Materials Science and Engineering R 42 (2003) 115–155
Secondorder nonlinear optical properties of chiral materials
´ Sonja Sioncke, Thierry Verbiest, Andre Persoons*
Department of Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200D, 3001 Heverlee, Belgium Accepted 9 September 2003
Abstract
This paper reviews work on the secondorder nonlinear optical properties of chiral thin ﬁlms and surfaces. We give an overview of the theoretical formalism and experimental techniques to describe the secondharmonic generation (SHG) from chiral thin ﬁlms and surfaces. We also discuss the secondharmonic response of thin ﬁlms and surfaces composed of chiral synthetic materials and biological molecules. In addition, we point out possible applications and the future prospects in this ﬁeld. # 2003 Elsevier B.V. All rights reserved. Keywords: Chirality; Secondharmonic generation; Nonlinear optics; Surfaces; Optical activity; Thin films
1. Introduction Chirality is equivalent to the lack of mirror planes in a materials system. As a consequence, chiral molecules occur in two enantiomers that are mirror images of each other. Because of the importance of chirality in the fields of biochemistry, biology, catalysis and pharmacology, chirality has been a widely studied phenomenon. In order to probe chirality, wellestablished techniques are needed. Characterization techniques are usually based on the fact that chiral molecules exhibit optical activity effects, i.e. they interact differently with left and righthand circularlypolarized light. The circulardifference response changes sign between the two enantiomers of the chiral molecules. Wellknown examples of optical activity effects are optical rotatory dispersion (ORD), optical rotation and circulardichroism. These effects are routinely used to determine the absolute configuration of chiral molecules, their enantiomeric purity, as well as the secondary structure of proteins and DNA. Recently, optical activity effects have also been observed in nonlinear optical processes, i.e. chiral molecules have a different interaction with left and righthand circularlypolarized light in a nonlinear optical process. Such nonlinear optical activity effects were demonstrated in secondharmonic generation (SHG) from chiral surfaces, first from chiral molecules adsorbed at an air– water interface, and later from Langmuir–Blodgett films from chiral molecules and polymers. The circulardifference effects observed in secondharmonic generation were much larger than in the linear optical regime and therefore this new characterization technique was put forth as a sensitive tool to study surface chirality. Owing to the similarity with traditional circulardichroism, the technique was referred to as secondharmonic generation: circulardichroism. The unique combination of a
Corresponding author. Tel.: þ3216327169; fax: þ3216327982. Email address: andre.persoons@fys.kuleuven.ac.be (A. Persoons). 0927796X/$ – see front matter # 2003 Elsevier B.V. All rights reserved. doi:10.1016/j.mser.2003.09.002
*
116
S. Sioncke et al. / Materials Science and Engineering R 42 (2003) 115–155
nonlinear optical process and circulardichroism makes it an ideal tool to study surface chirality: secondharmonic generation is surface sensitive because of symmetry reasons and circulardichroism is sensitive to chirality. More recently, other techniques sensitive to surface chiralty, all based on secondharmonic generation, have been demonstrated and applied in a variety of systems. In this work, we will give an overview of these techniques. Another virtue of chirality in secondorder nonlinear optics is the inherent noncentrosymmetry of chiral materials, a necessary requirement for secondorder nonlinear optical processes to occur. Introducing noncentrosymmetry in traditional nonlinear optical materials has always been a challenge. Because of their inherent noncentrosymmetry, chiral materials can therefore be extremely useful for nonlinear optical applications. Furthermore, it has been shown that chirality can favor the nonlinear optical response, either through supramolecular aggregation or through magneticdipole contributions to the nonlinear response. However, the role of chiral materials in nonlinear optics is a relatively new domain of research, and a lot of work remains to be done to optimize chiral molecules and polymers for nonlinear optical applications. In this review we give an overview of some of the recent developments in this field. When appropriate we will point out the problems that remain to be solved and give suggestions for future directions of research.
2. Optical activity and molecular structure [1] In the early 19th century, the French physicist Jean Baptiste Biot discovered that some substances of biological origin cause the polarization of the light rays passing through them to be rotated about the direction of travel. The phenomenon is known as optical rotation, and the substances which exhibit it are said to be optically active. Biot repeated the experiments of his colleague Franc ¸ois Arago in 1812 and interpreted the effects as optical rotation. Disks of quartz crystals were placed between a polarizer and an analyzer and Biot was able to observe a rotation of the polarization of light which was different for different colors of light. His measurements enabled him to conclude that the angle of optical rotation is proportional to the thickness of the quartz plate and inversely proportional to the square of the wavelength. Biot also discovered that quartz crystals occur in two forms which rotate the polarized light in opposite directions. Two questions arose upon the study of Biot. What is the physical nature of light that makes possible the phenomena of polarization and optical rotation? What is the property of optically active molecules that enables them to rotate polarized light? Fresnel discovered circularlypolarized light, in which the electric field in the wave rotates in a circle instead of oscillating linearly (linear polarization). Fresnel explained optical rotation in terms of a transverse wave by showing mathematically that a linearly polarized ray can be composed of two circularlypolarized rays rotating in opposite directions (a rightcircularlypolarized ray and a leftcircularlypolarized ray) and that the direction of linear polarization rotates if the two circularly components travel through the medium at different velocities. Fresnel already suggested that a helical arrangement of molecules could explain a different interaction for the two circularlypolarizations although up to then, scientists did not know what the relation was between optical activity and molecular structure [2]. The answer was found by Louis Pasteur (1850). Pasteur made the important finding that for a number of substances the occurrence of dissymmetric (chiral) crystals was correlated with the existence of optical activity in solution [3]. In 1874 the Dutch chemist Jacobus H. van’t Hoff and the French chemist Joseph A. Le Bel both published papers proposing a tetrahedral arrangement of atoms attached to carbon atoms as the basis for molecular dissymmetry. They argued that such a structure would be dissymmetric if the four atoms or radicals
S. Sioncke et al. / Materials Science and Engineering R 42 (2003) 115–155
117
attached to carbon were different and would be symmetric if any two were identical [4,5]. The explanation of how a dissymmetric tetrahedral molecule could be the source of optical activity was put forth by Max Born in Berlin, Carl Wilhelm Oseen in Uppsala and Frank Gray in Wisconsin [6–8]. Their idea was to take the simplest known active molecule, CHFClBr, and examine the induced dipole in the molecule in the presence of both right and leftcircularlypolarized light: different induced dipoles would explain the difference in refractive index. The dipole induced in the molecule is different in the two cases because all the other atoms with which carbon interacts see different fields in the two waves. ´ In 1895 the French physicist Aime Cotton found that optically active compounds showed unequal absorption of right and leftcircularlypolarized light in the wavelength region were absorption occurs [9]. ‘‘Circulardichroism’’, as the effect is known, was soon understood to arise from the same mechanism as optical rotation. This is because absorption occurs when the induced molecular dipole oscillates outofphase with the light wave. Optical rotation was already observed in the 19th century but it took some time before the scientists discovered what the link was between optical activity and molecular structure. It was Pasteur who suggested that ‘‘dissymmetric’’ crystals were correlated with optical activity. Now, we know that chiral molecules are responsible for optical activity effects. An object is chiral when it is not superimposable upon its mirror image and achiral when it is superimposable. A more practical way to evaluate if a molecule is chiral or not is to determine the symmetry elements present in a molecule. A molecule is achiral when it possesses reflectional symmetry. Reflectional symmetry exists if any of the improper symmetry elements are present (Sn, i, s). Biot’s findings have brought insights to important problems in physics, chemistry, and biology. Optical activity has been traced to the effects of classical interactions among electric charges in a molecule, making it possible to treat the physics of optical activity and related molecular properties. Chemistry aims to understand the behavior of increasingly complex substances in terms of their molecular structures, and optical activity has given new value to this phenomenon as a tool for determining structures. Some fields of modern biology seek to understand life at the level of molecular structure, and the optical activity of many complex biological molecules provide one of the major keys to the subtle structural features that control biological function. 2.1. Optical rotation and circulardichroism in linear optics [10] Optical rotation is the phenomenon of rotation of linearly polarized light when passing through an optical active medium. Experimentally this can be demonstrated by placing an optically active medium between a crossed polarizer and analyzer. We can observe a leakage of light. By rotating the analyzer by some number of degrees Æf, no light passes trough the analyzer. So we can conclude that the optically active medium has rotated the plane of polarization by f degrees in a positive or negative (right or lefthanded) sense. Furthermore, the sense of rotation is related to the direction of propagation of the light. If the light traverses the same medium in each of the opposite directions— as when it is returned trough the medium by reflection at a mirror, the net rotation vanishes. The question of what is happening when light passes through an optically active medium is easily answered at the macroscopic level. The linearly polarized light can be replaced by the representation of two circularlypolarized beams travelling, respectively, clockwise and counterclockwise. Then if the material exhibits different properties with respect to the two beams, for example, that its indices of refraction are different for rightcircularlypolarized light than for leftcircularlypolarized light, one of the components will lag behind the other—the lag being proportional to the difference between the two indices of refraction and the length of the path through the material and inversely
118
S. Sioncke et al. / Materials Science and Engineering R 42 (2003) 115–155
+x
+x
θl
y
θr
+y y
θl
θr
+y
x
x
Entering the active medium
Leaving the active medium
Fig. 1. After leaving the active medium the planepolarized wave will be rotated by (yr À yl )/2 from its original orientation.
proportional to the wavelength of the light. To examine the meaning of the statement that one component will lag behind the other, we will determine the values of the rightcircularlypolarized beam, Er and of the leftcircularlypolarized beam, El at a time the values of their phases, yr and yl (initially identical) will differ because the refractive indices nr and nl are unequal (Fig. 1). The amplitude of the planewave propagating in the zdirection and polarized along the xdirection can be described by the following equation: x E ¼ E0^ cos y (1)
x where y ¼ 2pn½t À ðnz=cÞ, and E0 is the maximum amplitude of the wave, and ^ is the unit vector in the direction of the xaxis. The two circularlypolarized waves composing this planewave are given by x y Er ¼ E0 ð^ cos yr À ^ sin yr Þ El ¼ E0 ð^ cos yl þ ^ sin yl Þ x y (2) (3)
where ^ is the unit vector in the ydirection. Initially yr ¼ yl ¼ y, after passing through the optically y active medium, they will differ. From the definition of y, we can describe yr and yl as nr z yr ¼ 2pn t À (4) c nl z (5) yl ¼ 2pn t À c 2pnz (6) ðnl À nr Þ yr À yl ¼ c The difference, which is known as the phase lag, is just twice the angle by which the incident planepolarized wave has been rotated by the optically active medium. This can be seen when we represent the two circularlypolarized waves by a planepolarized wave x y E ¼ Er þ El ¼ E0^ðcos yr þ cos yl Þ À E0^ðsin yr À sin yl Þ; 1 1 E ¼ 2E0 cos ð2 yr þ yl Þ½^ cos ð2 yr À yl Þ À ^ sin ð1 yr À yl Þ x y 2
(7)
We now see that because yr 6¼ yl , E must now have an x and y component (^ and ^). E is therefore no x y longer parallel to the xaxis. From Fig. 1 it can be seen that E is now a planepolarized wave rotated by (yr À yl Þ=2 from its original orientation in the x–z plane. This rotation is caused by the difference
3lC (13)
. which describes how each of the circularlypolarized beams is differentially absorbed as it travels through z cm of the active material (circulardichroism). If the optically active medium is not transparent at the wavelength of the incident radiation. The ellipse may be characterized by the angle c whose tangent is equal to the ratio of the major to the minor amplitudes of the ellipse. tanh pðKl À Kr Þz=l. because the extinction difference Kl À Kr is rarely greater than 10À6 or 10À7. Otherwise the amplitudes of the components E0^ and E0^ of the circularlypolarized radiation would have to be modified not only by the phase angle y which describes the velocity difference with which they travel through the medium. (11) can be shown to be equal to the hyperbolic tangent.and rightcircularlypolarized light are different. but also by an exponential factor expðÀ4pKl z=lÞ and expðÀ4pKr z=lÞ. Not only do the two circularlypolarized beams leave the material outofphase. The relation between the rotation and the difference in the indices of refraction is d¼ yr À yl pnz ðnl À nr Þ ¼ c 2 (8)
or since the wavelength l ¼ c=n d¼ pz ðnl À nr Þ l (9)
d is thus the angle by which the planepolarized wave has been rotated in traversing the optically active medium of thickness z. the function on the righthandside of Eq. The hyperbolic tangent of c is very nearly equal to c for values of c less than 1. the rotation is specified in degrees per decimeter f¼ 1800 ðnl À nr Þ l (10)
It is important to remember that we have been discussing a transparent optically active material for which Kl and Kr % 0 (where K is the complex part of the refractive index and is linked to x y absorption). More commonly. from the differential absorption of the circularlypolarized component beams. then the transmitted intensity is substantially reduced. the extinction coefficient e (in MÀ1 cmÀ1) is related to the absorption index by e¼ 4pK 2. which is a measure of the eccentricity of the ellipse results. The ellipticity c. but also one of the components is absorbed more strongly than the other. When we express them in terms of the extinction difference. of course.S. Sioncke et al. Consequently C¼ pz ðKl À Kr Þ l (12)
In the more commonly used units for absorption. Therefore tan C ¼ jEr j À jEl j jEr j þ jEl j (11)
El and Er are of course no longer equal when the extinction for left. but not precisely the same amount as the isotropic absorption measured under the same conditions using unpolarized light. The measured ellipticity is rarely greater than 1 even for short wavelengths. / Materials Science and Engineering R 42 (2003) 115–155
119
in refraction nr À nl of the optically active medium.
wme are the firstorder chiral (or magnetic) susceptibilities. The ladder diagrams for the susceptibilities wee. The sum of both fields is a new field with its polarization rotated over an angle y.120
S. no optical rotation can occur. In the absence of magnetic interaction. Optical activity can be understood intuitively. / Materials Science and Engineering R 42 (2003) 115–155
Ein
P
M θ E(P
Eout E(M)
Fig.2. Substituting in Eq. while the magnetization radiates a horizontally polarized field. (12). the ellipticity in radians is c ¼ ð1 2. wem refers to an interaction where a photon is annihilated through a magneticdipole interaction and a photon is being created through an electricdipole interaction. 2. The two firstorder chiral susceptibilities can be related to each other: wem ¼ Àwme . For example. The rotation angle y has the same magnitude but differs in sign for both enantiomers. wee is a real quantity while wem and wme are imaginary quantities. Sioncke et al. 3CzÞðel À er Þ 4 The circulardifference can also be expressed as a normalized quantity De/e De 2ðel À er Þ ¼ e el þ er 2. 3. depending on the relative magnitude of P and M. The susceptibilities wem and wme are only present in chiral media and are responsible for all optical activity effects in linear optics. Polarization and magnetization in linear optics [11] Another approach to optical activity in linear optics can be made starting from the linear polarization and magnetization induced by the electric field E and magnetic field B of the incoming light up to the firstorder within the magneticdipole transition (Fig. a vertically directed polarization and magnetization will be created inside the medium.
where C is the concentration in moles per liter. For an achiral medium the refractive index can be related to the linear susceptibility n2 ¼ 1 þ 4pwee (18)
. Both polarization and magnetization act as new sources of radiation: the polarization radiates a vertically polarized field. The superscript ‘‘e’’ refers to an electricdipole transition and the superscript ‘‘m’’ refers to a magneticdipole transition. Notice that for a nonresonant excitation. wem and wme are given in Fig. 2) P ¼ weeð1Þ E þ wemð1Þ B M ¼ wmeð1Þ E (16) (17) (15) (14)
where wee is the firstorder (or linear) susceptibility and wem. If we consider light that is vertically polarized and incident on a chiral isotropic medium.
S. the induced charge distribution can be described on a molecular (macroscopic) scale by the induced electricdipole moment m (the polarization P) [15] m ¼ Àer and P ¼ ÀNer (21) (20)
with e the electric charge. reflection. When a medium is subject to an optical field. Rayleigh light scattering. sumfrequency generation [13]. These nonlinear optical effects were already predicted theoretically in the firsthalf of the 20th century. For wee.and rightcircularlypolarized light. The most commonly observed effects are linear. m ¼ aE (22)
. For wem. The induced electricdipole moment and polarization are. Ladder diagrams for the susceptibilities wee. the electrooptic effect.em
ω m ω m
χ(1). only be experimentally observed after the development of the laser in the 1960s. Nonlinear optics So far. when the fundamental intensity of the light source becomes sufficiently intense. the presence of the magnetic susceptibility explains the difference in refractive index for left. second. and wme. onephoton optical processes. the input photon is annhilated by a magnetic interaction. wem. we have considered optical activity of chiral compounds in linear optics. the output photon is created while for wme. c nl ¼ pﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ o ð1 þ 4pwee Þ À i8p2 wem c (19)
As a result. r the displacement induced by the electric field. [14]. and refraction are examples of linear optical processes.me
ω e
Fig. because of the high intensities needed. linearly dependent on the electric field. within the electricdipole approximation. still in the assumption of a relatively weak electric field. one can detect twoand threephoton processes such as hyperRayleigh scattering [12]. We assume that the medium is nonconducting and nonmagnetic and that the electrons are tightly bound to the nuclei (as compared with their attraction to the nuclei of neighboring molecules). this equation becomes nr ¼ pﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ o ð1 þ 4pwee Þ þ i8p2 wem . However. etc. we find that for a chiral medium. / Materials Science and Engineering R 42 (2003) 115–155
121
χ(1). the electric field polarizes the molecules of that medium. Sioncke et al. which makes optical rotation possible. and N the electron density.
Based on an expression stated in [10].
3.ee
ω e ω e ω e
χ(1). Then. one photon is annihilated and one photon is created through an electricdipole interaction.and thirdharmonic generation. onephoton absorption. but could. 3.
P ¼ wð1Þ E þ wð2Þ : EE þ wð3Þ . Tensor properties of the nonlinear susceptibility w Note that the secondorder susceptibility.EEE þ Á Á Á (25) (24)
with b the secondorder polarizability or first nonlinear polarizability. more specifically. the first susceptibility. Note that the susceptibility of a medium is related to its dielectric constant and index of refraction by n2 ðoÞ ¼ eðoÞ ¼ 1 þ 4pwð1Þ ðoÞ. in this case between all the components of the polarization and the electricfield vectors. (25)). The principle of Neumann states that under any symmetry operation on the system. In this review. On the other hand. Sioncke et al. Fortunately. (25) as E ¼ E0 cosðot À kzÞ (26)
with E0 the electricfield amplitude. There is a part that is frequencyindependent. o the frequency. and kz the relative phase. (25) gives
2 P ¼ wð1Þ E0 cosðot À kzÞ þ 1 wð2Þ E0 ½1 þ cosð2ot À 2kzÞ þ Á Á Á 2
(27)
This equation clearly demonstrates the presence of components at other frequencies than the fundamental frequency of the input field. secondharmonic generation. . The origin of secondharmonic generation can be understood by describing the fundamental electric field in Eq. The induced electricdipole moment and polarization become . and . and w(1). there is also a contribution at the double frequency which is a secondharmonic generation. when the amplitude of the incident electric field is sufficiently large. Secondharmonic generation is the generation of light with the double frequency of the incident radiation. we have to include higherorder interactions. giving rise to the phenomenon known as optical rectification. we will focus on the secondorder effects originating from the secondorder susceptibility.1. the sign and the amplitude of the physical properties have to remain unchanged [16].EEE þ Á Á Á . is actually a tensor (see Eq. In addition. 3.122
S. In order to illustrate the strength of this principle. w(2). Substitution in Eq. / Materials Science and Engineering R 42 (2003) 115–155
and P ¼ wð1Þ E (23)
with a the linear polarizability. Such intense fields can easily be generated by lasers. although treated thus far as a scalar. this large number of tensor of elements can be often reduced by taking into account the symmetry of the system. we will take the case of a centrosymmetric system. and w(2) the secondorder susceptibility or first nonlinear susceptibility. We will examine the influence of the inversion symmetry on the polarization that leads to
. m ¼ aE þ b : EE þ g. w(2). w(2) is a thirdrank tensor and contains 27 (3 Â 3 Â 3) elements. A tensor describes the relation between different vectors.
When including magneticdipole and quadrupole interaction noncentrosymmetry is not a strict requirement any more to observe a secondharmonic response [21]. we have to rewrite Eq. To clearly indicate the tensor properties of w(2). (28) as X ð2Þ ð2Þ wijk Ej Ek (31) Pi ¼
j. liquid crystals. According to the principle of Neumann. This expression has great importance in secondharmonic generation. no secondharmonic generation can be observed from a centrosymmetric system. (28) then becomes ÀPð2Þ ¼ wð2Þ ðÀEÞ2 ¼ wð2Þ E2 ) Pð2Þ ¼ Àwð2Þ E2 (29)
As we can see. One of the textbook examples is paranitroaniline (Fig. Sioncke et al.
. (28) and (29) Pð2Þ ¼ wð2Þ E2 ¼ Àwð2Þ E2 (30)
This relation can only be valid if wð2Þ ¼ 0. on the macroscopic level. However. Paranitroaniline. Alternatively. most systems can be explained within the electricdipole approximation although we have observed some materials were electricdipole approximation fails to describe the nonlinear response. We still need to take a closer look to reduce the components of the susceptibility tensor w(2). the sign of the secondorder polarization has changed under inversion. Crystal growth is a tedious process and not every system crystallizes in a noncentrosymmetric crystal and liquid crystals tend to have low nonlinearity due to detrimental aggregation. This is the reason why nonlinear optical processes as SFG are possible in solutions [13. etc. selfassembly. A chiral molecule is inherently noncentrosymmetric and even a random distribution of enantiomerically pure molecules will never lead to systems with inversion symmetry. The Langmuir–Blodgett technique is time consuming and the films obtained by this way have often low optical quality which is also the problem with selfassembled films.20]. This condition is easily fulfilled on the molecular level by constructing a D–p–A system where an electrondonor is connected to an electronacceptor by a pconjugated system [17]. the Langmuir–Blodgett technique [18]. the electric field and the polarization transform as E ! ÀE and P ! ÀP. This is why on the macroscopic level. one can compare Eqs.S. Pð2Þ ¼ wð2Þ Eð2Þ (28)
Under inversion. some of these techniques still suffer from some disadvantages: relaxation will occur after electricfield poling [19]. / Materials Science and Engineering R 42 (2003) 115–155
123
secondharmonic generation. these D–p–A systems take a randomly distributed orientation and we end up with a centrosymmetric situation which is not able to give rise to secondharmonic generation. the secondorder susceptibility w(2) has to be zero or otherwise stated. This is the point where chirality can be introduced in nonlinear optics. Only noncentrosymmetric systems will give a secondharmonic response.k
H 2N
NO2
Fig. 4. 4). Nevertheless. crystal growth. This can be achieved by electricfield poling. we still have to introduce a polar order in our systems. Eq. However.
To simplify this procedure. respectively. consider the relation Px ¼ wxxz Ex Ez . Then because of the principle of Neumann wxxx ¼ 0.and C1symmetry. Under the fourfold rotation. the verification that wxxx ¼ Àwxxx after the symmetry operation can be reduced to verifying that xxx ¼ Àxxx. for secondharmonic generation within the electricdipole approximation for an achiral and a chiral surface that has inplane isotropy. As a consequence. the component will not be cancelled under reflection. respectively. Sioncke et al.124
S. the coordinates transform as x!y y ! Àx z!z (34)
C4 Z YZ mirror plane Y XZ mirror plane X Achiral surface with C4v (C∞v) symmetry Z
C4
Y
X Chiral surface with C4 (C∞) symmetry
Fig. It was demonstrated that the components of a tensor transform as the product of their respective coordinates. a tensor component will be zero if its index changes after a symmetry operation. In addition. respectively.and C1symmetry of the surface can be treated as C4v. 5).and C4symmetry. 5. we will examine the influence of a mirror plane in the y–z plane on the secondorder susceptibility. Therefore. we have to examine the effect of the mirror plane on each tensor component. As a second example. We consider a righthanded coordinate axis system with the zaxis along the surface normal and the surface being in the x–z plane.
. These surfaces have C1v.and C4symmetry. In other words. As an example. Scheme presenting the main symmetry operations in a chiral and achiral isotropic surface with C4v. This will be transformed into ÀPx ¼ wxxz ðÀEx ÞðEz Þ ¼ Àwxxz Ex Ez ) Px ¼ wxxz Ex Ez . because a higherorder symmetry introduces no further simplification of the susceptibility tensor (see Fig. The C1v. since the sign of the tensor component wxxz remains unchanged. The fourfold rotation axis coincides with the zaxis. Under reflection in this plane the coordinates transform as x ! Àx y ! y z!z (32)
The physical quantities in Eq. / Materials Science and Engineering R 42 (2003) 115–155
where the subscripts ijk refer to the Cartesian coordinates in the laboratory frame. For the component wxxx the reflection will transform the relation Px ¼ wxxx Ex Ex into ÀPx ¼ wxxx ðÀEx ÞðÀEx Þ ¼ wxxx Ex Ex ) Px ¼ Àwxxx Ex Ex . (31) transform as Ex ! ÀEx Px ! ÀPx Ey ! Ey Py ! Py Ez ! Ez Pz ! Pz (33)
Now. Fumi has derived a technique called the ‘‘direct inspection’’ method [22]. The symmetry operations present for a chiral isotropic surface with C4symmetry are a fourfold rotation (that implies also a twofold rotation). We will now analyze the susceptibility tensor w(2). for the C4vsymmetry the mirror planes are the x–z plane and the y–z plane.
For an achiral isotropic surface. an achiral isotropic surface can be described by the three independent components. all remaining 11 components are not independent. the additional two mirror planes transform the coordinates as x!x y ! Ày z!z (36)
for the x–z mirror plane and x ! Àx y ! y z!z (37)
for the y–z mirror plane. wzxx is related to wzyy by the fourfold symmetry. Thus.S. Sioncke et al. When we take a closer look to the tensor components that vanish. For example. the secondorder susceptibility tensor. Under twofold rotation this index becomes ðÀxÞðÀxÞðÀxÞ ¼ Àxxx. wxzy. / Materials Science and Engineering R 42 (2003) 115–155
125
and for a twofold rotation axis x ! Àx y ! Ày z!z (35)
Let us consider wxxx. As in linear optics where we described optical activity effects through magneticdipole interactions. Similarly. Note that all these considerations are made within the electricdipole approximation. wzxy and wzyx will also be zero because under the fourfold rotation zxy transforms into Àzyx. wyyy. Therefore. we conclude that every tensor component where the sum of the number of x’s and y’s in its index is odd must be zero. and similarly. and wyxz are only allowed for chiral isotropic surfaces and are designated as chiral tensor components. that describes the secondharmonic signal generated in a chiral isotropic surface. will be zero. wxxy. wzyx will be zero. In addition. wxzx ¼ wyzy . Therefore wzxy. wyzx. wxyy. The remaining components are allowed for all isotropic surfaces and are therefore referred to as achiral tensor components. and wxxz ¼ wyyz . etc. The total number of vanishing components is now 16. wyzx. listed in Table 1. one can also take account of magneticdipole interactions in the case of nonlinear optics. wxxx must vanish. wxzx ¼ wxxz . The tensor components: wxyz. will have four independent components listed in Table 1. Indeed. and wyxz. wxzy. We can define the nonlinear polarization and magnetization up to the firstorder in magneticdipole transitions as Pi ð2oÞ ¼ weee Ej Ek þ weem Ej Bk ijk ijk Mi ð2oÞ ¼ wmee Ej Ek ijk (38) (39)
Table 1 Nonvanishing components of the secondorder susceptibility tensor for secondharmonic generation in the electricdipole approximation for achiral and chiral isotropic surfaces Chiral isotropic surface Tensor components wijk zzz zxx ¼ zyy xxz ¼ yyz ¼ yzy ¼ xzx xyz ¼ Àyxz ¼ Àyzx ¼ xzy Achiral isotropic surface zzz zxx ¼ zyy xxz ¼ yyz ¼ yzy ¼ xzx
The surface is in the x–y plane. This procedure leads to the elimination of 14 components. we will examine the index xxx. wyxy. because of intrinsic permutation symmetry (no distinction can be made between ExEy and EyEx) the last two indices can be exchanged and this results in zxy ¼ Àzyx ¼ Àzxy. However. This causes the elimination of the four components that have three different indices: wxyz. Hence. According to the direct inspection method. Note that because of permutation symmetry. wzxx ¼ wzyy . Hence.
.
the number of independent components is limited to three for weee. the magnetic quantities will transform differently Bx ! Bx Mx ! Mx By ! ÀBy My ! ÀMy Bz ! ÀBz Mz ! ÀMz (42)
Therefore. (38) and (39) refer to electric. wmee will be zzz zzz zzz zero for an achiral isotropic surface. the electric quantities transform as Ex ! ÀEx Px ! ÀPx Ey ! Ey Py ! Py Ez ! Ez Pz ! Pz (41)
However. Therefore.mee
ω
e
2ω e
ω
e
2ω m
ω
e
2ω e
Fig. For an achiral isotropic surface (C1vsymmetry). However. which results in fewer independent
. wmee are given in Fig. in Eqs. an axial vector transforms as the position vector under proper transformations (rotations) only.eem
ω m
χ(2). two input photons of frequency o are annihilated and one photon at frequency 2o is created through electricdipole interactions. there is a fundamental difference between an electricfield vector and a magnetic field vector. The numbers of components of the susceptibility tensors weem and wmee can be reduced in a similar manner as demonstrated for the tensor weee. For a chiral isotropic surface (C1symmetry) weee has four independent components. the superscript ‘‘eem’’ of the susceptibility tensor weem refers to an interaction where a photon at frequency 2o is generated through an electricdipole interaction. the mirror plane will transform Mz ¼ wmee Ez Ez into ÀMz ¼ wmee Ez Ez . Notice also that for a nonresonant excitation. weee is a real quantity while. Note that weee and wmee possess intrinsic permutation symmetry. For wmee. 6.and magneticdipole interactions. The ladder graphs for the tensors weee. and wmee four. For weee. the output photon is generated through a magnetic interaction. weem. On the other hand. because of the principle of Neumann. 6.24].eee
ω e ω e
χ(2). and two photons are annihilated by an electric.
The superscripts ‘‘e’’ and ‘‘m’’. For example. Under improper transformations (reflection inplane and inversion). for example. and one for wmee. A polar vector transforms as the position vector under all spatial transformations. The coordinates transform as x ! Àx y ! y z!z (40)
Consequently. one input photon at frequency o is annihilated by a magnetic interaction whereas the other interactions occur through electric dipoles. The first is a polar vector whereas the latter is an axial vector. consider the influence of a mirror plane in the y–z plane. and wmee. on the other hand.and magneticdipole interaction. Sioncke et al. For example. respectively. Photon diagrams for tensors weee. Let us. weem. respectively. three for weem. / Materials Science and Engineering R 42 (2003) 115–155
χ(2).126
S. For weem. the nonvanishing tensor components of tensor weee will be different as compared to the components of the tensors weem and wmee (see Table 2). weem and wmee are imaginary quantities [23. weem seven. each component of an axial vector transforms opposite to that of the position vector [21].
weem. Sioncke et al. for which there is no analogue in linear optics. the relative magnitude of the various interactions can depend on the structure of the material. It has been shown that chiral molecules and more specific helical molecules are such structures [26]. The components that are only allowed for chiral surfaces are referred to as chiral while those allowed for both chiral and achiral surfaces are called achiral tensor components.and righthanded circularlypolarized fundamental beams. the fascination grew also because one discovered the existence of optical activity in nonlinear optics [27].and magneticdipole interactions. and wmee for isotropic chiral and achiral surfaces Tensor weee Achiral components for all isotropic surfaces zzz zxx ¼ zyy xxz ¼ xzx ¼ yyz ¼ yzy xyz ¼ Àyxz zxy ¼ Àzyx xzy ¼ Àyzx xyz ¼ xzy ¼ Àyxz ¼ Àyzx Additional components for chiral surfaces xyz ¼ xzy ¼ Àyxz ¼ Àyzx
weem
zzz zxx ¼ zyy xxz ¼ yyz xzx ¼ yzy zzz zxx ¼ zyy xxz ¼ xzx ¼ yyz ¼ yzy
wmee
The surface is in the x–y plane. The astonishing fact was that the SHGCDeffect is several orders of magnitude higher than ordinary circulardichroism in linear optics. Notice also that for centrosymmetric systems. This means that including magnetic contributions. SHGCD. Besides the interest for chiral structures because of their symmetry properties. noncentrosymmetry is a strict requirement to observe secondorder NLO effects. some structures are favorable for magneticdipole transitions for which noncentrosymmetry is not a requirement. This effect is called secondharmonic generation circulardichroism (SHGCD). however will always be broken at surfaces and interfaces between two
. secondharmonic generation is only allowed in noncentrosymmetric structures. Chiral molecules would have a different efficiency for the generation of secondharmonic light for left. in practice. In linear optics optical activity effects arise from the interference between electric. The problem is that magnetic interactions are weaker than the electricdipole interactions by a factor given by the finestructure constant ($1/137) [25]. noncentrosymmetry is not a requirement any more in order to detect a secondharmonic response. The first reason is that symmetry is a very important issue for the secondharmonic response.
4. Chirality in nonlinear optics There is a growing interest in chiral molecules for nonlinear optical purposes. on the contrary. Similar effects as in linear optics were observed. Because chiral molecules are inherently noncentrosymmetric. / Materials Science and Engineering R 42 (2003) 115–155
127
Table 2 Nonvanishing tensor components weee. Other optical activity effects observed in nonlinear optics are secondharmonic generation linear difference (SHGLD).
components.S. In the electricdipole approximation. As we already mentioned. weem and wmee are not zero [21]. In addition. However. Centrosymmetry. they possess an electricdipole allowed secondorder and higher evenorder nonlinearity. can be explained within the electricdipole approximation.
Geometry of secondharmonic generation from a thin film or surface. however. ~ ¼ ~ cos y þ~sin y p x z (44)
where y is the angle of incidence. because chiral molecules are inherently noncentrosymmetric.128
S. SHGCD can be used to probe chiral surfaces but. / Materials Science and Engineering R 42 (2003) 115–155
centrosymmetric media and consequently the surface or interface can act as a source for secondharmonic light when irradiated with laser light [28]. 7. Hence. chirality can also be applied in nonlinear optics to enhance the nonlinear response. SHGCD can be used to investigate chiral surfaces and interfaces. As SHG is sensitive to surfaces and CDSHG is an effect specific to chiral materials. reflection in a plane containing the surface normal is an additional symmetry operation. The symmetry of such a sample is broken in the direction of the surface normal (zdirection). First. The p. SHG from chiral films: basic theory We consider an experimental configuration that is schematically shown in Fig. A laser beam at frequency o is incident on the sample with isotropic surface symmetry.
. 4. one could enhance the overall nonlinear response through magneticdipole contributions. z) vectors by ~ ¼ À~ s y.and spolarized components of the field and the respective unit vectors are related to the Cartesian (x. respectively.and spolarized secondharmonic fields are generated in reflected and transmitted directions. and polar order is therefore not a strict requirement. on the other hand. we will demonstrate the usefulness of this technique as a tool to study chiral surfaces. Second. Sioncke et al. In this review. z are the natural basis for analyzing the symmetry properties of the sample.1. y. For an achiral surface. We assume that the nonlinear layer is sufficiently thin that its linear optical
Z ω 2ω Reflection
p s
θ
p s
Thin film or surface
X Y
p s
2ω Transmission
Fig. Note that x. The fundamental beam at frequency o is incident on the film at angle y. y. the nonlinear optical response originates from electricdipole transitions as well as from magneticdipole transitions. arbitrary rotations about the surface normal remain symmetry operations. 7.30] sE EðoÞ ¼ ~ p ðoÞ þ~ s ðoÞ pE (43)
where Ep(o) and Es(o) are the p. The symmetry groups of the achiral and chiral isotropic surfaces are C1v and C1. The fundamental beam can be expressed in terms of the p–s basis as [29.
i. one could also include electricquadrupole interactions. As mentioned before fi.and spolarized components of the fundamental or secondharmonic fields. the magnetic field B(o) depends linearly on the electric field E(o). making separation between the two is extremely difficult [30]. and h is also dependent on the symmetry of the sample. weem and wmee. Furthermore. In addition. Hence. The reason that we do not include them here is that the magneticdipole interactions are actually somewhat stronger than the quadrupole interactions. We will only consider explicitly electric. respectively. weee. For an achiral and chiral isotropic surface. gi and hi are linear combinations of the components of the nonlinear susceptiblities weee. the importance of magnetic interactions in chiral media is well established and one can argue that chirality favors the magnetic interaction [31–33]. the general symmetry properties of magneticdipole and electricquadrupole interactions are very similar in secondorder nonlinear optics. / Materials Science and Engineering R 42 (2003) 115–155
129
activity does not appreciably mix the p. The nonlinear interaction of the fundamental field with the material can be described by the nonlinear polarization and magnetization up to firstorder in the magneticdipole interaction: Pi ð2oÞ ¼ weee Ej Ek þ weem Ej Bk ijk ijk Mi ð2oÞ ¼ wmee Ej Ek ijk (45) (46)
The nonlinear polarization P(2o) and magnetization M(2o) act as sources of secondharmonic radiation.e. This approach simplifies the discussion considerably and also facilitates highlighting the different symmetry properties of the electricdipole and highermultipole interactions. weem and wmee. respectively [29]:
Rs fTs ¼ Àsin yðÀ2weee cos y À weem þ wmee sin2 y þ wmee cos2 y Ç 2wmee cos2 yÞ xyz xzx zzz zxx xxz
(48) (49) (50)
gRs ¼ Àsin yðweem þ wmee Þ Ts xxz zxx hRs ¼ sin yð2weee À ðweem þ weem Þ cos y Ç 2wmee cos yÞ Ts xxz xzy xyz xyz
Rp fTp ¼ sin yðweee sin2 y þ weee cos2 y Ç 2weee cos2 y À weem cos y Æ weem cos y þ 2wmee cos yÞ zzz zxx xxz zxy xzy xyz
(51) gRp ¼ sin yðweee À weem cos y Ç weem cos yÞ Tp zxx zxy xyz hRp ¼ Àsin yðÇ2weee cos y þ ðweem À weem Þ sin2 y Ç ðweem þ weem Þ cos2 y À 2wmee Þ Tp xyz zzz zxx xzx xxz xxz (52) (53)
. Furthermore. In principle. The detailed form of the coefficients f. Sioncke et al.S. The electricfield amplitude of the secondharmonic generation is directly proportional to the two sources. The detailed forms of the coefficients are different depending on which contributions are included in the theory.and magneticdipole interactions. As a consequence. we derived the different independent components of the secondorder susceptibility within the electricdipole approximation. the quadrupole interaction is implicitly included in the magneticdipole interaction. we can write the secondharmonic generated field as
2 2 Ei ð2oÞ ¼ fi Ep ðoÞ þ gi Es ðoÞ þ hi Ep ðoÞEs ðoÞ
(47)
where fi. g. gi and hi are linear combinations of the components of the nonlinear susceptiblities weee.
Also for a CDeffect to occur. We will consider throughout this paper s.2. Since fs and gs and hp are zero for an achiral surface. chiral materials interact differently with left. no circulardifference effect can occur for p. One can probe these different characteristics by two measurements.and righthand circularlypolarized light. Because of the difference in refractive index for the circularlypolarized components. In the case of nonresonant excitation. An example of such a measurement is circulardichroism: the difference in output intensity is measured for left.and ppolarized detection. Chiral materials have a different linear absorbance and refractive index for the two different circular polarizations. the circulardifference effect will only occur for chiral materials and the effect will change sign for the two enantiomers of the sample. even though the sample is achiral. This problem will be treated in a later chapter [34–36]. It is clear that for an achiral surface only hs is nonvanishing (i.and ppolarized secondharmonic signals. Sioncke et al. one cannot use circularlypolarized input light to probe the difference in refractive index for the two polarizations. the intensity of the secondharmonic field is found from Eq. we can see that the mean difference is that f and g are the achiral components and h is the chiral component for ppolarized detection.130
S. Hence. i. The circulardifference response can be
. y is the angle of incidence. First. hs is an achiral component). we will consider circulardifference effects in secondharmonic generation (SHGCD). The chiral components are those that are nonvanishing only for chiral surfaces. In linear optics these effects arise from an interference between electric and magnetic susceptibilities. because this leads to no difference in the output intensity.or spolarized detection. We can conclude from Eq. Note also that the coefficient gs vanishes in the electricdipole approximation. gs and hs are nonvanishing (fs and gs are therefore chiral components). we have included in these coefficients the linear indices of refraction of the surface layer and the surrounding media. s refers to the polarization of the detected signal. For the case of circularlypolarized fundamental beams. to make the formalism easier. In this case it is better to use linearlypolarized input light. which is composed of equal amounts of the two circularlypolarized components. gi and hi can be considered as susceptibility components in the p–s basis. Circulardifference and lineardifference effects in secondharmonic generation In linear optics. Ep ðoÞ ¼ ÆiEs ðoÞ.and righthand circularlypolarized input light. However. a detection scheme that mixes p and s polarizations.e. optical rotation can be observed. and the surface normal is along the zdirection. If we analyze the equations for ppolarized detection.and righthand circularlypolarized input light. the linearlypolarized light will be rotated while travelling through the chiral material. (47) to be Ið2oÞ ¼ jÀf þ g Æ ihj2 jEs ðoÞj4 (54)
The circulardifference response is arising from the interference between the quantities g–f and h. while for a chiral surface fs. 4. respectively. Consequently. This is important because the role of f. chiral materials will also interact differently with left. gives rise to nonzero values of the three coefficients. this is not always the case for nonlinear optical activity. As we will point out. there has to be a phase difference between g–f and h. Also in nonlinear optics. and h as chiral or achiral components is reversed between the s. g.e. nonlinear optical activity. the achiral components are nonvanishing for chiral and achiral surfaces. / Materials Science and Engineering R 42 (2003) 115–155
where R and T refer to the secondharmonic fields generated in reflection and transmission direction. (47) that the coefficients fi. In nonlinear optics.
On the other hand. / Materials Science and Engineering R 42 (2003) 115–155
131
described by a normalized quantity (as in linear optics De/e): DIð2oÞ ILHC ð2oÞ À IRHC ð2oÞ ¼ Ið2oÞ jILHC ð2oÞ þ IRHC ð2oÞj=2 (55)
where LHC and RHC stand for left. have to be fulfilled simultaneously.37]. These spectra are similar to the UV spectra as expected by the relationship between SHG and resonance [27]. which is the amount of rotation of the SHG signal in comparison with a 50–50 mixture of enantiomers (an achiral surface). This lineardifference response has no analogue in linear optics. the required phase difference will also exist for nonresonant excitation. Within the electricdipole approximation this phase difference will exist if the fundamental and/or secondharmonic frequencies are tuned close to resonance frequencies of the material. it can be useful to probe the SHGCDresponse as a function of the SH wavelength. We can also use linear input polarizations to probe surface chirality. The basic idea of SHGORD is to use linearlypolarized fundamental light and to observe the polarization maximum of the outgoing SHG signal as a function of the rotation angle f. However. Note that for a chiral material the two conditions. The f can be defined as f ¼ tanÀ1 ½Rð2oÞ where R(2o) is the ratio of the spolarized component to the ppolarized component Rð2oÞ ¼
2 2 Es ð2oÞ fs Ep ðoÞ þ gs Es ðoÞ þ hs Ep ðoÞEs ðoÞ ¼ 2 2 Ep ð2oÞ fp Ep ðoÞ þ gp Es ðoÞ þ hp Ep ðoÞEs ðoÞ
(57)
(58)
. limits SHGCD to regions of the spectrum in which the molecules absorb light (o or 2o). The difference can therefore exist in nonresonant excitation in the electricdipole approximation. For the case of linear polarizations that are rotated by Æ458 from the ppolarized direction. In this respect. The main constraint of SHGCD is the fact that this technique is a resonance technique. Sioncke et al. f þ g and h must be nonvanishing (the material has to be chiral) and f þ g and h have to be inphase. when we include magneticdipole interactions. The observed SHGORD will be characterized by the angle f. chiral selective but not constrained to resonant wavelengths. on the other hand.S.and righthand circularlypolarized fundamental beams. Therefore. Ep ¼ ÆEs and the intensity of the secondharmonic field is Ið2oÞ ¼ j f þ g Æ hj2 jEs ðoÞj4 (56)
This result implies that in order to observe a lineardifference effect (SHGLD). is a technique that is surface sensitive. SHGORD. a nonlinear analogue of linearoptical rotation does exist and is called secondharmonic generation optical rotatory dispersion (SHGORD) [30. like ordinary CD spectroscopy. lineardifference effects are complementary to circulardifference effects in SHG (where a phase difference between the expansion coefficients is required) [37.38]. interference between chiral and achiral expansion coefficients and a phase difference between these coefficients. respectively. The requirement of complex susceptibility tensor components. Because SHGCD is a resonance technique. the lack of an SHGCDeffect cannot be used to conclude that the material is achiral.
No resonance is required for SHGORD to occur. (59). g and h (which are related to weee. different enantiomers of a chiral molecule can be distinguished by the sign of the SHGORD rotation angle.3. Such measurements are referred to as ‘‘polarization measurements’’. We can write the p. The intensity of the secondharmonic field then has the general functional form (cf. in transmission and reflection as a function of the rotation angle of the quarterwave plate. Sioncke et al. In this case the polarization pattern also contains information on the circulardifference response. f changes sign between the two enantiomers. However. Hence. we introduced SHGCD and SHGLD and SHGORD as nonlinear techniques to probe surface chirality. 4. and P(j) and S(j) represent the functional dependence of the fundamentalfield components on the rotation angle. the sign of fs reverses between two enantiomers. The method is based on a series of continuous polarization measurements. / Materials Science and Engineering R 42 (2003) 115–155
when using ppolarized fundamental light. it would be extremely useful to know the relative values of all components of this tensor. The polarization of the fundamental is continuously varied by a rotating quarterwave plate (QWP). The intensity of the secondharmonic light is recorded. fs can be resonantly enhanced which would increase the ratio in Eq. The chirality of the sample is reflected through the sign and magnitude of fs. j is the rotation angle between the ppolarized direction and the axis of the wave plate. Using this relationship. all structural information is embedded in the nonlinear susceptibility tensors. Here we describe a method that is able to determine the relative complex values of the coefficients f. while in linear optics optical rotation can add up unlimited by propagating through the chiral medium. As a consequense. The polarization pattern of the secondharmonic intensity then has the form: Is ðjÞ ¼ jh2 jjPðjÞSðjÞj2 s (63)
. Continuous polarization measurements In the previous section. the expression is considerably simplified À1 fs f ¼ tan fp
(59)
The angle f is dependent upon the chirality of the sample. As we know. However. The magnitude of the SHGORD effect will depend on the ratio of chiral and achiral components. While these techniques are useful for the detection of surface chirality. and the sign of the achiral coefficient fp does not change. the only nonvanishing expansion coefficient is hs. (47)): IðjÞ ¼ jEð2oÞj2 ¼ jfP2 ðjÞ þ gS2 ðjÞ þ hPðjÞSðjÞj2 (62)
When the detected signal is spolarized and the surface is achiral. polarization measurements provide also direct information on the chirality of the sample. Eq. weem and wmee) for various secondharmonic signals in a unique way. it is difficult to differentiate between the enantiomers.and spolarized components of the fundamental beam as Ep ðoÞ ¼ E0 ðcos2 j þ i sin2 jÞ ¼ PðjÞ Es ðoÞ ¼ E0 sin j cos jð1 À iÞ ¼ SðjÞ (60) (61)
where E0 is the amplitude of the initial fundamental field. f will be large if fs is not zero and large compared to fp. though. Note also that the rotation angle is limited to Æ908.132
S.
Hence. When we detect the ppolarized secondharmonic signal.5
18013590 45 0 45 90 135 180 Rotation angle ϕ ( degrees) (a)
0
180135 90 45 0 45 90 135 180 Rotation angle ϕ ( degrees) (b)
0
Fig. This asymmetry is reversed if the handedness of the sample is reversed. 8(a). Quantitative information can be obtained from these patterns by fitting them to the following equation [39]:
1 Ið2oÞ ¼ 16 ½fRe À gRe þ 4fIm cos 2y À ðfRe À gRe Þcos 4y þ 2hIm sin 2y À hRe sin 4y2 I 2 ðoÞ 1 þ 16 ½fIm À gIm À 4fRe cos 2y À ðfIm À gIm Þcos 4y À 2hRe sin 2y À hIm sin 4y2 I 2 ðoÞ
(65) where fRe. it is necessary to fix the overall phase. On the other hand. isotropic surface. fIm. One can see that in the case of an achiral sample the secondharmonic intensity is Ip ðjÞ ¼ jfp P2 ðjÞ þ gp S2 ðjÞj2 (64)
which is an even function of the rotation angle j. and h can then subsequently be used to calculate the values of the components of the
. which has no well defined parity with respect to j. To fit the experimental results. and gs. The phase relation between the achiral and chiral components will only change the details of the asymmetry. the nonzero expansion coefficients for an achiral surface are fp and gp. hRe. for example. gIm. and h. gRe. by defining h as a real quantity (hIm ¼ 0). because P2(j) and S2(j) are even functions of j. for the case of a chiral sample. g. isotropic surface. Therefore there does not exist a typical achiral line shape for ppolarized detected signals.or spolarized signals is an evidence of chirality.u.u. g. This is a typical line shape for an achiral surface and any deviation would imply that the surface is chiral. From this equation.)
secondharmonic intensity (a. for SHGCD and SHGLD effects certain requirements of resonance are to be fulfilled in order to detect the chirality of a sample. are the real and imaginary parts of the coefficients f. one can extract the values of f. (a) Normalized line shape of spolarized signals for quarterwave plate measurements for an achiral. 5
0. The values found for the coefficients f. g. While. hs.S. Sioncke et al. (b) Normalized line shape of ppolarized signal for quarterwave plate measurements for a chiral.)
1
1
0. Chirality leads to a leftright asymmetry in the polarization pattern Ip(j) (Fig. and y is the rotation angle of the quarterwave plate. / Materials Science and Engineering R 42 (2003) 115–155
133
secondharmonic intensity (a. 8. and h respectively. however we can find evidence of chirality in the properties of the line shape of ppolarized signals. when there does not exist a mirror plane in respect to the 1808 rotation angle j. Note that this result is independent of the existence or lack of a phase difference between the components fs.
This pattern is shown in Fig. This can be done. asymmetry in the polarization pattern is a direct evidence of chirality. 8(b)). We can conclude that the lack of a mirror plane in respect to the 1808 rotation angle j in the p. and hIm. the intensity has the general form of Eq. (62). Similar arguments are also valid for the spolarized secondharmonic signals. the sample is chiral.
Sioncke et al. 9). absolute values of a component can be determined by calibration with a quartz wedge [40]. control beams with linear polarization were used. Experimental setup. so that no absolute magnitude of a component can be calculated. The wave vectors of the beam (k1 and k2) are in the same plane of incidence. However. Also in this case (in contrast to the photoemission effect) a circulardifference response was observed. the reflection symmetry of the setup is broken and leads to different secondharmonic efficiency for left. In both cases. The spin of the control polarization can be
k1+k2 2ω QWP ω probe beam k2 ω
surface normal QWP k2 ω probe beam
k1+k2 2ω
surface normal thin film
thin film k1 s (s ± p) / p
ω
k1 s (s ± ip) / 2 p
2
Fig.e. Three different cases were investigated. 4. 9. This was the case if the molecular axis. i. a similar experiment as in linear optics was carried out. The chirality in the setup was introduced by using two input beams: a control beam and a probe beam [34]. First.e. was chiral. optical activity effects would occur even if the sample was achiral. When the polarization of the control beam is considered. Two beams at the fundamental frequency are applied on the same spot of an isotropic achiral surface. all secondharmonic intensities are recorded in arbitrary units. A film of polymaleimide functionalized by a disperseredtype chromophore was spincoated and gave an C1vsymmetry after poling. The sign of the effect will also change between the two enantiomers of the molecule. Optical activity effects can also arise from achiral samples. Secondharmonic light is detected in the transmitted direction k1 þ k2 . The absolute phase cannot be determined because of the arbitrary choice of hIm ¼ 0. Such optical activity effects are possible if the experimental setup itself was chiral. This has been observed in linear optics: the efficiency for photoelectron emission from oriented molecules was different for left. The reflection symmetry of the setup can be broken with linear (a) or circular (b) control polarizations. i. The magnitude of the effects was $15%. In the first experiment. the wave vector of the incoming light and the direction of detection of photoelectrons were not coplanar [41–43]. Extramaterial chirality Chirality is usually associated with molecular structure and gives rise to optical activity effects in linear optics as well as in nonlinear optics. the setup can possess two opposite handednesses. the setup is chiral. By using linear control polarizations. circular control polarizations were used. Note that both phase and magnitude of all tensor components are relative values. possesses a definite handedness and is characterized by three noncoplanar vectors. The wave vectors k1 and k2 of the control and probe beam are in the same plane of incidence (Fig. The same findings were made in nonlinear optics: if the experimental setup could be defined by three noncoplanar vectors. The two control polarizations are related to each other by reflection in the plane of incidence. w(2). In the second experiment.134
S.4.and righthand circularlypolarized light. / Materials Science and Engineering R 42 (2003) 115–155
secondorder susceptibility.and righthand circular probe polarizations. A circulardifference response was observed and changed sign when the handedness of the setup was reversed.
. also circular control polarizations can be used to break the reflection symmetry. Moreover. The probe polarization is controlled by a rotating quarterwave plate. The polar axis coincides with the surface normal. In addition.
as one of the angles y and f changes sign. respectively. As expected. i. the ansitropy axis and the input beam form a coordinate system with a definite handedness. substantial difference effects were observed and changed sign when the sign of f was reversed. The anisotropy axis and the surface normal are along the x. Experimental geometry: fundamental laser beam (wave vector k. Such an anisotropic Langmuir–Blodgett film of an achiral material was investigated [44].
. These results show that the circulardifference response reverses sign as the handedness of the sample orientation is reversed. 180 À90 þ90 Circulardifference effect (%) (0 Æ 2) À(6 Æ 1) þ(7 Æ 1) þ(1 Æ 2) þ(7 Æ 1) À(8 Æ 1)
À43
The intensity of the ppolarized secondharmonic field in transmission was detected. Sioncke et al. 10 shows that for some orientations the setup becomes chiral. The sample is mounted on a rotation stage and is allowed to rotate around its surface normal.
associated with a coordinate system with a welldefined handedness. 50 Hz. the setup becomes chiral for some orientations of the film in respect with the incident beam. The chirality of the setup was defined by the control polarization. Furthermore. In this case the surface normal. s. The arrows on the sample indicate the alignment of the achiral molecules along the dipping direction that creates the anisotropy axis.and ppolarized field components) is incident on the sample at an angle y.e. Other combinations of noncoplanar vectors associated with an experimental setup can be found. The circulardifference effects were much larger ($80%) then in the first experiment. The azimuthal rotation of the sample is characterized by f. The experiments were carried out with a Qswitched Nd:YAG laser (1064 nm. / Materials Science and Engineering R 42 (2003) 115–155
135
p z s k θ x y
φ
Fig. When the orientation of the molecules does not coincide with the surface normal. For any other values of these angles. 10. the probe polarization and the surface normal. the setup is chiral and the handedness can be reversed by reflection operations. $10 ns). The magnitude of the difference effects remains unchanged. Fig. The experimental results for all combinations of the angles y and f are summarized in Table 3. For the value f ¼ Æ90 . 180 À90 þ90 0.
Table 3 Experimentally observed circulardifference effects DI/I ¼ 2ðIl À Ir Þ/ðIl þ Ir Þ for different sample orientations f and angles of incidence y Incidence angle y (8) þ43 Sample orientation f (8) 0. Note that for the angles f ¼ 0 or 1808 and y ¼ 0 or 1808.and zdirections. These three noncoplanar vectors broke the reflection symmetry. the difference effects also change sign between positive and negative angles of incidence y. the plane of incidence is a mirror plane and the setup is achiral.S. no circulardifference effects were observed for f ¼ 0 and 1808.
45. They change value when the polarization measurements would be carried out for other azimuthal rotation angles. the individual tensor components shown in Table 4 are anisotropic.77 i0. and 908). The solutions for the tensor components are given in Table 4. no evidence of magnetic contributions could be found in these films.58 28.2 5. For such a symmetry the circulardifference response as a function of the azimuthal rotation angle is DI ¼ a1 þ a cos 2f þ b sin 2f þ c cos 4f þ d sin 4f
Table 4 Determined values of the components of the susceptibility tensor Tensor component or isotropic combination xxz yyz xyz yxz zzz zxx zyy zxy xyz À yxz xxz þ yyz zxx þ zyy The magnitudes are referenced to quartz (0. Langmuir–Blodgett films of the chiral material were prepared.18 À þ À þ À þ À À À þ À i0. A chiral. are dependent not only on the nonlinear susceptibility components and the angle of incidence y. The sample had a C2symmetry. wzxx þ wzyy . First.5 24 26 3.42 2.33 i11. The secondharmonic signal was recorded as a function of the azimuthal rotation angle. A measurement technique was presented in [35]. The question was now how to distinguish between circulardifference effects arising from anisotropy and the chirality of the sample.93 2. The results show that the chiral part of the nonlinearity completely dominates the response of the sample. which describe the nonlinear response. wxxz þ wyyz and the chiral isotropic combination is wxyz À wyxz .0 1.136
S.18 1. anisotropic film with C2symmetry was prepared from a helicene bisquinone.16 i20. the circulardifference effects are expected to change sign as the handedness is changed.9 50 2.52 60. 50 Hz) generated the secondharmonic light at 532 nm. but also on the azimuthal rotation angle f.62 Magnitude (pm/V) 1.16 i0. It can be shown in general that Àf þ g or h. gi.13 i1. the symmetry of the films was determined. one must be concerned about the possibilities of magnetic contributions to the nonlinearities. 11. The experiments were performed on a Langmuir–Blodgett film of a nonracemic helicene shown in Fig.8 2. The pattern indicated that film had a C2symmetry.7
(66)
.3 pm/V).44 i2.76 7. Because the material is chiral. A second way to distinguish between circulardifference effects arising from chirality of the material and the chirality present in the setup is to examine SHGCD as a function of the azimuthal rotation angle f [36]. Sioncke et al. polarization measurements can be used to calculate the values of the tensor components. As mentioned earlier.59 4.8 2. The achiral isotropic combinations are wzzz. 8 ns. $1 mJ.60 3. The fundamental beam of a Qswitched Nd:YAG laser (1064 nm. However.62 i1.74 i1.84 À32. Polarization measurements were done for three different azimuthal rotation angles f (0. First.09 À4.0 3.40 i1. and hi. / Materials Science and Engineering R 42 (2003) 115–155
The theoretical origin of these results can be found in the fact that the expansion coefficients fi. Two possible solutions were put forth. Because of the anisotropy of the sample.02 i9. The measurement technique proposed in [35] is based on these polarization measurements. taking into account that the equations of fi. but not both reverses sign under reflection operation. Results 1. Only certain combinations (also shown in Table 4) are isotropic and can be uniquely classified as chiral or achiral. one can do a full analysis of the tensor components. gi and hi will depend on the azimuthal rotation angle f. Hence.
is large compared to the total variation (30 on the scale in Fig. 12. Sioncke et al. 11. As a consequence the average of Eq. the circulardifference response reduces to DI ¼ b0 sin 2f þ d0 sin 4f (67)
where b0 and d0 are coefficients that depend on the susceptibility components and the angle of incidence y. (66) is not. which provides a way to differentiate nonlinear optical CDeffects originating from chirality and those originating from anisotropy. depends on the azimuthal rotation angle f. We measured the CDresponse as a function of the azimuthal rotation angle f.S. while that of Eq. (67) over 3608 is always zero. a. 12. a1. b. One can conclude that chirality of materials is linked to a nonzero rotational average for DI. As a conclusion. that is isotropic. 12). This value represents the isotropic part of the response and implies that the sample is chiral. Helicene bisquinone. the CDeffects arise from the
120 90
CDSHG
60 30 0 30 60 0 50 100 150 200 250 300 350
Azimuthal rotation angle φ
Fig. / Materials Science and Engineering R 42 (2003) 115–155
137
OC 12H 25
C12H25O
S
O
C12 H25O S C12H25O
O O O
Fig. The sinusoidal variation indicates that the sample is highly anisotropic. In the case of a sample with inplane isotropy. a1.
. Circulardifference response in SHG as a function of the azimuthal rotation angle (the 08 orientation is arbitrary). the CDresponse averaged over 3608. It is comprised of a component that varies sinusoidally superimposed on one. This expression implies that the circulardifference response DI. c. and d are functions of the susceptibility components and of the angle of incidence y. The resulting pattern is shown in Fig. Moreover. (66) and (67) is the absence of the isotropic part a1. An important difference between Eqs. It is always important to determine the symmetry of the sample and then to interpret the results measured. it is clear that CDeffects in secondharmonic generation have to be handled with care. The average of the CDresponse over 3608 is 30 represented by the line.
where the coefficients a1. If the sample would be achiral and consequently have a C2vsymmetry.
10 binaphthyl molecules (Fig. The circulardifference effects DI/I reached values as high as 100% and the SHGCD spectra also resembled the (linear optical) CDspectra. the observed CDeffects had the same magnitude but opposite sign for the enantiomers.10 binaphthylbased helical polymer. Sioncke et al. 13) adsorbed at an air–water interface [27]. In the case of an anisotropic sample. They studied SHG from a chiral 2. aggregation of molecules which enhances SHGCD. However. They noticed that the SH intensity was different for left. SHGCD: a tool to probe surface chirality The first experimental evidence of SHGCD came from PetralliMallow et al. Possible explanations such as. 13. as far as there is no misalignment of the polarizer. but it was only in later publications that SHGCD was perceived as arising from the interference between chiral and achiral components within the electricdipole approximation [45]. 14).
. different absorption of the two circularlypolarized beams due to linear circulardichroism. were put forth. contributions of magneticdipole and quadrupole interactions originating from the bulk. The SHG signal from the surface was recorded versus wavelength in the reflection geometry.10 binaphthylbased monomeric units and optimized for nonlinear optics by adding a pconjugated bridge and electron donor and acceptor groups (Fig. More recently. at that time they were no explanation could be given for the and origin of the SHGCDeffect.20 Dihydroxy1. The polymers used in the study were prepared from chiral 1. 2.138
S. Chiral 1.10 binaphthyl. The monomer units can be considered as an ensemble of rigid
Fig.20 dihydroxy1.10 binaphthylbased helical polymer were studied [46]. CDeffects in the nonlinear response are no direct evidence of chirality of the sample: one should determine the tensor components or investigate the CDresponse as a function of the azimuthal rotation angle f. 14. 4. Langmuir–Blodgett films of a chiral 1.
chirality of the sample. using a circularlypolarized fundamental beam. Furthermore.and rightcircularlypolarized light. / Materials Science and Engineering R 42 (2003) 115–155
HO
OH
Fig.5.
Also the presence of a small (but nonnegligible) chiral component xyz reflects the chirality of the film. Both materials form Langmuir–Blodgett films with C1symmetry. There was no evidence of magnetic contributions to the nonlinearity. Note the peculiar structure of the molecules: chirality and nonlinearity are present on different levels of the molecular structure. zxx and xxz suggest favorable ordering of the chromophoric parts of the polymer in the LB film. Chirality is localized in the helical backbone of the molecule. Furthermore.48]. achiral chromophores. 4. Using the procedure of continuous polarization measurements. the absolute magnitude of each component was calibrated using a quartz wedge (Table 5). The samples were analyzed by a series of continuous polarization measurements in reflection and transmission geometry.S. Sioncke et al. Moreover. The first observation of magneticdipole contributions were observed from the films of chiral polyisocyanide and polythiophene. The chirality of the LB film manifests itself in the observed SHGCDeffects. The largest nonlinear magnetic susceptibility was found to be of the order of 10% of the largest pure electric susceptibility. we were able to characterize the complete susceptibility tensor. The high values for the components zzz. Evidence of strong magnetic contributions in chiral polymers Significant magnetic contributions to the nonlinearity of thin films of some chiral polymers have been observed. Polyisocyanide described in [50]. Strong circulardifference effects and strong asymmetric polarization patterns are an indication of chirality of the sample.6. It is believed that there exists a strong coupling between the backbone and the
C n N H 3C CH CH2 O C R O
R
N N NO2 N
C4H9
C4H9
Fig. the results could not be explained within the electricdipole approximation and we had to include magnetic contributions. / Materials Science and Engineering R 42 (2003) 115–155
139
Table 5 Absolute values of the secondharmonic susceptibility components of the binaphthylbased helical polymer and classification of the components as chiral or achiral Secondorder susceptibility component xyz xxz zxx zzz Absolute value (pm/V) 2 7 5 35 Chirality classification Chiral Achiral Achiral Achiral
electricdipole units that form a propellerlike threedimensional conformation due to the chirality of the binaphthyl units [47. The polyisocyanides investigated are shown in Fig.
. while the nonlinearity is localized in the pendant. 15. Chirality and nonlinearity are not present on the same level of the molecule although chirality effects are observed in the nonlinear optical response [50]. 15 [49].
Films of a similar polyisocyanide mixed with poly(S1acetoxymethylethyl isocyanide) (Fig. more research is needed to prove this hypothesis. However.00 0. the largest magneticdipole component of this system would be approximately 2 pm/V.15 0.
chromophores.62 0. / Materials Science and Engineering R 42 (2003) 115–155
O C n N H3C CH CH2 O C R O NO2 R N N N CH2 CH2 O C O CH3 CH2 CH2 O C CH3
Fig. Analysis of the polarization pattern allowed the determination of the relative amplitudes of all electric.13 0.01 0. Therefore.140
S.and magneticdipole susceptibility components (Table 6).23 0.00 0. 16) were analyzed in detail [51]. A simultaneous excitation of the NLO chromophores leads to a helical charge displacement along the backbone of the polymer. Polyisocyanide described in [51].60 0.
Table 6 Relative magnitudes of the components of weee.08 0. The absolute value of the electricdipole component zzz of Langmuir–Blodgett films of a similar polymer system was determined to be of the order of 9 pm/V [52]. 16.03
weem
wmee
.12 0.06 0. and wmee for the poly(isocyanide) mixed with poly(S1acetoxymethylethyl isocyanide) Tensor w
eee
Components zzz zxx ¼ zyy xxz ¼ xzx ¼ yyz ¼ yzy xyz ¼ xzy ¼ Àyxz ¼ Àyzx zzz zxx ¼ zyy xxz ¼ yyz xzx ¼ yzy xyz ¼ Àyxz zxy ¼ Àzyx xzy ¼ Àyzx zzz zxx ¼ zyy xxz ¼ xzx ¼ yyz ¼ yzy xyz ¼ xzy ¼ Àyxz ¼ Àyzx
Chirality Achiral Achiral Achiral Chiral Chiral Chiral Chiral Chiral Achiral Achiral Achiral Chiral Chiral Chiral Achiral
Relative amplitude 1. This indicates that magnetic contributions to the nonlinearity are not negligible and that optimization of the secondorder nonlinear response can be made throughout the magnetic contributions. Sioncke et al. Important to note is that the largest magnetic component is 20% of the largest electric component and that the largest magnetic component is associated with chirality.06 0.00 0. It is still unclear why the magnetic nonlinearities play such an important role in these specific molecules. The reason could be that in these films the chromophores that are responsible for the nonlinear response are randomly distributed which suppresses the electricdipole nonlinearity. weem.05 0.
due to the instability of the sample. The results are shown in Table 7. The chiral magneticdipole contributions were of the same order of
* Et2N
+
N * OH

ClO4
Fig. The sample studied was a ten layer Langmuir–Blodgett film of the regioregular chiral polythiophene poly[3[2((S)2methylbutoxy)ethyl]thiophene] [54. To prepare the Langmuir– Blodgett films. From these data they extracted the relative values of the tensor components. [56] studied spincoated films of the chiral dye shown in Fig. in poor solvents. 18 and separated the electric. An analysis of the spolarized secondharmonic signal provided clear proof of the presence of the strong magneticdipole contributions (same order of magnitude as the electric contributions) in the nonlinearity of the films.and the magneticdipole contributions to the nonlinearity. the polymer is dissolved in chloroform (in which the polymer is in a random coil) and spread on a water surface. Upon evaporation of the solvent. However. in the solid state.S. They performed continuous polarization measurements and determined the SHGCD and SHGLD values. the polymer folds into the chiral conformation and changes color from yellow to purple. This association with a chiral conformation is accompanied by a strong solvatochroism and the films have a purple/red color (lmax ¼ 512 nm).55]. 17) [53]. 18. weem. the authors were not able to determine absolute magnitudes of the components of weee. Sioncke et al. The stars indicate the asymmetric carbons. while the random coil conformation has an orange/yellow color (lmax ¼ 445 nm). They also measured SHGORD. SchanneKlein et al. Chiral polythiophene. Chemical structure of chiral penthamethinium salt. like CHCL3.
. or in appropriate combinations of solvents. Unfortunately. the polymer is associated in small domains and the chiral side groups induce an enormous optical activity in the p–pÃ transition of the polythiophene.
Evidence of high magneticdipole contributions to the nonlinearity has also been found in Langmuir–Blodgett films of a chiral poly(thiophene) (Fig. / Materials Science and Engineering R 42 (2003) 115–155
141
CH3
O
S
n
Fig. The SHG from the films was measured by continuously varying a quarterwave plate in the path of the fundamental beam (1064 nm). the polymer is in a random coil conformation and does not exhibit optical activity in its p–pÃ transition of the polythiophene. and wmee. In good solvents. The magneticdipole contributions observed in these LB films are of the same order of magnitude as the electricdipole nonlinearities. 17.
bmee /
z'
io e3 ra zb c m2
with a þ b ¼ 4
(68)
eρ x'
ζ
y'
Fig.00 0. and therefore the dipolar electric nonlinearities are not expected to be strong. beee. 18 Tensor component weee zzz weee zxx weee xxz weee xyz 2weem xxz Chirality Achiral Achiral Achiral Chiral Chiral Relative magnitude 1. The helical motion of the electron causes optical activity in the secondorder response.
. but also the macroscopic secondorder response (characterized by the nonlinear susceptibility w) of both surfaces and solutions of chiral molecules. These conclusions were also drawn from the theoretical approach of the nonlinear optical activity. beem . We can conclude that optical activity can occur in surface secondharmonic generation from the electriconly response.03
þ wmee zxx
magnitude as the chiral electricdipole contributions: weem % wmee . The dipolar electric contributions arise from the pelectrons on xyz the carbonyl chain but they are not strongly delocalized between the two nitrogen atoms. weem.080 0. Maki and Persoons calculated the oneelectron secondorder optical activity of a helix [26]. these components have typically xxz zxx the same order of magnitude as weee . The previous experiment illustrates the relative strength of electric.012–0. Sioncke et al. Electron bound to a helical path of radius r and pitch z. / Materials Science and Engineering R 42 (2003) 115–155
Table 7 Relative magnitude of the components (or combination of components) of weee. These experiments provided evidence that the magneticdipole contributions can be important even in nonresonant conditions (the dye does not absorb at the secondharmonic wavelength). but we find that the magnetic response can make a similar contribution and thus should not be ignored.018 0.310 0. beem and bmee can be written as a function of the pitch (z) and the radius (r) of the helix: beee / e3 ra zb m2 with a þ b ¼ 3. The optical response is classically modeled by using a single electron bound to a helical path (Fig. 19. From the equations for b and w one can see that the magnetic contributions are enhanced in a helical molecule. That is probably the reason why magnetic effects are as strong as dipolar electric ones concerning the chiral components.and magneticdipole transitions in secondorder optical activity. The microscopic secondorder response is (characterized by the hyperpolarizability b) calculated for a chiral molecule. and wmee for the chiral compound in Fig.142
S. 19).
beem and bmee depend on r and z with an overall order of 4. for chiral molecules. Experiments were also performed on the diastereoisomer BocLTrpDTrp. Tryptophan gives the strongest SHG signal. spolarized second harmonic). There is a significant difference in the SHG signals observed for left. the dipeptide BocTrpTrp. $20 mJ) operating at wavelengths between 550 and 580 nm was used to record the SHGCDresponse. SHGORD spectra were measured between 276 and 286 nm. [57] explored the possibilities of this technique to study biological systems. The sign of the ORD of the LL form was opposite to that of the DD form. The SHGORD wavelength dependence of the BocLTrpDTrp is similar to the LL and DD forms but the magnitude of the rotation angle is approximately twice that observed for the LL and DD isomers. beem and bmee are the molecular analogues of weee. Achiral molecules adsorbed at the air–water liquid interface give rise to no SHG signals from the polarization combination p–s (ppolarized fundamental. The air–water interface of aqueous (tbutyloxycarbonyl)tryptophantryptophan (BocTrpTrp) has been studied by surface SHGCD (Fig.S. 20). 4. The molecular hyperpolarizability bxyz is expected to be zero since tryptophan chromophore is planar. shows significant SHGCD and SHGORD. and phenylalanine) using 532 nm fundamental radiation. However. a nonzero p–s signal can be observed. In these experiments. The DD form of the BocTrpTrp gives a SHGCDresponse of equal magnitude but opposite sign compared with the response of the LL form of the same molecule. SHG has already been observed for some amino acids (tryptophan. The 50/50 racemic mixture gave no SHGCDresponse. 10 Hz. However. / Materials Science and Engineering R 42 (2003) 115–155
143
O H2N CH C HN CH2
O CH3 CH C O C CH3 CH3 CH2
HN
HN
Fig. The SHGCD signal can be explained by the presence of the tensor component wxyz. As a consequence.7. Biological systems studied with SHGCD SHGCD is a surface sensitive technique and can be used to study interfaces and surfaces.
. Chemical formula of (tbutyloxycarbonyl)tryptophantryptophan. Crawford et al. the rings are tilted with respect to each other (like the two rings in binaphthol). from the surface of aqueous solutions [58]. tryptophan did not show any secondharmonic optical activity. m and e are the mass and the electric charge of the electron. In contrast. Sioncke et al.and rightcircularlypolarized fundamental incident radiation and ppolarized SHG radiation. The beam was incident at the liquid surface at 608 to the surface normal. beee. a Nd:YAG pumped dye laser (5 ns. The SHGCDeffect increases towards longer wavelengths (for pdetection). The macroscopic response (w) can be found by averaging the microscopic response for the various orientations of the helix in space. on the other hand.
where beee. weem and wmee. and over the 270–300 nm region for tryptophan and tyrosine. tyrosine. This will in turn lead to a nonzero wxyz term. The SHGCDresponse reached values near 150% at 276 nm. depends on r and z with an overall order of 3. o is the frequency of the applied fundamental field. being chiral. which explains a significant molecular hyperpolarizability bxyz of the dipeptide. which can only be nonzero for chiral surfaces. the magnetic contributions increase more rapidly than the electric when the molecule has more helical character. In the BocTrpTrp molecule. 20.
HBMs are electrically addressable using a underlying gold film as working electrode. on hydrophylic SAM and on hydrophobic SAM. as is consistent with the sensitivity of SHG to the chirality of the heme. In the purple membrane. The SHGCDresponse for spolarized detection at 798 nm was studied for cytochrome c adsorbed at three surfaces: HBM. the film constitutes an isotropic surface with full rotational symmetry about the surface normal. These samples also exhibit a strong circulardifference response. more practical. the molecules are randomly distributed on a scale much smaller than the optical wavelength. This inhomogeneity is most likely an indication of aggregation of the purplemembrane fragments. The laser system used for the SHGCD studies consisted of a modelocked titaniumsapphire (TiS) laser (150 fs. Cytochrome c is an interesting redox species due to its membraneassociated activity and its biological role in electron transport. horse heart cytochrome c. which for the spolarized signal is $100%. Sioncke et al. When cytochrome c adsorbed on the SAMs it was reduced by adding an excess ascorbate. Bacteriorhodopsin also exhibits strong nonlinear optical activity. resulted in a
. In spite of this local ordering. adsorbed at several model membrane surfaces [60]. $5 nJ/pulse) pumped by a beamlocked argon ion laser. In the films. the SHGCDresponse DI/I of cytochrome c is negative. Hybrid bilayer membranes (HBMs) have been shown to have many properties of cell and model membranes. a drop of purple membrane suspension in water was placed between two glass slides. types of samples. 21. the spolarized SHGCD became more positive. The SHGCDresponse is shown to be affected by the oxidation state of the heme within the surfaceadsorbed cytochrome c. In contrast. First. Hence. Linear circulardichroism spectra of suspensions of purple membrane in water typically show a relative circulardifference effect of De=e ¼ 0:1%. cytochrome c forms a stable and electroactive layer that is reducible by applying an electrode potential or by the addition of a reducing agent to the solution. / Materials Science and Engineering R 42 (2003) 115–155
+ N H
Lys
Fig. The circulardifference effect was about 25%. To assess the usefulness of the effect for other. In such a film. This technique results in samples for which the overall efficiency of secondharmonic generation depends on the spot on the sample that is illuminated by the laser. The incidence angle used was in the range of 45–518 from the surface normal. For the spolarized component. the bacteriorhodopsin molecules were embedded in a Langmuir–Blodgett film. Bacteriorhodopsin is a lightenergytransducing protein that is present in the purple membrane of halophilic bacteria. 21).
Another biological molecule probed with SHGCD is bacteriorhodopsin [59] (Fig. the bacteriorhodopsin molecules can exhibit local ordering in a lattice similar to the one that occurs in the purple membrane. Chemical formula of the optically active part in bacteriorhodopsin. At carboxylic acidterminated selfassembled monolayers (SAMs). The very strong circulardifference response is due to supramolecular chirality of bacteriorhodopsin trimers. The secondharmonic generation of the ppolarized transmitted component was dependent on the helicity of the fundamental beam. the introduction of ascorbate to cytochrome c adsorbed at the HBM surface. the protein is arranged into clusters of three that show stronger optical activity than individual molecules. In the oxidized state. the circulardifference effect was about 13%. The bacteriorhodopsin sample was analyzed using continuous polarization measurements. the bacteriorhodpsin molecules were in a soya phosphatidylcholine matrix in a molar ratio of 1:28. SHGCD has also been used to follow the adsorption and redox properties of a peripheral membrane protein.144
S.
Therefore. and eventually return to their original isotropic centrosymmetric state [19]. and they depend on all three spatial coordinates. 22. Unfortunately. The sample has only axial. For example. the polymer film is heated to its glass transition temperature and a strong static electric field is applied to orient the chromophores in the polymer matrix. (a) A thin film with C1symmetry. Consequently. Sioncke et al. The SHGCD is consistent with results reported in literature that indicate that cytochrome c is reducible by ascorbic acid when associated with hydrophobic or negatively charged monolayers. spincoated films. it would be beneficial to relax the requirement of polar ordering along the film normal. 4. Any rotation about the film normal is a symmetry operation. reflections in a plane containing the normal and in the plane of the film are also symmetry operations. Such films have axial ordering along the surface normal. the polymer film is cooled below Tg in the presence of the field. one can then rely on ytype deposition of Langmuir–Blodgett films. In addition. respectively (Fig. When the molecules are achiral. Then. where transfer occurs both at up and down strokes. poling can be quite complex and time consuming. etc. Any rotation about the film normal is a symmetry operation. will easily aggregate due to dipole–dipole interactions. 1808 rotation about any axis in the plane of the film is a symmetry operation.
. Furthermore. the electricdipole tensor vanishes unless the sample is chiral. (b) A thin film with D1symmetry. The sample has polar order along the film normal but the orientational distribution of the molecules is isotropic in the plane of the film. This aggregation will reduce the efficiency of the poling process [61–64]. When the molecules are achiral. This work demonstrates the potential for SHGCD studies of native biological surfaces. One of the most widely used methods to induce macroscopic noncentrosymmetry is electricfield poling of nonlinear optical polymers. The symmetry groups of chiral and achiral samples are D1 and D1h. reflection in the plane containing the normal is also a symmetry operation. The D1. The polymer containing a nonlinear optical chromophore is spincoated on a substrate. The nonvanishing tensor components for these groups are listed in Table 8. Subsequently. Chromophores with high dipole moments embedded in a polymer matrix. adsorbed at surfaces.and D1hsymmetry can also be found in other systems: liquid crystals. respectively (Fig. to freeze in the orientation.
(a)
Film normal
(b)
Film normal
Twofold rotation axis
Fig. / Materials Science and Engineering R 42 (2003) 115–155
145
negative SHGCDeffect. The result suggests that HBMassociated cytochrome c is not reduced by ascorbic acid.S. Chirality as a tool for nonlinear optical applications The requirement of noncentrosymmetry in nonlinear optics can be achieved in several ways. cytochrome c.8. One of the obstacles of efficient poling is the aggregation of chromophores. However. The symmetry of such films is C1 and C1v for chiral and achiral samples. but no polar order. but not when they are bound to mixed lipid layers containing zwitterionic and negatively charged phospholipids. 22b). 22a). This work demonstrates for the first time that SHGCD can be used to probe the oxidation state of a redox protein. chirality allows electricdipole nonlinearities without polar order. Removal of polar ordering results in a sample with twofold rotation axis in the plane of the film. poled films are thermodynamically unstable.
it is clear that the p–s signal is due to the
O O
O
O
H25C12O
OC12H25
OC12H25
OC12H25
Fig. These fibers comprise columnar stacks of helicene molecules. Similar columnar stacks form in appropriate solvents when the concentrations are greater than $1 mM. corresponding to a $30fold enhancement in the value of the susceptibility. Tetrasubstituted helicenebisquinone. 23. 23 [65]. a symmetry that also lacks polar order. (48). prepared LB films of a chiral helicene. The molecules studied were those of the tetrasubstituted helicenebisquinone. In bulk samples the enantiomerically pure form of the material spontaneously organizes into long fibers clearly visible under an optical microscope. When examining Eq. In a recent study. shown in Fig. / Materials Science and Engineering R 42 (2003) 115–155
Table 8 Nonvanishing components ijk of tensors weee. Sioncke et al. CD spectra and atomic force microscopy (AFM) clearly showed that the helicene bisquinone was present in its aggregated form in both racemic and nonracemic films [65. This formation of aggregates is associated with an increase in the circulardichroism of the solution [66]. whereas. Although. the symmetry of the film was very close to D2. A clear difference between the nonracemic and racemic films was observed in their SHG properties: the strongest SHG signal from a onelayer nonracemic film was approximately 1000 times as intense as that from a similar racemic film. for the racemic film the p–p signal was the strongest. In fact. Langmuir–Blodgett films were made of the helicene by spreading a dilute chloroform solution (2 Â 10À4 M) onto the pure water subphase of an LB trough.146
S. the experiment definitely proved that polar order is not a necessary requirement for secondorder nonlinear optics. UVVis absorption spectra. Good optical and structural quality of the films was confirmed through the quadratical growth of the SHG signal with the thickness of the sample. while the racemic form does not aggregate. The samples were analyzed by a series of continuous polarization measurements. and wmee for achiral and chiral thin films with inplane isotropy and only axial ordering along the film normal (D1h and D1 groups) Susceptibility tensor w
eee
Achiral D1h –
Chiral D1 xyz ¼ Àyxz xzy ¼ Àyzx zxy ¼ Àzyx xyz ¼ Àyxz xzy ¼ Àyzx zxy ¼ Àzyx
weem and wmee
xyz ¼ Àyxz xzy ¼ Àyzx zxy ¼ Àzyx
Films with D1symmetry can in principle be made by the Langmuir–Blodgett technique. The strongest signal for the nonracemic film was p–s (ppolarized fundamental and spolarized SHG).
. Verbiest et al. the symmetry of the film was not a perfect D1symmetry. Subsequently. weem. the layer was compressed to a surface pressure of 20 mN/m and transferred to a hydrophobic glass substrate by horizontal dipping.67].
Above the melting point. For an spolarized fundamental beam no secondharmonic signal was detected.or D1symmetry. Continuous polarization measurements were carried out on the samples. The nonlinear optical response of the nonracemic films was dominated by the combination: xyz–yxz. To investigate these possibilities the authors first had to analyze the susceptibility components of the two films. / Materials Science and Engineering R 42 (2003) 115–155
147
Table 9 Absolute values of chiral and achiral rotational invariants of the susceptibility of the nonracemic LB films of the helicene bisquinone Rotational invariant zzz xxz þ yyz zxx þ zyy xyz À yxz Absolute value 6 2 4 50 Chirality Achiral Achiral Achiral Chiral
components of the secondorder susceptibility tensor that are nonvanishing only in the presence of chirality.
. relaxation cannot occur. Sioncke et al. As the nonracemic films showed SHG response. The high magnitude of the chiral susceptibility. Moreover the films showed good thermal stability over a wide range of temperatures. The magnitude of the chiral combination xyz–yxz is within one order of magnitude of the highest values ever observed in LB films. makes this is a promising material for device applications. The p–p signal is allowed for all isotropic surfaces and thus is due to the achiral tensor components. This implies a D1symmetry with only one nonvanishing tensor component wxyz. This experiment again illustrates the potential of chiral materials in NLO. An explanation for the different behavior of the two types of samples is that the helicene packs differently in the racemic and nonracemic films. the symmetry of the films had to be at least D1. Note that the NLO response of LB films is usually dominated by the zzz component. Because no polar order had to be introduced by an external force. To discriminate between those two. the dominant part of the susceptibility can be associated with chirality. In another experiment.and ydirections are arbitrary. All the rotational invariants were determined by analyzing SHG polarization patterns. This result implies that for the nonracemic sample. In the racemic samples. combined with the good thermal stability (stable up to 2008). No evidence was found of the presence of magneticdipole contributions. while in racemic films they cancel. yielding films of 0. Heating the films up to 200 8C did not affect the SHG efficiency. only the spolarized secondharmonic was nonvanishing.1–0. The reason for this is that for a surface with a twofold symmetry the x. This combination is associated with chirality.S. They had to examine combinations of susceptibility components. The exact symmetry was determined by detecting the SHG signal while rotating the sample about its surface normal. these nonlinearities add up. From UVVis absorption spectra it was seen that the molecules selfassembled in corkscrewshaped structures [67]. For the ppolarized fundamental. films of a similar helicene derivative were spincoated onto glass substrates.6 mm. In films made of the pure enantiomerically material. The advantages of such films are clear. The reason for the high nonlinearity of the supramolecular structure was attributed to the formation of supramolecular aggregates with high nonlinearity. the material becomes an isotropic liquid and the SHG signal drops to zero. this part must cancel. which are invariant under rotation operations around the surface normal and are given in Table 9. The analysis was not straightforward because the film exhibited twofold symmetry. polarization combinations of the fundamental and secondharmonic were analyzed. The magnitude of the component was determined to be 2 pm/V. The films were isotropic in the plane which corresponds to a C1.
wzxx ¼ ðÀ0:58 À i0:002Þ pm/V. The SHGCDresponse which is depended on chiral and achiral components. the symmetry should be D1. As a result the mixtures exhibit a chiral discotic nematic phase [68]. 24.13 pm/V. When an electric field was applied to the cell. The solution (1. 20 wt. Rotating the sample about its surface normal did not change the magnitude of the secondharmonic signal. It is also notable that when the polarity of the field is reversed. The samples were probed by continuous polarization measurements.148
S. wxxz ¼ À0:47 pm/V. spolarized secondharmonic). the values of the polar tensor components change sign while the sign of the apolar tensor component remains unchanged. The result is that additional polar tensor components appear: wxxz. and wzzz ¼ ð1:22 þ i0:1Þ pm/V. The magnitude of the component was measured and compared to a quartz reference (d11 ¼ 0:3 pm/V) and was 0. / Materials Science and Engineering R 42 (2003) 115–155
R'O R'O O RO O
OR' OR + R'O O
O R' RO O
OR' OR
R= O
R' = C12 H25
Fig. These were remarkable results because spincoating results used in isotropic films. When switched off.5 when applying the electric field. it is nonvanishing in samples without polar order. A headtotail aggregation of the molecules is favored by the steric hindrance of the bulkier ends that keeps the molecules apart. In Fig. The ability to reverse the sign of the tensor components can be used in quasiphasematching to prepare efficient frequencyconversion devices.
Nevertheless. Binary mixtures of isomeric nonracemic (M)(À)helicenes shown in Fig. For the same reasons mentioned above. Another illustration of the potential of chiral molecules in NLO is given by the following experiment. Note that this effect cannot be observed in linear optics since the refractive index cannot change sign. wzxx ¼ ð0:59 þ i0:03Þ pm/V. and wzzz ¼ ðÀ0:78 À i0:015Þ pm/V. wxxz ¼ 0:51 pm/V.
. This is explained by the fact that only the achiral components change sign under reversion of the polarity of the electric field. cooling the liquid restores the initial symmetry and the original SHG values are detected. will change sign when the polarity of the applied field is reversed. Chemical structure of chiral liquid crystal. the signal decreases again to the original value. The only nonvanishing component for this system is the chiral wxyz component: this is an apolar component. 25. The D1symmetry can be explained by the organization of the molecules in liquid crystallinelike layers that stack together. The magnitudes are unaffected within the experimental errors. Sioncke et al. The only secondharmonic signal detected was the p–s signal (ppolarized fundamental. wzxx and wzzz. For the spolarized component of the secondharmonic field. The applied electric field was þ10 V/mm.% dissolved in dodecane) was placed between a rubbed 4 mm LC cell at room temperature. the symmetry of the sample changed from a nonpolar D1 to a polar C1. wxyz ¼ ðÀ0:64þ i0:15Þ pm/V. 24 and dodecane tend to form liquid crystals. the CDresponse changes from À43 to þ45%. The values of all tensor components were measured and calibrated against a quartz reference: wxyz ¼ ðÀ0:68 þ i0:16Þ pm/V. one can see that the total signal increases by a factor 3.
all experiments above are proof that chiral samples without polar order can exhibit nonlinear optical activity. In this procedure. an external electric field can increase the existing signal by introducing a polar order. 25. Because of some limitations. for example. Plot of the secondharmonic signal intensity (I(2o).u. is frequently used. / Materials Science and Engineering R 42 (2003) 115–155
149
3000
Secondharmonic intensity (a. 4. Consequently. because refractive indices of materials change with the wavelength. phaseshifters and quasiphasematching are possible applications for this system. The interaction must be phasematched. the source polarization and generated field are outofphase. after a distance Lc ¼ p/jDk j.9. known as the coherence length.
To conclude. an alternative to perfect phasematching. In secondharmonic generation. for the chiral liquid crystal. Because no external force is needed to introduce a Dnsymmetry. in arbitrary units) vs. Phasematching is hard to realize. optical switches. because their refractive indices depend on the polarizations of the interacting fields. these films are thermodynamically stable which is a great advantage over poled polymer films which tend to relax in time. Because the reversibility of the effect and the ability to change the sign of the polar tensor components by reversing the polarity of the external field. the signs of the nonlinear optical coefficients are reversed after every coherence length. Phasematching can be achieved in birefringent materials. Sioncke et al. the wave vectors of the fundamental and secondharmonic beams ko and k2o are proportional to the indices no and n2o at the two frequencies. time t. or after any odd multiple of it. Because for enantiomers the nonlinear coefficients associated
. known as quasiphasematching. Quasiphasematching in chiral materials In order to detect a secondorder nonlinear response from a material. the material has to be noncentrosymmetric and the nonlinear source polarization and the generated field must propagate through it in phase.)
2500 2000 1500 1000 500 0 t1 t2
0
100
200
300
400
500
600
700
800
Time (sec)
Fig.S. This restores the phase relation between the source polarization and the generated field. allowing the nonlinear signal to grow quasicontinuously. In addition. The phase (or wave vector) mismatch for copropagating fundamental and secondharmonic beams is thus Dk ¼ 2ko À k2o ¼ 4pðno À n2o Þ lo (69)
where lo is the fundamental wavelength. At time t2 the field was switched off.
this work is an example of the possibility to create completely new frequency converters. and repeating the sequence if necessary. According to the above equation. in which the sign of the secondorder nonlinearity alternates. Here the quasiphasematching is a consequence of the chirality of the material and it was established in reflection symmetry. The experiments were analyzed by considering a model for the structure that consists of p stacks. Magneticdipole nonlinearity from chiral materials in solution Strong evidence of magneticdipole contributions have been observed from chiral films and it is clear that the nonlinear optical response can be enhanced through the magneticdipole transitions. Sioncke et al. Multilayers were prepared by depositing a stack with a given number of molecular layers of the (P)(þ)enantiomer.150
S. The growth should be quadratic when the material does not absorb the secondharmonic light (a ! 0). Busson et al. a series of films were prepared with two stacks. The secondharmonic amplitude E2 along the zdirection is given by the following equation: E2 ðpLÞ / G 1 À eÀðaþi DkÞL Â ðeÀapL À ðÀ1Þp ei DkpL Þ a þ i Dk 1 þ eÀðaþi DkÞL (70)
where G is a constant numerical factor proportional to the squared amplitude of the fundamental beam. quasiphasematched frequency conversion should be possible in periodically alternating stacks of enantiomers [69]. the output intensities from a series of films with a fixed number of stacks p. where L reached the coherence length. However. quasiphasematching should be limited neither to this process nor to this geometry. and Dk is the wave vector mismatch. The secondharmonic intensity was somewhat less than quadratic only because the samples absorb light at the secondharmonic wavelength. and 6 stacks. It is clear that quasiphasematching can be achieved by making structures consisting of stacks of chiral molecules where the two enantiomers alternate. prepared such alternating stacks of enantiomers and demonstrated that they can be used for quasiphasematched secondharmonic generation. but with increasing thickness L. However. a new series of samples was prepared with 1–4. following it by a stack with the same number of layers of the (M)(À)enantiomer. 4. p ¼ 2 (P/M) and a series of films with p ¼ 4 (P/M/P/M). each of thickness L. First.10. A drawback is that a very large number of layers is needed to attain the thickness of even one coherence length. Nevertheless. The problem is that there is no wellestablished theory of the relationship of molecular structure and magneticdipole susceptibilities. the intensity is expected to grow with the number of stacks p. until L ¼ Lc . There has been theoretical evidence that chirality favors magnetic
. are expected to grow until L ¼ Lc and then to decrease. The total number of molecular layers within the stacks was varied. and than decreased. / Materials Science and Engineering R 42 (2003) 115–155
with chirality are opposite in sign. When the thickness of each stack equals the coherence length. Than. Films were prepared by spreading 2 Â 10À4 M chloroform solutions of the enantiomers of the helicenebisquinone onto MilliQ water in a Langmuir–Blodgett trough. The advantage of the Langmuir–Blodgett technique is that the thickness of the stacks can be controlled to a precision of one molecular layer. A series of samples was investigated in which equally thick stacks of the two enantiomers alternated. a is the linear absorption coefficient at the secondharmonic wavelength. Quasiphasematching is verified by measuring the intensity of the secondharmonic signal associated with chirality as a function of the thickness of the stacks. One could see that the secondharmonic intensities grow with increasing thickness of the stacks. the coherence length is must shorter if the secondharmonic light is detected in the reflected instead of the more common transmitted direction.
However. This difference in phase between the z. In the presence of magneticdipole nonlinearities. 0Þ. Out of resonance the opposite is true. needed to detect SHG are introduced by applying an external electric field. In general. in resonance conditions.k
X Mi ð2oÞ ¼ wmee Ej ðoÞEk ðoÞ ijk
ijk
(73)
The subscripts refer to Cartesian coordinates in the macroscopic (laboratory) frame. the electric susceptibility components will differ in phase from the magnetic susceptibility components. but no experiment technique has been able to link molecular structure to the presence of strong magneticdipole contributions. we can define an effective polarization Peff(2o) [28. We take a chiral solution with a net orientation along the zdirection and the propagating laser beam along the xdirection and polarized in the zdirection. The nonvanishing susceptibility components are listed in Table 2. The zpolarized component originates from a pure electricdipole transition while the ypolarized component originates from a pure magneticdipole transition. We modified the classical EFISHG setup to investigate the magnetic contributions to the hyperpolarizability tensor. We will now apply these equations to a particular experimental setup.S. Electricfieldinduced secondharmonic generation (EFISHG) is a technique that measures the molecular hyperpolarizabilities in solution [71–74]. We recently proposed a new technique. There are four independent components for the weee and wmee tensors and seven independent components for the weem tensor. Sioncke et al. / Materials Science and Engineering R 42 (2003) 115–155
151
transitions [26]. The components of the electric and magnetic fields are EðoÞ ¼ Eð0. yzy Mz ð2oÞ ¼ wmee Ez ðoÞEz ðoÞ zzz (74) Hence. The noncentrosymmetry conditions. For this particular situation. The presence of
. 0. to analyze these molecular properties [70]. there is need for experimental methods to solve this fundamental question.75] Peff ð2oÞ ¼ Pð2oÞ þ c r Â Mð2oÞ i2o (71)
where the nonlinear polarization P(2o) and the nonlinear magnetization M(2o) can be written as X Pi ð2oÞ ¼ ½weee Ej ðoÞEk ðoÞ þ weem Ej ðoÞBk ðoÞ (72) ijk ijk
j. the electric susceptibilities weee are imaginary values quantities and the magnetic susceptibilities weem and wmee are essentially real [23.24]. The result is an SH signal rotated about a certain angle in comparison to the polarization direction of the incoming beam (zpolarized). based on EFISHG. the effective polarization is the source for the secondharmonic signal. The resulting solution has a polar order and SHG can be detected. zzz Py ð2oÞ ¼ weem Ez ðoÞBy ðoÞ. Ez Þ and BðoÞ ¼ Bð0.and ycomponent of the SH signal will result in elliptically polarized light. This would be the case if the electric and magnetic susceptibilities would have the same phase. the nonlinear polarization and magnetization that are able to radiate are Pz ð2oÞ ¼ weee Ez ðoÞEz ðoÞ. The symmetry of the solution is C1. it is clear that the secondharmonic will consist of a component polarized along the zdirection and one component polarized along the ydirection. By . Hence. the effective polarization becomes Peff ðoÞ ¼ weee Ez ðoÞEz ðoÞz þ ðweem þ wmee ÞEz ðoÞEz ðoÞy zzz yzy zzz (75)
Since.
The difference DI as a function of the angle of the quarterwave plate y. The susceptibilities measured. Sioncke et al.5 360
1
0
1 0.5 1 0. When the EFISHG cell is filled with a solution of chiral molecules with magnetic contributions. The beam is vertically polarized. In the second case (b) the ratio E2/E1 ¼ 0:3 and the phase difference f is taken to be p/4. A modified EFISHG setup can be used.5 0 0.5
1
∆I
∆I 0 60 120 180 240 300 Rotation angle θ of the quarterwave plate 2. the combination weem þ wmee is only nonvanishing in chiral materials and the detection yzy zzz of ellipticallypolarized light is therefore also an indication of the chirality of the material.
.and verticallypolarized components of this ellipticallypolarized light can be written as Ez ð2oÞ ¼ E1 eiot . Ey ð2oÞ ¼ E2 eiðotþfÞ (77)
2 2
1. can be related to their molecular hyperpolarizabilities weee ¼ Nf hbeee i. wmee ¼ Nf hbmee i (76)
where N is the number density of the molecules in solution and f the local field factor. A detection scheme has to be setup in order to detect ellipticallypolarized light. The horizontally.5 2 0 0 60 120 180 240 300 Rotation angle θ of the quarterwave plate 360
(a)
(b)
∆I
0
(c)
60 120 180 240 300 Rotation angle θ of the quarterwave plate
360
Fig. weem ¼ Nf hbeem i. The last curve (c) shows the situation where E2/E1 ¼ 0:05 and f ¼ p/4.5 2 1. A Nd:YAG laser (1064 nm) is incident on the EFISHG cell.152
S. / Materials Science and Engineering R 42 (2003) 115–155
ellipticity in the SH light is thus and evidence of magneticdipole contributions to the nonlinearity. the SH will be elliptically polarized. In the first case (a) there is no magnetic contribution (E2 ¼ 0). 26. Moreover.
5. it is clear that nonlinear optical activity is an extremely useful method to study surface chirality. (ii) is there a relation between the magnitude of the chiral susceptibility components and the magnitude of the traditional CD or ORD effects. In the first case (Fig. 26c) depicts the situation where E2/E1 ¼ 0:05 and f ¼ p/4. since the linear analogues such as CD and ORD are not surface sensitive. It can be clearly seen that the curve is highly asymmetric about the 1808 rotation axis. the curve is asymmetric. the study of enantiomeric excess obtained in asymmetric surface reactions and the determination of the enantiomeric excess in pharmaceutical products should help in establishing nonlinear optical activity as a powerful tool of research. from an experimental and theoretical point of view. Fig. Issues that have to be resolved: (i) what is the relationship between the magnetic susceptibilities and molecular structure. and can therefore be extremely useful in establishing clear structure property relationships in chiral materials.S. adsorption of racemic mixtures of molecules on chiral surfaces. However. The resulting curve is symmetric about the 1808 rotation axis of the quarterwave plate. The ellipticallypolarized light is then directed through a quarterwave plate which is varied continuously. Conclusion Secondharmonic generation from surfaces and thin films provides a new tool to study surface chirality. the technique still has to mature. Even if the magnetic contributions are 5% of the electric contributions. In addition. this modified EFISHG technique shows promise to evolve into a sensitive probe of magneticdipole contributions. From an experimental point of view. Moreover. Sioncke et al. the study of chiral nonlinear optical materials might lead to insights to design completely new materials for applications in the field of nonlinear optics and photonics. To conclude. The vertically. We gave an overview of the theoretical formalism to describe the nonlinear optical response of chiral surfaces and thin films and experimental procedures to study polarization rotation and intensitydifference effects in SHG from chiral surfaces. In the second case (Fig. To test this formalism.and horizontallypolarized light is resolved and detected by twophoto multipliers. the usefulness of the technique could be demonstrated in research fields such as biochemistry. The difference DI is measured as a function of the angle of the quarterwave plate and can be fitted to the following equation: DI ¼ ½ðE1 À sinð2yÞsinðfÞE2 Þ2 þ ðcosð2yÞE1 þ sinð2yÞcosðfÞE2 Þ2
2 À ððcosðfÞ þ cosð2yÞsinðfÞÞ2 E2 þ ðsinð2yÞE1 þ E2 ðsinðfÞ À cosð2yÞcosðfÞÞÞ2 Þ
(78) where y is the angle of the quarterwave plate. 26a) there are no magnetic contributions to the SHG signal or E2 ¼ 0. respectively.
. SHGCD could also be used in a new sort of imaging technique: SHGCD microscopy. we gave a series of experimental results. The last curve (Fig. A chiral medium with magnetic nonlinearities to the SHG gives a rotation pattern that is asymmetric with respect to the 1808 rotation angle of the quarterwave plate even for weak magnetic contributions. catalysis or pharmacology. For example.and magneticdipole contributions. 26b) the ratio of E2/E1 ¼ 0:3 and the phase difference is taken to be f ¼ p/4. From the examples discussed in this review. the study of configurational changes in proteins adsorbed at surfaces. 26 shows three curves. we made some simulations. before it can be routinely used as a measurement technique. / Materials Science and Engineering R 42 (2003) 115–155
153
with f the phase difference and E1 and E2 are directly proportional to the electric.
Quant. S. 1992. 101 (1994) 6233–6241. Bredas. Rev.L. Nolte. Langmuir–Blodgett Films. T. S. G. Fumi. Yang. Phys. Bellingham.J. ´ J. The Principles of Nonlinear Optics. Phys. 97 (1993) 1383–1388. J. M. A 39 (1989) 2256. Wecht. H. Katz. Phys. Selected Papers on Natural Optical Activity.W.0338. Opt. Persoons. IEEE J. Charney. 28 (1992) 2057.A. E.J. Mater. Chem.R. J.L.Electron. 16 (1915) 251–258. Phys. 1866. B 24 (1981) 4271–4278. Lett. Huang. A. T. T. D. F. T. is research assistant of the Fund for Scientific ResearchFlanders and T. Wiley. Phys. Williams.A. Lett. 89 (1996) 61–80. Lett. 45 (1998) 403–423. Rev. S. Persoons. Phys. 1991. is a postdoctoral fellow of the Fund for scientific ResearchFlanders. R. Oxford.
References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36] [37] [38] [39] [40] [41] [42] [43] A. Chandra. Verbiest. The Elements of Nonlinear Optics. Maki. G. Clays. Lakhtakia. J. Academic Press. M. Plenum Press. D.S. M. Fresnel. Adv. T. Kauranen. van’t Hoff. ` ´ A.G.N. Maki.J.L. Met. Pasteur. Phys. T. Van Elshocht. Barron.W. 101 (1994) 8193–8199. 8 (1999) 171–189.
. Verbiest. Phys. Paris. Hicks. Adler. E. Rev. Phys. 82 (1999) 3601–3604. Wiley/ Interscience. L. Pershan. Ann.E. 113 (2000) 7578–7580. Shuai. R. E. Born. M. Phys. Wong. M. Kauranen. Mod.0407. J. 7 (1997) 2175–2189. Meijer for providing us with products and for their valuable discussions. R. Lett. Chem. Bull.N. Phys. Phys. Schonhense. Pattanayak. J. V. J. Westphal. Mater. G. New York. J. A. 5 (1942) 44. S. Houbrechts. Maki. 7 (1916) 472–488. Chem. Soc. 48 (1915) 1–56. 16 (1966) 792–794. 130 (1963) 919. J. Butcher. F. Getzlaff.M. S. The Quantum Theory of Light. ´ A. Verbiest. Chem.M.A. ¨ C. Verbiest.M. Oxford University Press.E. Comptes Rendus Hebdomadaires Seances l’Acad.J. L. T. P. New York. / Materials Science and Engineering R 42 (2003) 115–155
Acknowledgements This work was supported by the National Science Foundation (CHE0094723). New York. Van Elshocht. L. Chem. Phys. Chem.S. T.W.D. M. Opt. A. S. Wiley/Interscience. Rev. Rev. J. 28 (1850) 56–99. Zeitschrift Phys. Rev. K.I. Cotton.E. 63 (1989) 151.H. J. Persoons. P. C. Phys. Havinga. H. J. Sioncke et al. Birman. Exactes Naturelles 9 (1874) 445–454. Prasad. S. A. 65 (1990) 37. Clays. Phys. Chim. Persoons. P. T. Shen. 4010 (1993) 55–57. Phys. Mol. Yee.M. 134 (1964) A728.N. Phys. Miller. The Molecular Basis of Optical Activity. Walsh.V. Dixit. Gray. Burland.K. J. J.N. McKoy. Mater. D. the Belgian government (IUAP P4/11). Annalen Phys. 1991. Verbiest. Cambridge University Press. Byers.D. Am. 1984. Chem. P. Phys. Rev. J. Roberts. 6 (1994) 486. Cambridge.J.154
S. 1990. T. We gratefully acknowledge J. L.98 and 9.A. Persoons.D. San Diego. Loudon. K. B 15 (1998) 1698–1706.W. C. Imprimerie Imperiale. Y. M. Persoons. 112 (1999) 1497–1502. Arch. and from the University of Leuven (GOA/2000/03). Rev. New York. Bansmann. M. Phillips.D. Synth. 1983. Rev. A. T.M. 120 (1895) 989–991. Hecht.S. J.Y. A. Paris 22 (1874) 337–347. Rikken. Acta Cryst. Persoons. Kauranen. Boyd. Roberts. the Fund for Scientific ResearchFlanders (G. Rev. 94 (1994) 31–75. A. Katz. Neerlandaises Sci. Havinga. Verbiest. Rentzepis. PetralliMallow. Meijer. Phys. J. J. Kauranen. E. Hicks. E. D.98).L.W. 1979. Sioncke. Introduction to Nonlinear Optical Effects in Molecules and Polymers. J. Dubs. T. Van Elshocht. J. Rev. Soc. Chem. SPIE. 54 (1985) 1249. D. A. J. Le Bel. Meijer. Giordmaine. J. A. Persoons. Persoons. Nonlinear Opt. Pu and E. E. Chim. R. M. Persoons. Chem. A. K. K. Kauranen.M. M. P. 104 (1996) 9340–9348. J. Phys. Kauranen. 105 (1996) 767–772. Verbiest. Rev.W. Lett. Byers. WA. Cotton. J. J.I. Oeuvres Completes. Phys. N.J. Kauranen. 66 (1991) 2980. 1990.J. Sci. Oseen. Yee. Nonlinear Optics. Verbiest. ´ Z. Kauranen. Lett.
107 (1997) 8201–8203.W. SchanneKlein. Flytzanis.L. [51] M. Am. Castellanos. N.N. Persoons.W. Verbiest. Kauranen. Lett. Nuckolls.C. Kauranen. Chem. Van Rompaey. Photobiol. E. Soc. A. Teerenstra. J. L. Adv. Kauranen.I. Opt. Mater. Crawford. Persoons. Kauranen. [75] J. Sioncke. Phys. Plant. A. Hagting. Katz. Rev. Smiley. Katz. Carlson.A. C. J.G. Phelan. Chem.N. Persoons. T.J. M. M.T.M. Phys. T. Mater.F.L. A. Jang.J. Lemmetyinen. [65] T. E. Jen. B. N. Pu. [49] M. Kauranen. Q. Chem. Frey. J. Kauranen. 14 (2002) 773–776. Phys. Zhang.M.J. T.R. A. J. Thin Solid Films 248 (1994) 110–114. [74] J. Phys.D.M. [61] L. Katz. Kuball. Marder. Cryst. Mol. Persoons.R. L. M. Soc. J. Opt. Levine. Dalton. Rev. C. Probert. J. Ikonen.Y. Lewis. Pu. H. Nuckolls. 7 (1995) 641–644. Verbiest. Chem. Verbiest. R.D. L. Kauranen. Schouten. S. Macromolecules 29 (1996) 4876. Robinson. [70] T. Van Elshocht. Katz. Y. Phys. T. Adv.G. Dalton. Zhang. Pu. Kincaid. [69] B.P. B 49 (1994) 14643–14647. T. Bethea. J. Meijer.C. E. J. A. W. Appl. C. [52] M. Am. Kiesewalter. [60] T.G. Verbiest. Verbiest. Katz. [64] L. C. [55] M. Nolte. Clark. Kippelen. PetralliMallow. B. Peyghambarian. Photoch. Chem. J. Nolte. Lett. J. Kurkela. [59] T. [57] M. Chem. 63 (1975) 2666. LangeveldVoss.L. Van Elshocht. Verbiest.R. 39 (2000) 589–595.W. Teerenstra. S. M. [62] Y. PetralliMallow. C. Chem. Gruzdkov.M. [68] C.G. T. M. Lovinger. 108 (1998) 9436–9443. Chem.N. Commun. Cryst. Science 288 (2000) 119–122. L. Macromolecules 31 (1998) 2933–2942. Persoons. Van Elshocht. Persoons. B.R. L. Levine. J.J. L. [66] C.J. 48 (1997) 116–141. S. L.W. [47] L. Van Elshocht. M. Zhang. Rev. J. Lett. Bethea. Verbiest. Havinga. A.S.H.H. C. 309 (1999) 315–320. Hu. M. W. Mater. T. New York. Nuckolls.J. Liq. Am. SPIE 1922. H. A. A. F. [67] C. Amend. M. T. C. Phys. A.L. Havinga. Persoons. Shao. Nuckolls. Steier. Musick. Soc. Science 282 (1998) 913–915. C. A. Verbiest. Ren.E. Nature 388 (1997) 845–851. Fifield. A. T. 1992. Busson. Meijer. T. 9 (1999) 1905–1920. H. [58] V. Nolte. Acta Polym. 116 (1994) 9203–9205. A.K. [54] M. Snauwaert. Haslam.J. A. Bouman. B 55 (1997) R1985–R1988. Meijer. H. B. 118 (1996) 3767–3768. [50] M. S. Hicks.E. 229 (1994) 260–264. Maki. Hagting. B.M. [46] S. Jen. 1999. 77 (1996) 1456–1459. 7 (1995) 385–387. Oostergetel. R. A.F. Jackson. M. 120 (1998) 8656–8660. Byers.M. Teerenstra. E. Hellemans. J. Persoons. Verbiest.J. J. K. Verbiest. Mater.A. J. T.M. A. G. A. Van Elshocht. Steier. L. 15 (1975) 258. B. A. [63] S. Roy.G. Bethea. E. Schouten. Persoons.J. J.M. Chem. [71] B. T. 256 (1994) 439–448. J. H. Persoons. Chem. Levine.J. A. T. [53] S. Sioncke et al. [56] M. Garner. Classical Electrodynamics. Londergan. 24 (1974) 445. [72] B. A 145 (2001) 113–115. Yee.G. Le Person. Persoons. 37 (1974) 516.S. Walba. M. Irwin. R. Robinson. Shi. Phys.M. Vogel. [73] B.
. E. Bouman.A.J. S. R. S. J. Janssen.J. Chen. H. M.M.H. G. Lett.F.Y.J.G.A. S. Hicks. Cheng. Kauranen.H. Lett. R.J. Oudar. Ma. Bechtel. Wiley/Interscience. A.W. Lett. Phys. Devillers. J. C. Eng. Kauranen. City. Nuckolls. / Materials Science and Engineering R 42 (2003) 115–155
155
[44] T. [45] J.H. Phys. 84 (2000) 79–82. Langmuir 16 (2000) 5960–5966. Meijer. Hache. A.G. Rev. Chem.Y. D. A. W. Schouten. Dalton. Phys. Y.J. Musick. Phys. [48] K.