy of dilute
solutions with concentration studies can elucidate the
microscopicnonlinearity of moleculesin the absenceof any = x’, + D: + L; +2x,Dt + R2 +I2
orderingeffects. This techniqueis sensitiveto resonancewith S2+lY2
rg
electronicone and two photon allowed statesin the medium. (1)
Therefore by variation of the electronic resonanceconditions + 2WcnrR+DtR+W) _ 2Irg(IXm+Q-LtR)
whilst probing a single Ramanresonance,it is possibleto 82+r2rg g2+r2rg
quantify the variouscontributionsto the nonlinearityandisolate
the intrinsic responseof the materialunder study. This allows
different chemical systemsto be meaningfully compared. which canbe simplifiedto
CoherentRamanmay give complimentaryinformationto other
third-ordertechniquesdueto the different resonances probed. 2 =A+B+- 2&C
We have studiedtrans+carotene, a conjugatedmolecule (2)
82+r2 Tg 62 +Irg2
with elevendoublebonds,which hasbeenstudiedin the past
due its relatively high third-order nonlinearity and the interest where
in using a simple polyene as a molecule for theoretical
modelling.A variety of techniqueshavebeenusedpreviouslyto
studythis molecule.1-4

2. Experimental B = -2TrgIxnr + R2 + I2 + 2TrgL,R - 2TrglDt

The coherentRamanspectrometerusedtwo high repetition

rate, picosecond
dye lasersin a crossbeamgeometry.Variation
in the intensities of the pump and Stokes beams were
eliminatedusing a two compartmentspinningcell containing The termshere are all macroscopic,as is the nature of third-
the sampleand &dmso as a nonresonantreference.The full order nonlinear measurements.& is the non-resonant
detailshave beenpublishedelsewhere.’ backgroundterm due to the solvent, assumedhere to have no

0379-6779/971$17.008 1997ElsevimScienceS.kAUrightsreserved
PII SO379-6779(96)04223-3
946 KJ. Atherton et al. /Synthetic
one or two-photon resonance at these wavelengths. Dt and LI are
the real and imaginary parts of the two-photon term for the
sample. The real and imaginary parts of the Raman resonant
contribution are R and I with S being the dettming from exact
Raman resonance and Irg the damping constant obtained from
the HWHM for the Raman transition. This term can be fixed by
using the spontaneous Raman linewidth that we have measured
previously.
In equation (2) the initial term is a background term, which
would be expected to be constant. The second term consists of
two Lorentzians, a Raman resonant contribution which becomes
dominant at high concentration and a cross-term that can add or
subtract to the spectrum, depending upon the sign of I and
becoming important where one-photon resonance occurs. The
third term is a dispersive cross-term, increasing in importance
as the concentration decreases as can be seen in figure 1.
26 L’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ‘-I
24
22
20
420 1440 1460 1480 IS00 1520 1540 1560 1580 1600
Ramat?
%ifi / cm”
Fig 1. CARS spectraof tmm$carotene in chloroformat
difIerent concentrations
(i) lO%I, (ii) 5x10%, (iii) 10%
The CARS spectrahave been fitted to this equationto
extract A, B and C rather than the actual macroscopicterms
directly becauseof the high degreeof correlationbetweenthese
terms,By scanninga concentrationseriesfor the sameRaman
resonancethe concentrationdependence of A, B and C can be
determined.The Lorentz localfield correctionfactor
xc3)= Nf‘+)
canbe usedto considerA, B andC in termsof the microscopic
nonlinerities and with the concentration dependencethe
moleculartermscan be elucidated.The refractive index at the
pumpwavelengthwastaken asthat of the solvent.7By usinga
Metals 84 (I 997) 945-946
literature value of 0.87 x 10‘i4esu for b of chloroforms,the
nonresonantsolventterm, the varioussamplecontibutionscan
be quantitativelydetermined.The valuesthat we haveobtained
for this pump wavelength are shown in table 1. We have
assumedthat two-photon resonanceis unimportant at this
wavelengthandfixed Lt aszero.
Table 1. Nonlinearparameters
of trans-p-carotene
1033/esu
13 &4
390Lk40
170k 50
The instrument responsefunction, determined by the
bandwidth of the two lasers was reconvoluted with the
calculatedCARS spectrum.By fixing this term and also the
Ramanlinewidth in our analysiswe are improving the fitting
routineby reducingthe numberof variableparameters.
The background for our CARS spectra have caused
difficulties, insteadof a constantbackground,we have a curved
background.This is a well known problemfor CARS as the
phasematchingconditionsalter asa CARSspectrumis scanned
due to the dispersivenature of the refractive index of the
solution.Also the different concentrationsolutionswill have
different refractive indices and therefore unique phase
matching.For our presentinterpretationof the CARS data we
haveapproximatedthe backgroundwith a lineartrend.
The errorsare large due to a smallamountof correlation
betweenthe parametersandalsothe dueto the phasematching
problemmentionedabove.
4. Conclusions
Due to the nonresonantterm of the third-order optical
nonlinearityeffectingthe coherentRamanlineshapewe canuse
this resonanceto study the nonresonantnonlinearity which is
experimentally easier. By studying the concentration
dependence of the lineshapewe have beenable to separatethe
one and two-photonmolecularcontributionsto the third-order
nonlinearity.The valuethat we have obtainedfor the molecular
nonresonant third-orderopticalnonlinearityfor tram+p-carotene
is ~(-59lnm,65Onm,-721.4nrn,65Onm)= (13i4)x1r33esu.
This valueis in goodagreement thoseobtainedpreviously.4
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