Abstract
This paper reviews work on the secondorder nonlinear optical properties of chiral thin lms and surfaces. We give an overview of the theoretical formalism and experimental techniques to describe the secondharmonic generation (SHG) from chiral thin lms and surfaces. We also discuss the secondharmonic response of thin lms and surfaces composed of chiral synthetic materials and biological molecules. In addition, we point out possible applications and the future prospects in this eld. # 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 LangmuirBlodgett 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.: 3216327169; fax: 3216327982. 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
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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. vant 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
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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 [68]. 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). Biots 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 f, 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 otherthe lag being proportional to the difference between the two indices of refraction and the length of the path through the material and inversely
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+x
+x
l
y
r
+y y
r
+y
x
x
Fig. 1. After leaving the active medium the planepolarized wave will be rotated by (yr 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 E0^ cos y (1)
x where y 2pnt nz=c, 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 E0 ^ cos yr ^ sin yr El E0 ^ cos yl ^ sin yl x y (2) (3)
where ^ is the unit vector in the ydirection. Initially yr yl 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 2pn t (4) c nl z (5) yl 2pn t c 2pnz (6) nl nr yr yl 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 Er El E0^cos yr cos yl E0^sin yr sin yl ; 1 1 E 2E0 cos 2 yr yl ^ cos 2 yr yl ^ sin 1 yr yl x y 2
(7)
We now see that because yr 6 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 yl =2 from its original orientation in the xz plane. This rotation is caused by the difference
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in refraction nr nl of the optically active medium. The relation between the rotation and the difference in the indices of refraction is d yr yl pnz nl nr c 2 (8)
d is thus the angle by which the planepolarized wave has been rotated in traversing the optically active medium of thickness z. More commonly, the rotation is specified in degrees per decimeter f 1800 nl nr 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). 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, but also by an exponential factor exp4pKl z=l and exp4pKr z=l, 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, then the transmitted intensity is substantially reduced, but not precisely the same amount as the isotropic absorption measured under the same conditions using unpolarized light. Not only do the two circularlypolarized beams leave the material outofphase, but also one of the components is absorbed more strongly than the other. The ellipticity c, which is a measure of the eccentricity of the ellipse results, of course, from the differential absorption of the circularlypolarized component beams. 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. Therefore tan C jEr j jEl j jEr j jEl j (11)
El and Er are of course no longer equal when the extinction for left and rightcircularlypolarized light are different. When we express them in terms of the extinction difference, the function on the righthandside of Eq. (11) can be shown to be equal to the hyperbolic tangent, tanh pKl Kr z=l. The hyperbolic tangent of c is very nearly equal to c for values of c less than 1. The measured ellipticity is rarely greater than 1 even for short wavelengths, because the extinction difference Kl Kr is rarely greater than 106 or 107. Consequently C pz Kl Kr l (12)
In the more commonly used units for absorption, the extinction coefficient e (in M1 cm1) is related to the absorption index by e 4pK 2; 3lC (13)
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Ein
M E(P
Eout E(M)
Fig. 2. Optical activity can be understood intuitively. If we consider light that is vertically polarized and incident on a chiral isotropic medium, a vertically directed polarization and magnetization will be created inside the medium. Both polarization and magnetization act as new sources of radiation: the polarization radiates a vertically polarized field, while the magnetization radiates a horizontally polarized field. The sum of both fields is a new field with its polarization rotated over an angle y, depending on the relative magnitude of P and M. The rotation angle y has the same magnitude but differs in sign for both enantiomers. In the absence of magnetic interaction, no optical rotation can occur.
where C is the concentration in moles per liter. Substituting in Eq. (12), the ellipticity in radians is c 1 2; 3Czel er 4 The circulardifference can also be expressed as a normalized quantity De/e De 2el er e el er 2.2. 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. 2) P wee1 E wem1 B M wme1 E (16) (17) (15) (14)
where wee is the firstorder (or linear) susceptibility and wem, wme are the firstorder chiral (or magnetic) susceptibilities. The superscript e refers to an electricdipole transition and the superscript m refers to a magneticdipole transition. For example, wem refers to an interaction where a photon is annihilated through a magneticdipole interaction and a photon is being created through an electricdipole interaction. The ladder diagrams for the susceptibilities wee, wem and wme are given in Fig. 3. The susceptibilities wem and wme are only present in chiral media and are responsible for all optical activity effects in linear optics. The two firstorder chiral susceptibilities can be related to each other: wem wme . Notice that for a nonresonant excitation, wee is a real quantity while wem and wme are imaginary quantities. For an achiral medium the refractive index can be related to the linear susceptibility n2 1 4pwee (18)
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(1),ee
e e e
(1),em
m m
(1),me
e
Fig. 3. Ladder diagrams for the susceptibilities wee, wem, and wme. For wee, one photon is annihilated and one photon is created through an electricdipole interaction. For wem, the output photon is created while for wme, the input photon is annhilated by a magnetic interaction.
Based on an expression stated in [10], we find that for a chiral medium, this equation becomes nr p o 1 4pwee i8p2 wem ; c nl p o 1 4pwee i8p2 wem c (19)
As a result, the presence of the magnetic susceptibility explains the difference in refractive index for left and rightcircularlypolarized light, which makes optical rotation possible.
3. Nonlinear optics So far, we have considered optical activity of chiral compounds in linear optics. The most commonly observed effects are linear, onephoton optical processes. Rayleigh light scattering, onephoton absorption, reflection, and refraction are examples of linear optical processes. However, when the fundamental intensity of the light source becomes sufficiently intense, one can detect twoand threephoton processes such as hyperRayleigh scattering [12], sumfrequency generation [13], second and thirdharmonic generation, the electrooptic effect, etc. [14]. These nonlinear optical effects were already predicted theoretically in the firsthalf of the 20th century, but could, because of the high intensities needed, only be experimentally observed after the development of the laser in the 1960s. When a medium is subject to an optical field, the electric field polarizes the molecules of that medium. 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). Then, within the electricdipole approximation, the induced charge distribution can be described on a molecular (macroscopic) scale by the induced electricdipole moment m (the polarization P) [15] m er and P Ner (21) (20)
with e the electric charge, r the displacement induced by the electric field, and N the electron density. The induced electricdipole moment and polarization are, still in the assumption of a relatively weak electric field, linearly dependent on the electric field. m aE (22)
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and P w1 E (23)
with a the linear polarizability, and w(1), the first susceptibility. Note that the susceptibility of a medium is related to its dielectric constant and index of refraction by n2 o eo 1 4pw1 o. On the other hand, when the amplitude of the incident electric field is sufficiently large, we have to include higherorder interactions. Such intense fields can easily be generated by lasers. The induced electricdipole moment and polarization become . m aE b : EE g.EEE . and . . P w1 E w2 : EE w3 .EEE (25) (24)
with b the secondorder polarizability or first nonlinear polarizability, and w(2) the secondorder susceptibility or first nonlinear susceptibility. In this review, we will focus on the secondorder effects originating from the secondorder susceptibility, w(2), more specifically, secondharmonic generation. Secondharmonic generation is the generation of light with the double frequency of the incident radiation. The origin of secondharmonic generation can be understood by describing the fundamental electric field in Eq. (25) as E E0 cosot kz (26)
with E0 the electricfield amplitude, o the frequency, and kz the relative phase. Substitution in Eq. (25) gives
2 P w1 E0 cosot kz 1 w2 E0 1 cos2ot 2kz 2
(27)
This equation clearly demonstrates the presence of components at other frequencies than the fundamental frequency of the input field. There is a part that is frequencyindependent, giving rise to the phenomenon known as optical rectification. In addition, there is also a contribution at the double frequency which is a secondharmonic generation. 3.1. Tensor properties of the nonlinear susceptibility w Note that the secondorder susceptibility, w(2), although treated thus far as a scalar, is actually a tensor (see Eq. (25)). A tensor describes the relation between different vectors, in this case between all the components of the polarization and the electricfield vectors. w(2) is a thirdrank tensor and contains 27 (3 3 3) elements. Fortunately, this large number of tensor of elements can be often reduced by taking into account the symmetry of the system. The principle of Neumann states that under any symmetry operation on the system, the sign and the amplitude of the physical properties have to remain unchanged [16]. In order to illustrate the strength of this principle, we will take the case of a centrosymmetric system. We will examine the influence of the inversion symmetry on the polarization that leads to
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Under inversion, the electric field and the polarization transform as E ! E and P ! P. Eq. (28) then becomes P2 w2 E2 w2 E2 ) P2 w2 E2 (29)
As we can see, the sign of the secondorder polarization has changed under inversion. According to the principle of Neumann, the secondorder susceptibility w(2) has to be zero or otherwise stated, no secondharmonic generation can be observed from a centrosymmetric system. Alternatively, one can compare Eqs. (28) and (29) P2 w2 E2 w2 E2 (30)
This relation can only be valid if w2 0. This expression has great importance in secondharmonic generation. Only noncentrosymmetric systems will give a secondharmonic response. This condition is easily fulfilled on the molecular level by constructing a DpA system where an electrondonor is connected to an electronacceptor by a pconjugated system [17]. One of the textbook examples is paranitroaniline (Fig. 4). However, on the macroscopic level, these DpA systems take a randomly distributed orientation and we end up with a centrosymmetric situation which is not able to give rise to secondharmonic generation. This is why on the macroscopic level, we still have to introduce a polar order in our systems. This can be achieved by electricfield poling, crystal growth, the LangmuirBlodgett technique [18], selfassembly, liquid crystals, etc. Nevertheless, some of these techniques still suffer from some disadvantages: relaxation will occur after electricfield poling [19]. The LangmuirBlodgett technique is time consuming and the films obtained by this way have often low optical quality which is also the problem with selfassembled films. 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 point where chirality can be introduced in nonlinear optics. A chiral molecule is inherently noncentrosymmetric and even a random distribution of enantiomerically pure molecules will never lead to systems with inversion symmetry. This is the reason why nonlinear optical processes as SFG are possible in solutions [13,20]. When including magneticdipole and quadrupole interaction noncentrosymmetry is not a strict requirement any more to observe a secondharmonic response [21]. However, 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). To clearly indicate the tensor properties of w(2), we have to rewrite Eq. (28) as X 2 2 wijk Ej Ek (31) Pi
j;k
H 2N
NO2
Fig. 4. Paranitroaniline.
124
where the subscripts ijk refer to the Cartesian coordinates in the laboratory frame. As an example, we will examine the influence of a mirror plane in the yz plane on the secondorder susceptibility. Under reflection in this plane the coordinates transform as x ! x y ! y z!z (32)
Now, we have to examine the effect of the mirror plane on each tensor component. For the component wxxx the reflection will transform the relation Px wxxx Ex Ex into Px wxxx Ex Ex wxxx Ex Ex ) Px wxxx Ex Ex . Then because of the principle of Neumann wxxx 0. As a second example, consider the relation Px wxxz Ex Ez . This will be transformed into Px wxxz Ex Ez wxxz Ex Ez ) Px wxxz Ex Ez . Therefore, since the sign of the tensor component wxxz remains unchanged, the component will not be cancelled under reflection. To simplify this procedure, Fumi has derived a technique called the direct inspection method [22]. It was demonstrated that the components of a tensor transform as the product of their respective coordinates. As a consequence, a tensor component will be zero if its index changes after a symmetry operation. In other words, the verification that wxxx wxxx after the symmetry operation can be reduced to verifying that xxx xxx. We will now analyze the susceptibility tensor w(2), for secondharmonic generation within the electricdipole approximation for an achiral and a chiral surface that has inplane isotropy. These surfaces have C1v and C1symmetry, respectively. We consider a righthanded coordinate axis system with the zaxis along the surface normal and the surface being in the xz plane. The C1v and C1symmetry of the surface can be treated as C4v and C4symmetry, respectively, because a higherorder symmetry introduces no further simplification of the susceptibility tensor (see Fig. 5). The fourfold rotation axis coincides with the zaxis. In addition, for the C4vsymmetry the mirror planes are the xz plane and the yz plane. The symmetry operations present for a chiral isotropic surface with C4symmetry are a fourfold rotation (that implies also a twofold rotation). Under the fourfold rotation, the coordinates transform as x!y y ! x z!z (34)
C4 Z YZ mirror plane Y XZ mirror plane X Achiral surface with C4v (Cv) symmetry Z
C4
Fig. 5. Scheme presenting the main symmetry operations in a chiral and achiral isotropic surface with C4v and C4symmetry, respectively.
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Let us consider wxxx. According to the direct inspection method, we will examine the index xxx. Under twofold rotation this index becomes xxx xxx. Thus, wxxx must vanish. Similarly, wxxy, wxyy, wyyy, wyxy, etc. will be zero. When we take a closer look to the tensor components that vanish, we conclude that every tensor component where the sum of the number of xs and ys in its index is odd must be zero. This procedure leads to the elimination of 14 components. In addition, wzxy and wzyx will also be zero because under the fourfold rotation zxy transforms into zyx. Indeed, 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 zyx zxy. Therefore wzxy, and similarly, wzyx will be zero. The total number of vanishing components is now 16. However, all remaining 11 components are not independent. For example, wzxx is related to wzyy by the fourfold symmetry. Hence, wzxx wzyy , wxzx wyzy , and wxxz wyyz . Note that because of permutation symmetry, wxzx wxxz . Therefore, the secondorder susceptibility tensor, that describes the secondharmonic signal generated in a chiral isotropic surface, will have four independent components listed in Table 1. For an achiral isotropic surface, the additional two mirror planes transform the coordinates as x!x y ! y z!z (36)
for the yz mirror plane. This causes the elimination of the four components that have three different indices: wxyz, wxzy, wyzx, and wyxz. Hence, an achiral isotropic surface can be described by the three independent components, listed in Table 1. The tensor components: wxyz, wxzy, wyzx, and wyxz are only allowed for chiral isotropic surfaces and are designated as chiral tensor components. The remaining components are allowed for all isotropic surfaces and are therefore referred to as achiral tensor components. Note that all these considerations are made within the electricdipole approximation. As in linear optics where we described optical activity effects through magneticdipole interactions, one can also take account of magneticdipole interactions in the case of nonlinear optics. We can define the nonlinear polarization and magnetization up to the firstorder in magneticdipole transitions as Pi 2o weee Ej Ek weem Ej Bk ijk ijk Mi 2o 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 zyy xxz yyz yzy xzx xyz yxz yzx xzy Achiral isotropic surface zzz zxx zyy xxz yyz yzy xzx
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(2),eee
e e
(2),eem
m
(2),mee
2 e
2 m
2 e
Fig. 6. Photon diagrams for tensors weee, weem, and wmee. For weee, two input photons of frequency o are annihilated and one photon at frequency 2o is created through electricdipole interactions. For weem, one input photon at frequency o is annihilated by a magnetic interaction whereas the other interactions occur through electric dipoles. For wmee, on the other hand, the output photon is generated through a magnetic interaction.
The superscripts e and m, in Eqs. (38) and (39) refer to electric and magneticdipole interactions, respectively. For example, the superscript eem of the susceptibility tensor weem refers to an interaction where a photon at frequency 2o is generated through an electricdipole interaction, and two photons are annihilated by an electric and magneticdipole interaction, respectively. The ladder graphs for the tensors weee, weem, wmee are given in Fig. 6. Notice also that for a nonresonant excitation, weee is a real quantity while, weem and wmee are imaginary quantities [23,24]. The numbers of components of the susceptibility tensors weem and wmee can be reduced in a similar manner as demonstrated for the tensor weee. However, there is a fundamental difference between an electricfield vector and a magnetic field vector. The first is a polar vector whereas the latter is an axial vector. A polar vector transforms as the position vector under all spatial transformations. On the other hand, an axial vector transforms as the position vector under proper transformations (rotations) only. Under improper transformations (reflection inplane and inversion), each component of an axial vector transforms opposite to that of the position vector [21]. Let us, for example, consider the influence of a mirror plane in the yz plane. The coordinates transform as x ! x y ! y z!z (40)
Therefore, the nonvanishing tensor components of tensor weee will be different as compared to the components of the tensors weem and wmee (see Table 2). For example, the mirror plane will transform Mz wmee Ez Ez into Mz wmee Ez Ez . Therefore, because of the principle of Neumann, wmee will be zzz zzz zzz zero for an achiral isotropic surface. For a chiral isotropic surface (C1symmetry) weee has four independent components, weem seven, and wmee four. For an achiral isotropic surface (C1vsymmetry), the number of independent components is limited to three for weee, three for weem, and one for wmee. Note that weee and wmee possess intrinsic permutation symmetry, which results in fewer independent
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Table 2 Nonvanishing tensor components weee, weem, and wmee for isotropic chiral and achiral surfaces Tensor weee Achiral components for all isotropic surfaces zzz zxx zyy xxz xzx yyz yzy xyz yxz zxy zyx xzy yzx xyz xzy yxz yzx Additional components for chiral surfaces xyz xzy yxz yzx
weem
zzz zxx zyy xxz yyz xzx yzy zzz zxx zyy xxz xzx yyz yzy
wmee
components. 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. Notice also that for centrosymmetric systems, weem and wmee are not zero [21]. This means that including magnetic contributions, noncentrosymmetry is not a requirement any more in order to detect a secondharmonic response. The problem is that magnetic interactions are weaker than the electricdipole interactions by a factor given by the finestructure constant ($1/137) [25]. However, in practice, the relative magnitude of the various interactions can depend on the structure of the material.
4. Chirality in nonlinear optics There is a growing interest in chiral molecules for nonlinear optical purposes. The first reason is that symmetry is a very important issue for the secondharmonic response. In the electricdipole approximation, noncentrosymmetry is a strict requirement to observe secondorder NLO effects. Because chiral molecules are inherently noncentrosymmetric, they possess an electricdipole allowed secondorder and higher evenorder nonlinearity. In addition, some structures are favorable for magneticdipole transitions for which noncentrosymmetry is not a requirement. It has been shown that chiral molecules and more specific helical molecules are such structures [26]. Besides the interest for chiral structures because of their symmetry properties, the fascination grew also because one discovered the existence of optical activity in nonlinear optics [27]. Similar effects as in linear optics were observed. Chiral molecules would have a different efficiency for the generation of secondharmonic light for left and righthanded circularlypolarized fundamental beams. This effect is called secondharmonic generation circulardichroism (SHGCD). The astonishing fact was that the SHGCDeffect is several orders of magnitude higher than ordinary circulardichroism in linear optics. In linear optics optical activity effects arise from the interference between electric and magneticdipole interactions. SHGCD, on the contrary, can be explained within the electricdipole approximation. Other optical activity effects observed in nonlinear optics are secondharmonic generation linear difference (SHGLD), for which there is no analogue in linear optics. As we already mentioned, secondharmonic generation is only allowed in noncentrosymmetric structures. Centrosymmetry, however will always be broken at surfaces and interfaces between two
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centrosymmetric media and consequently the surface or interface can act as a source for secondharmonic light when irradiated with laser light [28]. As SHG is sensitive to surfaces and CDSHG is an effect specific to chiral materials, SHGCD can be used to investigate chiral surfaces and interfaces. In this review, we will demonstrate the usefulness of this technique as a tool to study chiral surfaces. SHGCD can be used to probe chiral surfaces but, on the other hand, chirality can also be applied in nonlinear optics to enhance the nonlinear response. First, because chiral molecules are inherently noncentrosymmetric, and polar order is therefore not a strict requirement. Second, the nonlinear optical response originates from electricdipole transitions as well as from magneticdipole transitions. Hence, one could enhance the overall nonlinear response through magneticdipole contributions. 4.1. SHG from chiral films: basic theory We consider an experimental configuration that is schematically shown in Fig. 7. A laser beam at frequency o is incident on the sample with isotropic surface symmetry. The symmetry of such a sample is broken in the direction of the surface normal (zdirection); however, arbitrary rotations about the surface normal remain symmetry operations. For an achiral surface, reflection in a plane containing the surface normal is an additional symmetry operation. The symmetry groups of the achiral and chiral isotropic surfaces are C1v and C1, respectively. The fundamental beam can be expressed in terms of the ps basis as [29,30] sE Eo ~ p o ~ s o pE (43)
where Ep(o) and Es(o) are the p and spolarized components of the field and the respective unit vectors are related to the Cartesian (x, y, z) vectors by ~ ~ s y; ~ ~ cos y ~sin y p x z (44)
where y is the angle of incidence. Note that x, y, z are the natural basis for analyzing the symmetry properties of the sample. We assume that the nonlinear layer is sufficiently thin that its linear optical
Z 2 Reflection
p s
p s
Thin film or surface
X Y
p s
2 Transmission
Fig. 7. Geometry of secondharmonic generation from a thin film or surface. The fundamental beam at frequency o is incident on the film at angle y. The p and spolarized secondharmonic fields are generated in reflected and transmitted directions.
129
activity does not appreciably mix the p and spolarized components of the fundamental or secondharmonic fields. 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 2o weee Ej Ek weem Ej Bk ijk ijk Mi 2o wmee Ej Ek ijk (45) (46)
The nonlinear polarization P(2o) and magnetization M(2o) act as sources of secondharmonic radiation. The electricfield amplitude of the secondharmonic generation is directly proportional to the two sources. In addition, the magnetic field B(o) depends linearly on the electric field E(o). As a consequence, we can write the secondharmonic generated field as
2 2 Ei 2o fi Ep o gi Es o hi Ep oEs o
(47)
where fi, gi and hi are linear combinations of the components of the nonlinear susceptiblities weee, weem and wmee, respectively. The detailed forms of the coefficients are different depending on which contributions are included in the theory. We will only consider explicitly electric and magneticdipole interactions. In principle, one could also include electricquadrupole interactions. The reason that we do not include them here is that the magneticdipole interactions are actually somewhat stronger than the quadrupole interactions. Furthermore, the importance of magnetic interactions in chiral media is well established and one can argue that chirality favors the magnetic interaction [3133]. Furthermore, the general symmetry properties of magneticdipole and electricquadrupole interactions are very similar in secondorder nonlinear optics, making separation between the two is extremely difficult [30]. Hence, the quadrupole interaction is implicitly included in the magneticdipole interaction. This approach simplifies the discussion considerably and also facilitates highlighting the different symmetry properties of the electricdipole and highermultipole interactions. The detailed form of the coefficients f, g, and h is also dependent on the symmetry of the sample. For an achiral and chiral isotropic surface, we derived the different independent components of the secondorder susceptibility within the electricdipole approximation, i.e. weee. As mentioned before fi, gi and hi are linear combinations of the components of the nonlinear susceptiblities weee, weem and wmee, respectively [29]:
Rs fTs sin y2weee cos y weem wmee sin2 y wmee cos2 y 2wmee cos2 y xyz xzx zzz zxx xxz
gRs sin yweem wmee Ts xxz zxx hRs sin y2weee weem weem cos y 2wmee cos y Ts xxz xzy xyz xyz
Rp fTp sin yweee sin2 y weee cos2 y 2weee cos2 y weem cos y weem cos y 2wmee cos y zzz zxx xxz zxy xzy xyz
(51) gRp sin yweee weem cos y weem cos y Tp zxx zxy xyz hRp sin y2weee cos y weem weem sin2 y weem weem cos2 y 2wmee Tp xyz zzz zxx xzx xxz xxz (52) (53)
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where R and T refer to the secondharmonic fields generated in reflection and transmission direction, respectively, s refers to the polarization of the detected signal, y is the angle of incidence, and the surface normal is along the zdirection. The chiral components are those that are nonvanishing only for chiral surfaces, the achiral components are nonvanishing for chiral and achiral surfaces. It is clear that for an achiral surface only hs is nonvanishing (i.e. hs is an achiral component), while for a chiral surface fs, gs and hs are nonvanishing (fs and gs are therefore chiral components). Note also that the coefficient gs vanishes in the electricdipole approximation. If we analyze the equations for ppolarized detection, 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. We can conclude from Eq. (47) that the coefficients fi, gi and hi can be considered as susceptibility components in the ps basis. However, to make the formalism easier, we have included in these coefficients the linear indices of refraction of the surface layer and the surrounding media. We will consider throughout this paper s and ppolarized detection. This is important because the role of f, g, and h as chiral or achiral components is reversed between the s and ppolarized secondharmonic signals. Consequently, a detection scheme that mixes p and s polarizations, gives rise to nonzero values of the three coefficients, even though the sample is achiral. This problem will be treated in a later chapter [3436]. 4.2. Circulardifference and lineardifference effects in secondharmonic generation In linear optics, chiral materials interact differently with left and righthand circularlypolarized light. Chiral materials have a different linear absorbance and refractive index for the two different circular polarizations. One can probe these different characteristics by two measurements. An example of such a measurement is circulardichroism: the difference in output intensity is measured for left and righthand circularlypolarized input light. In the case of nonresonant excitation, one cannot use circularlypolarized input light to probe the difference in refractive index for the two polarizations, because this leads to no difference in the output intensity. In this case it is better to use linearlypolarized input light, which is composed of equal amounts of the two circularlypolarized components. Because of the difference in refractive index for the circularlypolarized components, the linearlypolarized light will be rotated while travelling through the chiral material. Also in nonlinear optics, optical rotation can be observed. In nonlinear optics, chiral materials will also interact differently with left and righthand circularlypolarized input light, i.e. nonlinear optical activity. In linear optics these effects arise from an interference between electric and magnetic susceptibilities. As we will point out, this is not always the case for nonlinear optical activity. First, we will consider circulardifference effects in secondharmonic generation (SHGCD). For the case of circularlypolarized fundamental beams, Ep o iEs o, the intensity of the secondharmonic field is found from Eq. (47) to be I2o jf g ihj2 jEs oj4 (54)
The circulardifference response is arising from the interference between the quantities gf and h. Since fs and gs and hp are zero for an achiral surface, no circulardifference effect can occur for p or spolarized detection. Hence, the circulardifference effect will only occur for chiral materials and the effect will change sign for the two enantiomers of the sample. Also for a CDeffect to occur, there has to be a phase difference between gf and h. The circulardifference response can be
131
described by a normalized quantity (as in linear optics De/e): DI2o ILHC 2o IRHC 2o I2o jILHC 2o IRHC 2oj=2 (55)
where LHC and RHC stand for left and righthand circularlypolarized fundamental beams, respectively. 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. On the other hand, when we include magneticdipole interactions, the required phase difference will also exist for nonresonant excitation. Note that for a chiral material the two conditions, interference between chiral and achiral expansion coefficients and a phase difference between these coefficients, have to be fulfilled simultaneously. Therefore, the lack of an SHGCDeffect cannot be used to conclude that the material is achiral. Because SHGCD is a resonance technique, it can be useful to probe the SHGCDresponse as a function of the SH wavelength. These spectra are similar to the UV spectra as expected by the relationship between SHG and resonance [27]. We can also use linear input polarizations to probe surface chirality. For the case of linear polarizations that are rotated by 458 from the ppolarized direction, Ep Es and the intensity of the secondharmonic field is I2o j f g hj2 jEs oj4 (56)
This result implies that in order to observe a lineardifference effect (SHGLD), f g and h must be nonvanishing (the material has to be chiral) and f g and h have to be inphase. The difference can therefore exist in nonresonant excitation in the electricdipole approximation. In this respect, lineardifference effects are complementary to circulardifference effects in SHG (where a phase difference between the expansion coefficients is required) [37,38]. This lineardifference response has no analogue in linear optics. However, a nonlinear analogue of linearoptical rotation does exist and is called secondharmonic generation optical rotatory dispersion (SHGORD) [30,37]. The main constraint of SHGCD is the fact that this technique is a resonance technique, like ordinary CD spectroscopy. The requirement of complex susceptibility tensor components, limits SHGCD to regions of the spectrum in which the molecules absorb light (o or 2o). SHGORD, on the other hand, is a technique that is surface sensitive, chiral selective but not constrained to resonant wavelengths. 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. The observed SHGORD will be characterized by the angle f, which is the amount of rotation of the SHG signal in comparison with a 5050 mixture of enantiomers (an achiral surface). The f can be defined as f tan1 R2o where R(2o) is the ratio of the spolarized component to the ppolarized component R2o
2 2 Es 2o fs Ep o gs Es o hs Ep oEs o 2 2 Ep 2o fp Ep o gp Es o hp Ep oEs o
(57)
(58)
132
when using ppolarized fundamental light, the expression is considerably simplified 1 fs f tan fp
(59)
The angle f is dependent upon the chirality of the sample. The chirality of the sample is reflected through the sign and magnitude of fs. As we know, the sign of fs reverses between two enantiomers, and the sign of the achiral coefficient fp does not change. As a consequense, f changes sign between the two enantiomers. Using this relationship, different enantiomers of a chiral molecule can be distinguished by the sign of the SHGORD rotation angle. The magnitude of the SHGORD effect will depend on the ratio of chiral and achiral components. f will be large if fs is not zero and large compared to fp. No resonance is required for SHGORD to occur, though, fs can be resonantly enhanced which would increase the ratio in Eq. (59). Note also that the rotation angle is limited to 908, while in linear optics optical rotation can add up unlimited by propagating through the chiral medium. 4.3. Continuous polarization measurements In the previous section, we introduced SHGCD and SHGLD and SHGORD as nonlinear techniques to probe surface chirality. While these techniques are useful for the detection of surface chirality, it is difficult to differentiate between the enantiomers. However, all structural information is embedded in the nonlinear susceptibility tensors. Hence, it would be extremely useful to know the relative values of all components of this tensor. Here we describe a method that is able to determine the relative complex values of the coefficients f, g and h (which are related to weee, weem and wmee) for various secondharmonic signals in a unique way. The method is based on a series of continuous polarization measurements. The polarization of the fundamental is continuously varied by a rotating quarterwave plate (QWP). The intensity of the secondharmonic light is recorded, in transmission and reflection as a function of the rotation angle of the quarterwave plate. Such measurements are referred to as polarization measurements. In this case the polarization pattern also contains information on the circulardifference response. However, polarization measurements provide also direct information on the chirality of the sample. We can write the p and spolarized components of the fundamental beam as Ep o E0 cos2 j i sin2 j Pj Es o E0 sin j cos j1 i Sj (60) (61)
where E0 is the amplitude of the initial fundamental field, j is the rotation angle between the ppolarized direction and the axis of the wave plate, and P(j) and S(j) represent the functional dependence of the fundamentalfield components on the rotation angle. The intensity of the secondharmonic field then has the general functional form (cf. Eq. (47)): Ij jE2oj2 jfP2 j gS2 j hPjSjj2 (62)
When the detected signal is spolarized and the surface is achiral, the only nonvanishing expansion coefficient is hs. The polarization pattern of the secondharmonic intensity then has the form: Is j jh2 jjPjSjj2 s (63)
133
0. 5
0.5
Fig. 8. (a) Normalized line shape of spolarized signals for quarterwave plate measurements for an achiral, isotropic surface. (b) Normalized line shape of ppolarized signal for quarterwave plate measurements for a chiral, isotropic surface.
This pattern is shown in Fig. 8(a). This is a typical line shape for an achiral surface and any deviation would imply that the surface is chiral. Note that this result is independent of the existence or lack of a phase difference between the components fs, hs, and gs. When we detect the ppolarized secondharmonic signal, the nonzero expansion coefficients for an achiral surface are fp and gp. Therefore there does not exist a typical achiral line shape for ppolarized detected signals, however we can find evidence of chirality in the properties of the line shape of ppolarized signals. One can see that in the case of an achiral sample the secondharmonic intensity is Ip j jfp P2 j gp S2 jj2 (64)
which is an even function of the rotation angle j, because P2(j) and S2(j) are even functions of j. On the other hand, for the case of a chiral sample, the intensity has the general form of Eq. (62), which has no well defined parity with respect to j. Hence, when there does not exist a mirror plane in respect to the 1808 rotation angle j, the sample is chiral. Chirality leads to a leftright asymmetry in the polarization pattern Ip(j) (Fig. 8(b)). This asymmetry is reversed if the handedness of the sample is reversed. Similar arguments are also valid for the spolarized secondharmonic signals. We can conclude that the lack of a mirror plane in respect to the 1808 rotation angle j in the p or spolarized signals is an evidence of chirality. While, for SHGCD and SHGLD effects certain requirements of resonance are to be fulfilled in order to detect the chirality of a sample, asymmetry in the polarization pattern is a direct evidence of chirality. The phase relation between the achiral and chiral components will only change the details of the asymmetry. Quantitative information can be obtained from these patterns by fitting them to the following equation [39]:
1 I2o 16 fRe gRe 4fIm cos 2y fRe gRe cos 4y 2hIm sin 2y hRe sin 4y2 I 2 o 1 16 fIm gIm 4fRe cos 2y fIm gIm cos 4y 2hRe sin 2y hIm sin 4y2 I 2 o
(65) where fRe, gRe, hRe, fIm, gIm, and hIm, are the real and imaginary parts of the coefficients f, g, and h respectively, and y is the rotation angle of the quarterwave plate. From this equation, one can extract the values of f, g, and h. To fit the experimental results, it is necessary to fix the overall phase. This can be done, for example, by defining h as a real quantity (hIm 0). The values found for the coefficients f, g, and h can then subsequently be used to calculate the values of the components of the
134
secondorder susceptibility, w(2). Note that both phase and magnitude of all tensor components are relative values. The absolute phase cannot be determined because of the arbitrary choice of hIm 0. In addition, all secondharmonic intensities are recorded in arbitrary units, so that no absolute magnitude of a component can be calculated. However, absolute values of a component can be determined by calibration with a quartz wedge [40]. 4.4. 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 sign of the effect will also change between the two enantiomers of the molecule. Optical activity effects can also arise from achiral samples. This has been observed in linear optics: the efficiency for photoelectron emission from oriented molecules was different for left and righthand circularlypolarized light. This was the case if the molecular axis, the wave vector of the incoming light and the direction of detection of photoelectrons were not coplanar [4143]. Such optical activity effects are possible if the experimental setup itself was chiral, i.e. possesses a definite handedness and is characterized by three noncoplanar vectors. The same findings were made in nonlinear optics: if the experimental setup could be defined by three noncoplanar vectors, i.e. was chiral, optical activity effects would occur even if the sample was achiral. Three different cases were investigated. First, 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]. By using linear control polarizations, the reflection symmetry of the setup is broken and leads to different secondharmonic efficiency for left and righthand circular probe polarizations. Moreover, also circular control polarizations can be used to break the reflection symmetry. A film of polymaleimide functionalized by a disperseredtype chromophore was spincoated and gave an C1vsymmetry after poling. The polar axis coincides with the surface normal. The wave vectors k1 and k2 of the control and probe beam are in the same plane of incidence (Fig. 9). When the polarization of the control beam is considered, the setup is chiral. In the first experiment, control beams with linear polarization were used. The two control polarizations are related to each other by reflection in the plane of incidence. A circulardifference response was observed and changed sign when the handedness of the setup was reversed. The magnitude of the effects was $15%. In the second experiment, circular control polarizations were used. Also in this case (in contrast to the photoemission effect) a circulardifference response was observed. The spin of the control polarization can be
k1+k2 2
thin film k1 s (s p) / p
k1 s (s ip) / 2 p
Fig. 9. Experimental setup. Two beams at the fundamental frequency are applied on the same spot of an isotropic achiral surface. The wave vectors of the beam (k1 and k2) are in the same plane of incidence. Secondharmonic light is detected in the transmitted direction k1 k2 . The reflection symmetry of the setup can be broken with linear (a) or circular (b) control polarizations. In both cases, the setup can possess two opposite handednesses. The probe polarization is controlled by a rotating quarterwave plate.
135
p z s k x y
Fig. 10. Experimental geometry: fundamental laser beam (wave vector k, s and ppolarized field components) is incident on the sample at an angle y. The azimuthal rotation of the sample is characterized by f. The arrows on the sample indicate the alignment of the achiral molecules along the dipping direction that creates the anisotropy axis. The anisotropy axis and the surface normal are along the x and zdirections, respectively.
associated with a coordinate system with a welldefined handedness. The circulardifference effects were much larger ($80%) then in the first experiment. The chirality of the setup was defined by the control polarization, the probe polarization and the surface normal. These three noncoplanar vectors broke the reflection symmetry. Other combinations of noncoplanar vectors associated with an experimental setup can be found. When the orientation of the molecules does not coincide with the surface normal, the setup becomes chiral for some orientations of the film in respect with the incident beam. In this case the surface normal, the ansitropy axis and the input beam form a coordinate system with a definite handedness. Such an anisotropic LangmuirBlodgett film of an achiral material was investigated [44]. Fig. 10 shows that for some orientations the setup becomes chiral. Note that for the angles f 0 or 1808 and y 0 or 1808, the plane of incidence is a mirror plane and the setup is achiral. For any other values of these angles, the setup is chiral and the handedness can be reversed by reflection operations. The experiments were carried out with a Qswitched Nd:YAG laser (1064 nm, 50 Hz, $10 ns). The sample is mounted on a rotation stage and is allowed to rotate around its surface normal. The experimental results for all combinations of the angles y and f are summarized in Table 3. As expected, no circulardifference effects were observed for f 0 and 1808. For the value f 90 , substantial difference effects were observed and changed sign when the sign of f was reversed. The magnitude of the difference effects remains unchanged. Furthermore, the difference effects also change sign between positive and negative angles of incidence y. These results show that the circulardifference response reverses sign as the handedness of the sample orientation is reversed, i.e. as one of the angles y and f changes sign.
Table 3 Experimentally observed circulardifference effects DI/I 2Il Ir /Il Ir for different sample orientations f and angles of incidence y Incidence angle y (8) 43 Sample orientation f (8) 0, 180 90 90 0, 180 90 90 Circulardifference effect (%) (0 2) (6 1) (7 1) (1 2) (7 1) (8 1)
43
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The theoretical origin of these results can be found in the fact that the expansion coefficients fi, gi, and hi, which describe the nonlinear response, are dependent not only on the nonlinear susceptibility components and the angle of incidence y, but also on the azimuthal rotation angle f. It can be shown in general that f g or h, but not both reverses sign under reflection operation. Hence, the circulardifference effects are expected to change sign as the handedness is changed. The question was now how to distinguish between circulardifference effects arising from anisotropy and the chirality of the sample. Two possible solutions were put forth. First, one can do a full analysis of the tensor components, taking into account that the equations of fi, gi and hi will depend on the azimuthal rotation angle f. A measurement technique was presented in [35]. A chiral, anisotropic film with C2symmetry was prepared from a helicene bisquinone. Because the material is chiral, one must be concerned about the possibilities of magnetic contributions to the nonlinearities. However, no evidence of magnetic contributions could be found in these films. LangmuirBlodgett films of the chiral material were prepared. The fundamental beam of a Qswitched Nd:YAG laser (1064 nm, 8 ns, $1 mJ, 50 Hz) generated the secondharmonic light at 532 nm. First, the symmetry of the films was determined. The secondharmonic signal was recorded as a function of the azimuthal rotation angle. The pattern indicated that film had a C2symmetry. As mentioned earlier, polarization measurements can be used to calculate the values of the tensor components. The measurement technique proposed in [35] is based on these polarization measurements. Polarization measurements were done for three different azimuthal rotation angles f (0, 45, and 908). The solutions for the tensor components are given in Table 4. Because of the anisotropy of the sample, the individual tensor components shown in Table 4 are anisotropic. They change value when the polarization measurements would be carried out for other azimuthal rotation angles. Only certain combinations (also shown in Table 4) are isotropic and can be uniquely classified as chiral or achiral. The achiral isotropic combinations are wzzz, wzxx wzyy , wxxz wyyz and the chiral isotropic combination is wxyz wyxz . The results show that the chiral part of the nonlinearity completely dominates the response of the sample. 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]. The experiments were performed on a LangmuirBlodgett film of a nonracemic helicene shown in Fig. 11. The sample had a C2symmetry. For such a symmetry the circulardifference response as a function of the azimuthal rotation angle is DI a1 a cos 2f b sin 2f c cos 4f 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 yxz xxz yyz zxx zyy The magnitudes are referenced to quartz (0.3 pm/V). Results 1.18 1.58 28.84 32.09 4.42 2.59 4.60 3.52 60.93 2.76 7.18 i0.62 i1.02 i9.33 i11.44 i2.16 i0.13 i1.74 i1.16 i20.77 i0.40 i1.62 Magnitude (pm/V) 1.0 1.5 24 26 3.8 2.0 3.8 2.9 50 2.2 5.7
(66)
137
OC 12H 25
C12H25O
O O O
where the coefficients a1, a, b, c, and d are functions of the susceptibility components and of the angle of incidence y. This expression implies that the circulardifference response DI, depends on the azimuthal rotation angle f. It is comprised of a component that varies sinusoidally superimposed on one, a1, that is isotropic. If the sample would be achiral and consequently have a C2vsymmetry, the circulardifference response reduces to DI b0 sin 2f d0 sin 4f (67)
where b0 and d0 are coefficients that depend on the susceptibility components and the angle of incidence y. An important difference between Eqs. (66) and (67) is the absence of the isotropic part a1. As a consequence the average of Eq. (67) over 3608 is always zero, while that of Eq. (66) is not. One can conclude that chirality of materials is linked to a nonzero rotational average for DI, which provides a way to differentiate nonlinear optical CDeffects originating from chirality and those originating from anisotropy. We measured the CDresponse as a function of the azimuthal rotation angle f. The resulting pattern is shown in Fig. 12. The sinusoidal variation indicates that the sample is highly anisotropic. Moreover, a1, the CDresponse averaged over 3608, is large compared to the total variation (30 on the scale in Fig. 12). This value represents the isotropic part of the response and implies that the sample is chiral. As a conclusion, it is clear that CDeffects in secondharmonic generation have to be handled with care. It is always important to determine the symmetry of the sample and then to interpret the results measured. In the case of a sample with inplane isotropy, the CDeffects arise from the
120 90
CDSHG
Fig. 12. Circulardifference response in SHG as a function of the azimuthal rotation angle (the 08 orientation is arbitrary). The average of the CDresponse over 3608 is 30 represented by the line.
138
HO
OH
chirality of the sample, as far as there is no misalignment of the polarizer. In the case of an anisotropic sample, 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. 4.5. SHGCD: a tool to probe surface chirality The first experimental evidence of SHGCD came from PetralliMallow et al. They studied SHG from a chiral 2,20 dihydroxy1,10 binaphthyl molecules (Fig. 13) adsorbed at an airwater interface [27]. The SHG signal from the surface was recorded versus wavelength in the reflection geometry, using a circularlypolarized fundamental beam. They noticed that the SH intensity was different for left and rightcircularlypolarized light. Furthermore, the observed CDeffects had the same magnitude but opposite sign for the enantiomers. The circulardifference effects DI/I reached values as high as 100% and the SHGCD spectra also resembled the (linear optical) CDspectra. However, at that time they were no explanation could be given for the and origin of the SHGCDeffect. Possible explanations such as, different absorption of the two circularlypolarized beams due to linear circulardichroism, aggregation of molecules which enhances SHGCD, contributions of magneticdipole and quadrupole interactions originating from the bulk, were put forth, 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]. More recently, LangmuirBlodgett films of a chiral 1,10 binaphthylbased helical polymer were studied [46]. The polymers used in the study were prepared from chiral 1,10 binaphthylbased monomeric units and optimized for nonlinear optics by adding a pconjugated bridge and electron donor and acceptor groups (Fig. 14). The monomer units can be considered as an ensemble of rigid
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 [47,48]. Using the procedure of continuous polarization measurements, we were able to characterize the complete susceptibility tensor. Furthermore, the absolute magnitude of each component was calibrated using a quartz wedge (Table 5). There was no evidence of magnetic contributions to the nonlinearity. The high values for the components zzz, zxx and xxz suggest favorable ordering of the chromophoric parts of the polymer in the LB film. The chirality of the LB film manifests itself in the observed SHGCDeffects. Also the presence of a small (but nonnegligible) chiral component xyz reflects the chirality of the film. 4.6. Evidence of strong magnetic contributions in chiral polymers Significant magnetic contributions to the nonlinearity of thin films of some chiral polymers have been observed. The first observation of magneticdipole contributions were observed from the films of chiral polyisocyanide and polythiophene. Both materials form LangmuirBlodgett films with C1symmetry. The polyisocyanides investigated are shown in Fig. 15 [49]. The samples were analyzed by a series of continuous polarization measurements in reflection and transmission geometry. Note the peculiar structure of the molecules: chirality and nonlinearity are present on different levels of the molecular structure. Chirality is localized in the helical backbone of the molecule, while the nonlinearity is localized in the pendant, achiral chromophores. Strong circulardifference effects and strong asymmetric polarization patterns are an indication of chirality of the sample. Moreover, the results could not be explained within the electricdipole approximation and we had to include magnetic contributions. The largest nonlinear magnetic susceptibility was found to be of the order of 10% of the largest pure electric susceptibility. Chirality and nonlinearity are not present on the same level of the molecule although chirality effects are observed in the nonlinear optical response [50]. 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
N N NO2 N
C4H9
C4H9
140
chromophores. A simultaneous excitation of the NLO chromophores leads to a helical charge displacement along the backbone of the polymer. Films of a similar polyisocyanide mixed with poly(S1acetoxymethylethyl isocyanide) (Fig. 16) were analyzed in detail [51]. Analysis of the polarization pattern allowed the determination of the relative amplitudes of all electric and magneticdipole susceptibility components (Table 6). 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. The absolute value of the electricdipole component zzz of LangmuirBlodgett films of a similar polymer system was determined to be of the order of 9 pm/V [52]. Therefore, the largest magneticdipole component of this system would be approximately 2 pm/V. 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. 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. However, more research is needed to prove this hypothesis.
Table 6 Relative magnitudes of the components of weee, weem, and wmee for the poly(isocyanide) mixed with poly(S1acetoxymethylethyl isocyanide) Tensor w
eee
Components zzz zxx zyy xxz xzx yyz yzy xyz xzy yxz yzx zzz zxx zyy xxz yyz xzx yzy xyz yxz zxy zyx xzy yzx zzz zxx zyy xxz xzx yyz yzy xyz xzy yxz yzx
Chirality Achiral Achiral Achiral Chiral Chiral Chiral Chiral Chiral Achiral Achiral Achiral Chiral Chiral Chiral Achiral
Relative amplitude 1.00 0.62 0.60 0.08 0.23 0.12 0.01 0.05 0.06 0.13 0.06 0.15 0.00 0.00 0.03
weem
wmee
141
CH3
Evidence of high magneticdipole contributions to the nonlinearity has also been found in LangmuirBlodgett films of a chiral poly(thiophene) (Fig. 17) [53]. The magneticdipole contributions observed in these LB films are of the same order of magnitude as the electricdipole nonlinearities. The sample studied was a ten layer LangmuirBlodgett film of the regioregular chiral polythiophene poly[3[2((S)2methylbutoxy)ethyl]thiophene] [54,55]. In good solvents, like CHCL3, the polymer is in a random coil conformation and does not exhibit optical activity in its pp transition of the polythiophene. However, in the solid state, in poor solvents, or in appropriate combinations of solvents, the polymer is associated in small domains and the chiral side groups induce an enormous optical activity in the pp transition of the polythiophene. This association with a chiral conformation is accompanied by a strong solvatochroism and the films have a purple/red color (lmax 512 nm), while the random coil conformation has an orange/yellow color (lmax 445 nm). To prepare the Langmuir Blodgett films, 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, the polymer folds into the chiral conformation and changes color from yellow to purple. The SHG from the films was measured by continuously varying a quarterwave plate in the path of the fundamental beam (1064 nm). 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. Unfortunately, due to the instability of the sample, the authors were not able to determine absolute magnitudes of the components of weee, weem, and wmee. SchanneKlein et al. [56] studied spincoated films of the chiral dye shown in Fig. 18 and separated the electric and the magneticdipole contributions to the nonlinearity. They performed continuous polarization measurements and determined the SHGCD and SHGLD values. They also measured SHGORD. From these data they extracted the relative values of the tensor components. The results are shown in Table 7. The chiral magneticdipole contributions were of the same order of
* Et2N
+
N * OH

ClO4
Fig. 18. Chemical structure of chiral penthamethinium salt. The stars indicate the asymmetric carbons.
142
Table 7 Relative magnitude of the components (or combination of components) of weee, weem, and wmee for the chiral compound in Fig. 18 Tensor component weee zzz weee zxx weee xxz weee xyz 2weem xxz Chirality Achiral Achiral Achiral Chiral Chiral Relative magnitude 1.00 0.080 0.310 0.0120.018 0.03
wmee zxx
magnitude as the chiral electricdipole contributions: weem % wmee , these components have typically xxz zxx the same order of magnitude as weee . The dipolar electric contributions arise from the pelectrons on xyz the carbonyl chain but they are not strongly delocalized between the two nitrogen atoms, and therefore the dipolar electric nonlinearities are not expected to be strong. That is probably the reason why magnetic effects are as strong as dipolar electric ones concerning the chiral components. These experiments provided evidence that the magneticdipole contributions can be important even in nonresonant conditions (the dye does not absorb at the secondharmonic wavelength). The previous experiment illustrates the relative strength of electric and magneticdipole transitions in secondorder optical activity. We can conclude that optical activity can occur in surface secondharmonic generation from the electriconly response, but we find that the magnetic response can make a similar contribution and thus should not be ignored. These conclusions were also drawn from the theoretical approach of the nonlinear optical activity. Maki and Persoons calculated the oneelectron secondorder optical activity of a helix [26]. The optical response is classically modeled by using a single electron bound to a helical path (Fig. 19). The helical motion of the electron causes optical activity in the secondorder response. The microscopic secondorder response is (characterized by the hyperpolarizability b) calculated for a chiral molecule, but also the macroscopic secondorder response (characterized by the nonlinear susceptibility w) of both surfaces and solutions of chiral molecules. From the equations for b and w one can see that the magnetic contributions are enhanced in a helical molecule. beee, 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 b 3; beem ; bmee /
z'
io e3 ra zb c m2
with a b 4
(68)
e x'
y'
143
O H2N CH C HN CH2
HN
HN
where beee, beem and bmee are the molecular analogues of weee, weem and wmee, m and e are the mass and the electric charge of the electron. o is the frequency of the applied fundamental field. The macroscopic response (w) can be found by averaging the microscopic response for the various orientations of the helix in space. beem and bmee depend on r and z with an overall order of 4. beee, on the other hand, depends on r and z with an overall order of 3. As a consequence, the magnetic contributions increase more rapidly than the electric when the molecule has more helical character. 4.7. Biological systems studied with SHGCD SHGCD is a surface sensitive technique and can be used to study interfaces and surfaces. Crawford et al. [57] explored the possibilities of this technique to study biological systems. The airwater interface of aqueous (tbutyloxycarbonyl)tryptophantryptophan (BocTrpTrp) has been studied by surface SHGCD (Fig. 20). SHG has already been observed for some amino acids (tryptophan, tyrosine, and phenylalanine) using 532 nm fundamental radiation, from the surface of aqueous solutions [58], and over the 270300 nm region for tryptophan and tyrosine. Tryptophan gives the strongest SHG signal. However, being chiral, tryptophan did not show any secondharmonic optical activity. The molecular hyperpolarizability bxyz is expected to be zero since tryptophan chromophore is planar. In contrast, the dipeptide BocTrpTrp, shows significant SHGCD and SHGORD. In these experiments, a Nd:YAG pumped dye laser (5 ns, 10 Hz, $20 mJ) operating at wavelengths between 550 and 580 nm was used to record the SHGCDresponse. The beam was incident at the liquid surface at 608 to the surface normal. There is a significant difference in the SHG signals observed for left and rightcircularlypolarized fundamental incident radiation and ppolarized SHG radiation. The SHGCDresponse reached values near 150% at 276 nm. 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. The 50/50 racemic mixture gave no SHGCDresponse. Achiral molecules adsorbed at the airwater liquid interface give rise to no SHG signals from the polarization combination ps (ppolarized fundamental, spolarized second harmonic). However, for chiral molecules, a nonzero ps signal can be observed. SHGORD spectra were measured between 276 and 286 nm. The sign of the ORD of the LL form was opposite to that of the DD form. Experiments were also performed on the diastereoisomer BocLTrpDTrp. The SHGCDeffect increases towards longer wavelengths (for pdetection). 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. The SHGCD signal can be explained by the presence of the tensor component wxyz, which can only be nonzero for chiral surfaces. In the BocTrpTrp molecule, the rings are tilted with respect to each other (like the two rings in binaphthol), which explains a significant molecular hyperpolarizability bxyz of the dipeptide. This will in turn lead to a nonzero wxyz term.
144
+ N H
Lys
Another biological molecule probed with SHGCD is bacteriorhodopsin [59] (Fig. 21). Bacteriorhodopsin is a lightenergytransducing protein that is present in the purple membrane of halophilic bacteria. In the purple membrane, the protein is arranged into clusters of three that show stronger optical activity than individual molecules. Linear circulardichroism spectra of suspensions of purple membrane in water typically show a relative circulardifference effect of De=e 0:1%. Bacteriorhodopsin also exhibits strong nonlinear optical activity. The bacteriorhodopsin sample was analyzed using continuous polarization measurements. First, the bacteriorhodopsin molecules were embedded in a LangmuirBlodgett film. In the films, the bacteriorhodpsin molecules were in a soya phosphatidylcholine matrix in a molar ratio of 1:28. In such a film, the bacteriorhodopsin molecules can exhibit local ordering in a lattice similar to the one that occurs in the purple membrane. In spite of this local ordering, the molecules are randomly distributed on a scale much smaller than the optical wavelength. Hence, the film constitutes an isotropic surface with full rotational symmetry about the surface normal. The secondharmonic generation of the ppolarized transmitted component was dependent on the helicity of the fundamental beam. The circulardifference effect was about 25%. For the spolarized component, the circulardifference effect was about 13%. To assess the usefulness of the effect for other, more practical, types of samples, a drop of purple membrane suspension in water was placed between two glass slides. 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. This inhomogeneity is most likely an indication of aggregation of the purplemembrane fragments. These samples also exhibit a strong circulardifference response, which for the spolarized signal is $100%. The very strong circulardifference response is due to supramolecular chirality of bacteriorhodopsin trimers. SHGCD has also been used to follow the adsorption and redox properties of a peripheral membrane protein, horse heart cytochrome c, adsorbed at several model membrane surfaces [60]. The SHGCDresponse is shown to be affected by the oxidation state of the heme within the surfaceadsorbed cytochrome c, as is consistent with the sensitivity of SHG to the chirality of the heme. Cytochrome c is an interesting redox species due to its membraneassociated activity and its biological role in electron transport. At carboxylic acidterminated selfassembled monolayers (SAMs), 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. Hybrid bilayer membranes (HBMs) have been shown to have many properties of cell and model membranes. HBMs are electrically addressable using a underlying gold film as working electrode. The laser system used for the SHGCD studies consisted of a modelocked titaniumsapphire (TiS) laser (150 fs, $5 nJ/pulse) pumped by a beamlocked argon ion laser. The incidence angle used was in the range of 45518 from the surface normal. The SHGCDresponse for spolarized detection at 798 nm was studied for cytochrome c adsorbed at three surfaces: HBM, on hydrophylic SAM and on hydrophobic SAM. In the oxidized state, the SHGCDresponse DI/I of cytochrome c is negative. When cytochrome c adsorbed on the SAMs it was reduced by adding an excess ascorbate, the spolarized SHGCD became more positive. In contrast, the introduction of ascorbate to cytochrome c adsorbed at the HBM surface, resulted in a
145
negative SHGCDeffect. The result suggests that HBMassociated cytochrome c is not reduced by ascorbic acid. This work demonstrates for the first time that SHGCD can be used to probe the oxidation state of a redox protein, cytochrome c, adsorbed at surfaces. 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, but not when they are bound to mixed lipid layers containing zwitterionic and negatively charged phospholipids. This work demonstrates the potential for SHGCD studies of native biological surfaces. 4.8. Chirality as a tool for nonlinear optical applications The requirement of noncentrosymmetry in nonlinear optics can be achieved in several ways. One of the most widely used methods to induce macroscopic noncentrosymmetry is electricfield poling of nonlinear optical polymers. The polymer containing a nonlinear optical chromophore is spincoated on a substrate. Subsequently, 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. Then, the polymer film is cooled below Tg in the presence of the field, to freeze in the orientation. The symmetry of such films is C1 and C1v for chiral and achiral samples, respectively (Fig. 22a). Unfortunately, poled films are thermodynamically unstable, and eventually return to their original isotropic centrosymmetric state [19]. Furthermore, poling can be quite complex and time consuming. One of the obstacles of efficient poling is the aggregation of chromophores. Chromophores with high dipole moments embedded in a polymer matrix, will easily aggregate due to dipoledipole interactions. This aggregation will reduce the efficiency of the poling process [6164]. Therefore, it would be beneficial to relax the requirement of polar ordering along the film normal. For example, one can then rely on ytype deposition of LangmuirBlodgett films, where transfer occurs both at up and down strokes. Removal of polar ordering results in a sample with twofold rotation axis in the plane of the film. Such films have axial ordering along the surface normal. The symmetry groups of chiral and achiral samples are D1 and D1h, respectively (Fig. 22b). The nonvanishing tensor components for these groups are listed in Table 8, and they depend on all three spatial coordinates. Consequently, the electricdipole tensor vanishes unless the sample is chiral. However, chirality allows electricdipole nonlinearities without polar order. The D1 and D1hsymmetry can also be found in other systems: liquid crystals, spincoated films, etc.
(a)
Film normal
(b)
Film normal
Fig. 22. (a) A thin film with C1symmetry. The sample has polar order along the film normal but the orientational distribution of the molecules is isotropic in the plane of the film. Any rotation about the film normal is a symmetry operation. When the molecules are achiral, reflection in the plane containing the normal is also a symmetry operation. (b) A thin film with D1symmetry. The sample has only axial, but no polar order. Any rotation about the film normal is a symmetry operation. In addition, 1808 rotation about any axis in the plane of the film is a symmetry operation. When the molecules are achiral, reflections in a plane containing the normal and in the plane of the film are also symmetry operations.
146
Table 8 Nonvanishing components ijk of tensors weee, weem, 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 yxz xzy yzx zxy zyx xyz yxz xzy yzx zxy zyx
Films with D1symmetry can in principle be made by the LangmuirBlodgett technique. In a recent study, Verbiest et al. prepared LB films of a chiral helicene. Although, the symmetry of the film was not a perfect D1symmetry, the experiment definitely proved that polar order is not a necessary requirement for secondorder nonlinear optics. In fact, the symmetry of the film was very close to D2, a symmetry that also lacks polar order. The molecules studied were those of the tetrasubstituted helicenebisquinone, shown in Fig. 23 [65]. In bulk samples the enantiomerically pure form of the material spontaneously organizes into long fibers clearly visible under an optical microscope, while the racemic form does not aggregate. These fibers comprise columnar stacks of helicene molecules. Similar columnar stacks form in appropriate solvents when the concentrations are greater than $1 mM. This formation of aggregates is associated with an increase in the circulardichroism of the solution [66]. LangmuirBlodgett films were made of the helicene by spreading a dilute chloroform solution (2 104 M) onto the pure water subphase of an LB trough. Subsequently, the layer was compressed to a surface pressure of 20 mN/m and transferred to a hydrophobic glass substrate by horizontal dipping. UVVis absorption spectra, 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 [65,67]. The samples were analyzed by a series of continuous polarization measurements. Good optical and structural quality of the films was confirmed through the quadratical growth of the SHG signal with the thickness of the sample. 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, corresponding to a $30fold enhancement in the value of the susceptibility. The strongest signal for the nonracemic film was ps (ppolarized fundamental and spolarized SHG), whereas, for the racemic film the pp signal was the strongest. When examining Eq. (48), it is clear that the ps signal is due to the
O O
H25C12O
OC12H25
OC12H25
OC12H25
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 yyz zxx zyy xyz 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. The pp signal is allowed for all isotropic surfaces and thus is due to the achiral tensor components. This result implies that for the nonracemic sample, the dominant part of the susceptibility can be associated with chirality. In the racemic samples, this part must cancel. An explanation for the different behavior of the two types of samples is that the helicene packs differently in the racemic and nonracemic films. To investigate these possibilities the authors first had to analyze the susceptibility components of the two films. The analysis was not straightforward because the film exhibited twofold symmetry. They had to examine combinations of susceptibility components, which are invariant under rotation operations around the surface normal and are given in Table 9. The reason for this is that for a surface with a twofold symmetry the x and ydirections are arbitrary. All the rotational invariants were determined by analyzing SHG polarization patterns. No evidence was found of the presence of magneticdipole contributions. The nonlinear optical response of the nonracemic films was dominated by the combination: xyzyxz. This combination is associated with chirality. Note that the NLO response of LB films is usually dominated by the zzz component. The magnitude of the chiral combination xyzyxz is within one order of magnitude of the highest values ever observed in LB films. The high magnitude of the chiral susceptibility, combined with the good thermal stability (stable up to 2008), makes this is a promising material for device applications. The reason for the high nonlinearity of the supramolecular structure was attributed to the formation of supramolecular aggregates with high nonlinearity. In films made of the pure enantiomerically material, these nonlinearities add up, while in racemic films they cancel. In another experiment, films of a similar helicene derivative were spincoated onto glass substrates, yielding films of 0.10.6 mm. From UVVis absorption spectra it was seen that the molecules selfassembled in corkscrewshaped structures [67]. Continuous polarization measurements were carried out on the samples. As the nonracemic films showed SHG response, the symmetry of the films had to be at least D1. The exact symmetry was determined by detecting the SHG signal while rotating the sample about its surface normal. The films were isotropic in the plane which corresponds to a C1 or D1symmetry. To discriminate between those two, polarization combinations of the fundamental and secondharmonic were analyzed. For an spolarized fundamental beam no secondharmonic signal was detected. For the ppolarized fundamental, only the spolarized secondharmonic was nonvanishing. This implies a D1symmetry with only one nonvanishing tensor component wxyz. The magnitude of the component was determined to be 2 pm/V. This experiment again illustrates the potential of chiral materials in NLO. The advantages of such films are clear. Because no polar order had to be introduced by an external force, relaxation cannot occur. Moreover the films showed good thermal stability over a wide range of temperatures. Heating the films up to 200 8C did not affect the SHG efficiency. Above the melting point, the material becomes an isotropic liquid and the SHG signal drops to zero.
148
R'O R'O O RO O
OR' OR + R'O O
O R' RO O
OR' OR
R= O
Nevertheless, cooling the liquid restores the initial symmetry and the original SHG values are detected. These were remarkable results because spincoating results used in isotropic films. The D1symmetry can be explained by the organization of the molecules in liquid crystallinelike layers that stack together. Another illustration of the potential of chiral molecules in NLO is given by the following experiment. Binary mixtures of isomeric nonracemic (M)()helicenes shown in Fig. 24 and dodecane tend to form liquid crystals. A headtotail aggregation of the molecules is favored by the steric hindrance of the bulkier ends that keeps the molecules apart. As a result the mixtures exhibit a chiral discotic nematic phase [68]. The solution (1, 20 wt.% dissolved in dodecane) was placed between a rubbed 4 mm LC cell at room temperature. The samples were probed by continuous polarization measurements. The only secondharmonic signal detected was the ps signal (ppolarized fundamental, spolarized secondharmonic). Rotating the sample about its surface normal did not change the magnitude of the secondharmonic signal. For the same reasons mentioned above, the symmetry should be D1. The only nonvanishing component for this system is the chiral wxyz component: this is an apolar component, it is nonvanishing in samples without polar order. The magnitude of the component was measured and compared to a quartz reference (d11 0:3 pm/V) and was 0.13 pm/V. When an electric field was applied to the cell, the symmetry of the sample changed from a nonpolar D1 to a polar C1. The result is that additional polar tensor components appear: wxxz, wzxx and wzzz. The values of all tensor components were measured and calibrated against a quartz reference: wxyz 0:68 i0:16 pm/V, wxxz 0:51 pm/V, wzxx 0:59 i0:03 pm/V, and wzzz 1:22 i0:1 pm/V. The applied electric field was 10 V/mm. In Fig. 25, one can see that the total signal increases by a factor 3.5 when applying the electric field. When switched off, the signal decreases again to the original value. It is also notable that when the polarity of the field is reversed, the values of the polar tensor components change sign while the sign of the apolar tensor component remains unchanged. The magnitudes are unaffected within the experimental errors. wxyz 0:64 i0:15 pm/V, wxxz 0:47 pm/V, wzxx 0:58 i0:002 pm/V, and wzzz 0:78 i0:015 pm/V. The ability to reverse the sign of the tensor components can be used in quasiphasematching to prepare efficient frequencyconversion devices. The SHGCDresponse which is depended on chiral and achiral components, will change sign when the polarity of the applied field is reversed. This is explained by the fact that only the achiral components change sign under reversion of the polarity of the electric field. For the spolarized component of the secondharmonic field, the CDresponse changes from 43 to 45%. Note that this effect cannot be observed in linear optics since the refractive index cannot change sign.
149
3000
100
200
300
400
500
600
700
800
Time (sec)
Fig. 25. Plot of the secondharmonic signal intensity (I(2o), in arbitrary units) vs. time t. At time t2 the field was switched off.
To conclude, all experiments above are proof that chiral samples without polar order can exhibit nonlinear optical activity. Because no external force is needed to introduce a Dnsymmetry, these films are thermodynamically stable which is a great advantage over poled polymer films which tend to relax in time. In addition, for the chiral liquid crystal, an external electric field can increase the existing signal by introducing a polar order. 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, optical switches, phaseshifters and quasiphasematching are possible applications for this system. 4.9. 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. The interaction must be phasematched. Phasematching is hard to realize, because refractive indices of materials change with the wavelength. In secondharmonic generation, for example, the wave vectors of the fundamental and secondharmonic beams ko and k2o are proportional to the indices no and n2o at the two frequencies. The phase (or wave vector) mismatch for copropagating fundamental and secondharmonic beams is thus Dk 2ko k2o 4pno n2o lo (69)
where lo is the fundamental wavelength. Consequently, after a distance Lc p/jDk j, known as the coherence length, the source polarization and generated field are outofphase. Phasematching can be achieved in birefringent materials, because their refractive indices depend on the polarizations of the interacting fields. Because of some limitations, an alternative to perfect phasematching, known as quasiphasematching, is frequently used. In this procedure, the signs of the nonlinear optical coefficients are reversed after every coherence length, or after any odd multiple of it. This restores the phase relation between the source polarization and the generated field, allowing the nonlinear signal to grow quasicontinuously. Because for enantiomers the nonlinear coefficients associated
150
with chirality are opposite in sign, quasiphasematched frequency conversion should be possible in periodically alternating stacks of enantiomers [69]. Busson et al. prepared such alternating stacks of enantiomers and demonstrated that they can be used for quasiphasematched secondharmonic generation. A series of samples was investigated in which equally thick stacks of the two enantiomers alternated. Quasiphasematching is verified by measuring the intensity of the secondharmonic signal associated with chirality as a function of the thickness of the stacks. The experiments were analyzed by considering a model for the structure that consists of p stacks, each of thickness L, in which the sign of the secondorder nonlinearity alternates. The secondharmonic amplitude E2 along the zdirection is given by the following equation: E2 pL / G 1 eai DkL eapL 1p ei DkpL a i Dk 1 eai DkL (70)
where G is a constant numerical factor proportional to the squared amplitude of the fundamental beam, a is the linear absorption coefficient at the secondharmonic wavelength, and Dk is the wave vector mismatch. According to the above equation, the output intensities from a series of films with a fixed number of stacks p, but with increasing thickness L, are expected to grow until L Lc and then to decrease. When the thickness of each stack equals the coherence length, the intensity is expected to grow with the number of stacks p. The growth should be quadratic when the material does not absorb the secondharmonic light (a ! 0). Films were prepared by spreading 2 104 M chloroform solutions of the enantiomers of the helicenebisquinone onto MilliQ water in a LangmuirBlodgett trough. Multilayers were prepared by depositing a stack with a given number of molecular layers of the (P)()enantiomer, following it by a stack with the same number of layers of the (M)()enantiomer, and repeating the sequence if necessary. The advantage of the LangmuirBlodgett technique is that the thickness of the stacks can be controlled to a precision of one molecular layer. A drawback is that a very large number of layers is needed to attain the thickness of even one coherence length. However, the coherence length is must shorter if the secondharmonic light is detected in the reflected instead of the more common transmitted direction. First, a series of films were prepared with two stacks, p 2 (P/M) and a series of films with p 4 (P/M/P/M). The total number of molecular layers within the stacks was varied. One could see that the secondharmonic intensities grow with increasing thickness of the stacks, until L Lc , and than decreased. Than, a new series of samples was prepared with 14, and 6 stacks, where L reached the coherence length. The secondharmonic intensity was somewhat less than quadratic only because the samples absorb light at the secondharmonic wavelength. It is clear that quasiphasematching can be achieved by making structures consisting of stacks of chiral molecules where the two enantiomers alternate. Here the quasiphasematching is a consequence of the chirality of the material and it was established in reflection symmetry. However, quasiphasematching should be limited neither to this process nor to this geometry. Nevertheless, this work is an example of the possibility to create completely new frequency converters. 4.10. 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. The problem is that there is no wellestablished theory of the relationship of molecular structure and magneticdipole susceptibilities. There has been theoretical evidence that chirality favors magnetic
151
transitions [26], but no experiment technique has been able to link molecular structure to the presence of strong magneticdipole contributions. Hence, there is need for experimental methods to solve this fundamental question. We recently proposed a new technique, based on EFISHG, to analyze these molecular properties [70]. Electricfieldinduced secondharmonic generation (EFISHG) is a technique that measures the molecular hyperpolarizabilities in solution [7174]. The noncentrosymmetry conditions, needed to detect SHG are introduced by applying an external electric field. The resulting solution has a polar order and SHG can be detected. We modified the classical EFISHG setup to investigate the magnetic contributions to the hyperpolarizability tensor. In the presence of magneticdipole nonlinearities, we can define an effective polarization Peff(2o) [28,75] Peff 2o P2o c r M2o i2o (71)
where the nonlinear polarization P(2o) and the nonlinear magnetization M(2o) can be written as X Pi 2o weee Ej oEk o weem Ej oBk o (72) ijk ijk
j;k
(73)
The subscripts refer to Cartesian coordinates in the macroscopic (laboratory) frame. We will now apply these equations to a particular experimental setup. 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 symmetry of the solution is C1. The nonvanishing susceptibility components are listed in Table 2. There are four independent components for the weee and wmee tensors and seven independent components for the weem tensor. The components of the electric and magnetic fields are Eo E0; 0; Ez and Bo B0; By ; 0. For this particular situation, the nonlinear polarization and magnetization that are able to radiate are Pz 2o weee Ez oEz o; zzz Py 2o weem Ez oBy o; yzy Mz 2o wmee Ez oEz o zzz (74) Hence, the effective polarization becomes Peff o weee Ez oEz oz weem wmee Ez oEz oy zzz yzy zzz (75)
Since, the effective polarization is the source for the secondharmonic signal, it is clear that the secondharmonic will consist of a component polarized along the zdirection and one component polarized along the ydirection. The zpolarized component originates from a pure electricdipole transition while the ypolarized component originates from a pure magneticdipole transition. The result is an SH signal rotated about a certain angle in comparison to the polarization direction of the incoming beam (zpolarized). This would be the case if the electric and magnetic susceptibilities would have the same phase. However, in resonance conditions, the electric susceptibilities weee are imaginary values quantities and the magnetic susceptibilities weem and wmee are essentially real [23,24]. Out of resonance the opposite is true. In general, the electric susceptibility components will differ in phase from the magnetic susceptibility components. This difference in phase between the z and ycomponent of the SH signal will result in elliptically polarized light. The presence of
152
ellipticity in the SH light is thus and evidence of magneticdipole contributions to the nonlinearity. Moreover, the combination weem 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. The susceptibilities measured, can be related to their molecular hyperpolarizabilities weee Nf hbeee i; weem Nf hbeem i; wmee 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. A modified EFISHG setup can be used. A Nd:YAG laser (1064 nm) is incident on the EFISHG cell. The beam is vertically polarized. When the EFISHG cell is filled with a solution of chiral molecules with magnetic contributions, the SH will be elliptically polarized. The horizontally and verticallypolarized components of this ellipticallypolarized light can be written as Ez 2o E1 eiot ; Ey 2o E2 eiotf (77)
2 2
1.5
I 0 60 120 180 240 300 Rotation angle of the quarterwave plate 2.5 2 1.5 1 0.5 0 0.5 360
1 0.5 2 0 0 60 120 180 240 300 Rotation angle of the quarterwave plate 360
(a)
(b)
(c)
360
Fig. 26. The difference DI as a function of the angle of the quarterwave plate y. In the first case (a) there is no magnetic contribution (E2 0). In the second case (b) the ratio E2/E1 0:3 and the phase difference f is taken to be p/4. The last curve (c) shows the situation where E2/E1 0:05 and f p/4.
153
with f the phase difference and E1 and E2 are directly proportional to the electric and magneticdipole contributions, respectively. The ellipticallypolarized light is then directed through a quarterwave plate which is varied continuously. The vertically and horizontallypolarized light is resolved and detected by twophoto multipliers. The difference DI is measured as a function of the angle of the quarterwave plate and can be fitted to the following equation: DI E1 sin2ysinfE2 2 cos2yE1 sin2ycosfE2 2
2 cosf cos2ysinf2 E2 sin2yE1 E2 sinf cos2ycosf2
(78) where y is the angle of the quarterwave plate. To test this formalism, we made some simulations. Fig. 26 shows three curves. In the first case (Fig. 26a) there are no magnetic contributions to the SHG signal or E2 0. The resulting curve is symmetric about the 1808 rotation axis of the quarterwave plate. In the second case (Fig. 26b) the ratio of E2/E1 0:3 and the phase difference is taken to be f p/4. It can be clearly seen that the curve is highly asymmetric about the 1808 rotation axis. The last curve (Fig. 26c) depicts the situation where E2/E1 0:05 and f p/4. Even if the magnetic contributions are 5% of the electric contributions, the curve is asymmetric. 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. To conclude, this modified EFISHG technique shows promise to evolve into a sensitive probe of magneticdipole contributions, and can therefore be extremely useful in establishing clear structure property relationships in chiral materials.
5. Conclusion Secondharmonic generation from surfaces and thin films provides a new tool to study surface chirality. 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 addition, we gave a series of experimental results. From the examples discussed in this review, it is clear that nonlinear optical activity is an extremely useful method to study surface chirality, since the linear analogues such as CD and ORD are not surface sensitive. Moreover, 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. However, the technique still has to mature, from an experimental and theoretical point of view, before it can be routinely used as a measurement technique. Issues that have to be resolved: (i) what is the relationship between the magnetic susceptibilities and molecular structure; (ii) is there a relation between the magnitude of the chiral susceptibility components and the magnitude of the traditional CD or ORD effects. SHGCD could also be used in a new sort of imaging technique: SHGCD microscopy. From an experimental point of view, the usefulness of the technique could be demonstrated in research fields such as biochemistry, catalysis or pharmacology. For example, the study of configurational changes in proteins adsorbed at surfaces, adsorption of racemic mixtures of molecules on chiral surfaces, 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.
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Acknowledgements This work was supported by the National Science Foundation (CHE0094723), the Fund for Scientific ResearchFlanders (G.0338.98 and 9.0407.98), the Belgian government (IUAP P4/11), and from the University of Leuven (GOA/2000/03). S.S. is research assistant of the Fund for Scientific ResearchFlanders and T.V. is a postdoctoral fellow of the Fund for scientific ResearchFlanders. We gratefully acknowledge J.M. Nolte, T.J. Katz, L. Pu and E.W. Meijer for providing us with products and for their valuable discussions.
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