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F/Y2?M 7#V Fy.y/73*

Using the Kramers-Kronig Relations in the Study

of the Optical Activity in Crystals

Using Kramers-Kronig reiations it is shown that circuiar dichroism o f Gaussian shape does not iead to the quadratic Chan­ drasekhar's formula for optical rotatory dispersion in crystais, which are opticaliy active oniy in the crystaiiine state. On the other hand the circuiar dichroism curve with two extrema centered at maximum o f absorption ieads to Chandrasekhar's formuia.

The optica! rotatory power of an absorbing crystai may by considered to be a complex quantity being given by

p = p -tc r. (1)

Then by definition p = Rep is the rotatory power (in radians per cm) and o = Imp is the eiipticity of the emering light or simply the circular dichroism. Optical rotatory dispersion (ORD) and circular di­ chroism (CD) curves are related by Kramers-Kronig relations [1] 2to' ^ <7(12)t%2 (2a) 7t J 12(12'—to ')' 00 2to „ p(!2)t?12 7t J 12' —to' (2b)

The symbol P means that only the principal value of integral is to be taken. The complete CD spectrum determines the complete ORD spectrum and vice versa.

CD is very powerful in resolving the overlapping absorption bands. The CD curve is confined to a small region, in which the optically active medium absorbs while the tail of the ORD curve extends outside the region of absorption. Because the experimental difficul­ ties in making CD measurements have been overcome

[2] we hope that the measured data of CD will be soon available.

It has been assumed that the CD curve is of Gaus­ sian type and therefore o(m) may be expressed as

<?(<") =<7max<?

where (7^, is the maximum of a(m) attained at ai„ and 0o is a width parameter. Substituting (3) into (2a) we get (3) 2<7n,a*a)" ? e

" f

<K2 12(12' - a /) (4) Before evaluating the integral in (4) we introduce an important quantity P, that is the rotatory strength given by definition [3] as

P = 37tC f* f7(cu)i/w 4 7 ^

i

Using (3) we get approximately for P P 3 ^ c o r ^ 0 .

47r3'^VcOo

(5)

(6) We calculate a-,^ from (6) and substitute into (4) obtaining

(n-<°oT

87r'"AfPai'aP ^ e

37tcO<,

i

12(12'— ai') (7) Now, after evaluating the integral in (7) we get [4]

47riVPaP

(8)

2^c(aiQ— to')

This is the well known Drude's formula. The experimental data concerning crystals fit the formula of Chandrasekhar, that is

*) Department o f Theoreticaf Physics and Astronomy, Pafacky University, Leninova 26, Oiomouc, Czechoslovakia.

P to '

(to.—aP)2 \ 2 (9)

(2)

It should be pointed out that Chandrasekhar's formula holds for crystals the activity of which is due to their structure. We see that the Gaussian shape of the CD curve does not lead to the formula of Chandrasekhar.

Chandrasekhar's model is based upon the idea of coupled oscillators [5], [6]. In this model each mo­ lecule is represented by an linear harmonic oscillator. The oscillators are arrayed spirally in the crystal. Let the eigenfrequency of each oscillator be o,, when uncoupled Two oscillators form one compound oscil­ lator and all oscillators are identical As a result of the coupling the frequency would be split into fre­ quencies Co,, and a<2 which are the frequencies o f two normal modes of vibration of the compound oscillator. They are expressed as

= <UQ+27^e, (10)

= COg— 2 ^ 6 ,

where e is the coupling constant between the two adja­ cent single oscillators.

It follows from this model [5], [6] that final qua­ dratic formula (9) is a difference of two Drude's terms involving frequencies to, and co^. But it should be pointed out that Chandrasekhar's formula does not contain the rotatory strength.

We assume now that the rotatory power is a sum of and that is each mode of vibration has the proper rotatory power. Similarly the circular dichroism a has also two components o^, and <7^. Each of these components is of Gaussian shape. Then we have instead of (8)*) where ?? = 1,2. Then 47t AT? ^ to ^ Ttcfto^— o F ) ' (H) 4rrA P — P/? = ---and using (10) we obtain

4^5 } (12)

27iA(A,2-^<?i)

7iC (Og—

(^71 + ^9 2)

COg — (¿F .(13) If 7? ^ — 7? ^ then the second term is zero and (13) reduces to

1 6rFA /?g eoF

7tc(tOg—oF)2 (14)

where 27?„ = ¡7?^J + I7?^]. Under these conditions it follows from (12) that

Formulae (14) and (15) are identical. The first one contains coupling constant e and non-splitted frequency tOg, the second is then without e but con­ tains the splitted frequencies to,, and co^. If 7?^ and 7?^ are equal and positive then the first term in (13) k zero and we get Drude's formula. In the more general case when 7?^ and 7?^ are different we have the combined formula previously obtained by us in [7], which removes some simplifications in Chandra­ sekhar's theory.

Neverthless, there exists one more matter in the use of Kramers-Kronig relations. Introducing the damped forced vibration of the linear harmonic oscil­ lators into the model of compound oscillators we have obtained the following formula for circular dichroism of crystals [8]

_ zf(i)yo(aF-ta;;)<u3

' [ (to g -to T + d y g o F ? ^ _

^ (m 3-c,F)2+4y3aF '

where y„ is the damping constant of single linear har­ monic oscillator, and d ^ are the crystal constant described in [8]. If d f^ = 0 and cr is nonzero only in the vicinity of tOg we may put in (16) (oF—tOg) = 2o)g(co—tOg) and co^- cog. Then (16) reduces to the form

2d(t)(M -M o)yo [ ( c o g - c o ^ + y ^

We see that this formula is not of Gaussian shape. The quantity <7 is zero for to = cog and the CD curve has two extrema at

1

^ext = ^0 ± -F= 3A -

/3

(18) From the condition of extremum dtr/dto = 0 we get for d O

d") =

±

8<7.xtyo33/2 (19)

We see that in the case d ^ > 0 the circular dichroism is negative for to < to g and positive for to > tOg, and vice versa. Substituting (19) into (17) for, e.g. d ^ > 0 we have

1 6 ^ , y .( to - to .)

3 3 / 2 [ ( < U „ - a f ) 2 + y 3 ] 2 ' (20)

4*A'_/C

P = n r

tor— to cut— to^ (15)

*) We have neglected a factor 1/3 because the compound oscillators are not randomly oriented.

We return now to (2a) introducing tog into this equation 2oF r

7T J

<7 (D) dU D(i33 — CUg A CUg — 0)3)

(3)

2 ax' г = ---F 7Т J er (ß ) J ß 0 ß ( ^ - a E ) 1- - ^ --- ^ \ iO o - ^ / (2 t)

In region far from absorption band, ¡Mg— ^ ¡tO g -a ^ l because for D very ditferent from Mg, c(D) is smatt and negtigibte. Therefore (21) can be approximated by 2cu^ TC(&)Q— &)^)

f

q(ß)c/ß ß 2м^ 7t(tUg— M^)'

i

(n )5 - ß ^ )n ( ß )d ß " I ß ' (22)

Equation (22) has the same frequency dependence as (13). Now, we substitute (20) into (22) obtaining

cr(cu) = 32c,„a)^

J

yg (ß — (Dg) J ß +

32cr„,,nE 3 ^ ^ ( m g - cuT

i

(n)g — ß^) ( ß — Mg) yg J ß ß[(<Vg-ß)2 + y;;]h 2 .(23) Both integrals may be solved when taking ß ^ Mg, (nig—ß^) ^2wg(M g—ß ) and substituting

ß — I = X. Уо Then we have yg(ß— Mg) d ß

i

ß [ ( M . - ß ) ' + y 5]2i2 УоM0 —о + oo

i t

(1 + x ') 'xdx (24) 0. (25)

The lower limit is in fact, — (Mg/%) but Mg is very great in comparison to %. And the second inte­ gral - f 2 (ß — <Mg)^yg J ß [ ( M g - ß ) ^ + y g ]212 + oo = - )-g } 2x^dx (t + * T + oo — oo

Now from (26) and (23) we have , . -T - 32<r„x,ygM2

3^ ( M ^ - M T '

The minus sign holds for A > 0, which means that the crystal is laevorotatory. In the case of A

< 0 the crystal is dextrorotatory.

(26)

(27)

Thus from these considerations we may conclude that Gaussian shape of the CD curve leads to Drude's formula. The splitting of Mg into two normal frequen­ cies to, and < ^ 2 leads to the CD curve which shows two rotatory bands of opposite sign centered at cog. Using Kramers-Kronig relation it has been shown that the ^-shaped CD curve leads to the quadratic formula of Chandrasekhar. The more complicated situation which appears when we cannot neglect yl ^ in (16) will be studied in the future.

In a forthcoming paper an application of the pre­ sented consideration will be used in order to remove some discrepancies in the interpretation of ORD for a-quartz.

Application de la relation de Kramers-Kronig à l'étude de l'activité optique des cristaux

L'utilisation de la relation de Kramers-Kronig prouve que le dichroïsme circulaire à repartition de Gauss ne mène pas à la formule des carrés de Chandrasekhar pour la dispersion optique rotatoire des cristaux qui ne sont optiquement actifs qu'à l'état cristallin. D e l'autre côté la courbe du dichroïsme cir­ culaire avec deux extremums concentrés au maximum d'absorp­ tion mène à la formule de Chandrasekhar.

Применение соотношения Крамерса-Кронига для исследования оптической активности кристаллов Применение соотношения Крамерса-Кронига показы­ вает, что круговой дихроизм с гауссовым распределением не приводит к квадратной формуле Чандрасекхара для оптической вращательной дисперсии кристаллов, которые оптически активны только в кристаллическом состоянии. С другой стороны, кривая кругового дихроизма с двумя экстремумами, сосредоточенными в максимуме абсорбции, приводит к формуле Чандрасекхара. References

[1] EMEis C. A., OosTERHOFF L. J., de VRIES G., Proc. R oy. Soc. A 297, 54 (1967).

[2] VELLUZ L., LEGRAND M ., GROSJBAN M., Optical Circular Dichroism, Academie Press Inc., N ew York, N . Y . (1965). [3] MoFFiTT W., M oscowrrz A ., J. Chem. Phys., 30, 648

(1959).

[4] DjERASSi C., Optical Rotatory Dispersion, Mc G raw -H ill Book Co., Inc., New York, N . Y. (1960).

[5] CHANDRASEKHAR S., Proc. Indian Soc., A 37, 697 (195 3). [6] CHANDRASEKHAR S., Proc. Roy. Soc., A 259, 531 (1961). [7] VY§!N V., Proc. Phys. Soc., 87, 55 (1966).

[8] VYSiN V., Optics Communications I, 307 (1970).

Received, EeôriMry 10, 1973

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