Anisotropic Behavior in Superparamagnetic Systems

I. Yasumori, D. Reinen, and P. W. Selwood

Citation: J. Appl. Phys. 34, 3544 (1963); doi: 10.1063/1.1729255

View online: http://dx.doi.org/10.1063/1.1729255
View Table of Contents: http://jap.aip.org/resource/1/JAPIAU/v34/i12
Published by the American Institute of Physics.

Additional information on J. Appl. Phys.

Journal Homepage: http://jap.aip.org/
Journal Information: http://jap.aip.org/about/about_the_journal
Top downloads: http://jap.aip.org/features/most_downloaded
Information for Authors: http://jap.aip.org/authors

Downloaded 06 May 2012 to 139.184.30.132. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions
JOURNAL OF APPLIED PHYSICS VOLUME 34, NUMBER 12 DECEMBER 1963

Anisotropic Behavior in Superparamagnetic Systems

I. YASUMORI,· D. REINEN,t AND P. W. SELWOOD+
Department of Chemistry, Northwestern University, Evanston, Illinois
(Received 24 September 1962; in final form 17 June 1963)

,!,h~ relative I?agn~tization of an assembly of fine, ferromagnetic, single-domain particles which show
umaxI~1 magnetlc a~llsotropy has ?een formulated as a function of p and A, the ratios of magnetic energy
of partl<;le m0!llent ~n field ~nd amsotr~py energy to thermal energy, respectively, under various situations
for p~rtl~le one~tatlOn. Stnct ~~r~ulatl~n for the system where the anisotropic symmetry axes of particles
are distributed III thermal eqUlhbnum gives the simple Langevin equation without any influence of aniso-
tropy. In the c~se, howev~r, ?f particles with fixed random orientation of symmetry axes the observed
decrease ~f relatIVe magn.etlz~tlOn was deduced, while it was found that the Langevin equation is still valid as
low and high field approximatIOns. Several simpler cases where the symmetry axes of particles are constrained
o~ a plan~ parallel or I?erpendicular to the applied field were also treated and the deviations from the Lange-
Vlll equatIOn were estimated. These results confirm Bean and Livingston's view about the behavior of the
system in low and high field extremes, but show that Knappwost and Rust's formulation, which was devel-
oped to expl~in the anomaly in the magnetization of fine cobalt particles, is not reasonable, suggesting
sources of amsotropy other than those of magnetocrystalline origin.

INTRODUCTION magnetization of superparamagnetic particles for the

T HE relative magnetization of assemblies of fine,
ferromagnetic, single-domain particles-if their
magnetic energy simply depends on the orientations of
the magnetic moments in the external field-is de-
scribed by the usual Langevin equation, which was
originally derived for paramagnetic systems! :
M/Ms=cothp- (l/p).
In this expression M is the magnetization at the field H
and temperature T, Ms is the saturation magnetization
at the same temperature, and p=JJ.H/kT. JJ. is the mag-
netic moment of a particle and is given by the product of
the spontaneous magnetization Isp and the particle vol-
ume v. Systems showing this kind of magnetic behavior
are generally called "superparamagnetic." Two limiting
cases can be derived from the above equation:
MI M 8=pI3
and
M/M s = 1- (lip)
according to p«1 and p«1, respectively.
Attempts to include the influence of a magnetic
anisotropy arising from the crystal structure, the
mechanical stress, the surface, or the shape of the
particles:have been made by several investigators-
probably the earliest one being that of Stoner and
Wohlfarth,2 who derived expressions for the magnetiza-
tion of assemblies of uniaxially anisotropic particles at
OOK, without considering any temperature influence.
Bean3 has obtained an approximate equation for the
* Present address: Laboratory of Physical Chemistry, Tokyo
Institute of Technology, Tokyo, Japan.
t Present address: Inorganic Chemistry Institute, University
of Bonn, Germany.
t Present address: Department of Chemistry, University of
California, Santa Barbara, California.
1 C. P. Bean and J. D. Livingston, J. Appl. Phys. 30 120S
(1959). ' its energy is given by Ea=KIV sin2ift (neglecting the
2 E. C. Stoner and E. P. Wohlfarth, Phil. Trans. Roy. Soc. Lon-
don 240, 599 (1948).
3 C. P. Bean, J. App!. Phys. 26, 1381 (1955).
case of extremely large anisotropy. West4 has calculated
the magnetization of superparamagnetic systems in
thermal equilibrium under the assumption that the
magnetic field is applied along the directions of easy
magnetization of particle. Bean and Livingstonl con-
sidered the low- and high-field behavior [Eqs. (2a) and
(2b)] for the cases of the applied field being parallel
(1) and perpendiCUlar to the axes of easy magnetization.
They extended their consideration to the general case
of random distribution of the directions of easy magneti-
zation for p«1 and p»1. Knappwost and RustS have
recently treated systems of uniaxially anisotropic
particles in thermal equilibrium assuming that the
directions of the particle moments are always located
in the planes formed by the directions of easy magneti-
zation and that of the applied field and have tried to
explain the anomaly in the magnetic susceptibility of
(2a) finely dispersed cobalt particles in this way. This treat-
ment, however, cannot be considered to be general
(2b) because the calculation neglects partly the temperature
influence which tends to move the particle moment out
of that plane.
In the present paper an attempt is made to derive
expressions describing the magnetization of an assembly
of single-domain particles, which exhibit uniaxial
anisotropy, in thermal equilibrium for the general case
of every value of p and A, where A=K 1v/kT; Kl being
the first-order anisotropy constant.
MAGNETIZATION OF AN ASSEMBLY OF FINE
PARTICLES WITH THEIR SYMMETRY
AXES DISTRIBUTED IN THERMAL
EQUILIBRIUM
Case (la): Three-Dimensional
Distribution of Axes
We assume that the anisotropy is uniaxial and that
4 F. G. West, J. Appl. Phys. 32, 249S (1961).
5 A. Knappwost and G. Rust, Z. Elektrochem. 63, 701 (1959).
3544

Downloaded 06 May 2012 to 139.184.30.132. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions
 A N ISO T R 0 PIC B E H A V lOR INS U PER PAR A MAG NET I C S Y S T EMS 3545

second-order tenu K 2v sin-;y), and that all particles are which is just the simple Langevin function given by
unifonu in size. The definition of the angle if; and all Eq. (1). The same equation is obtained if one includes
other variables involved, together with the necessary the second-order anisotropy term. Therefore, the
geometrical explanations, are given in the caption to magnetization of an assembly of uniaxial anisotropic
Fig. 1. The relative magnetization is described by particles is not influenced by this anisotropy so long as
the symmetry axes are distributed in thenual equilib-
M I rium. This conclusion also holds for the more compli-
cated case of anisotropies of cubic symmetry. If the
Ms Z
directions of the symmetry axes are not allowed to
trrtrr e
} 0 } 0 } 0 } 0 P
cosh>" sin2,ycosO sinO sinxdOdadxd(3
distribute in a three-dimensional way, however, the
magnetization is influenced by the presence of anisot-
ropy as shown in the following examples.
r
r r
Jt~ J~ Jr~ J
21f

n eP cosH, sin2,ysinO sinxdOdadxd(3 Case (lb): The Axes of Easy Magnetization are
Restricted to the Plane Perpendicular
o 0 0 0 (3)
to the Applied Field
The angle if; is a function of x, 0, and l/>=a-(3, and sin2if; They are distributed in a two-dimensional thermal
can be substituted by a relation, equilibrium, which is a uniform distribution within the
cosif;=cosx cosO+sinx sinO cosl/> (4) mentioned plane. X in Eq. (3) becomes 11"/2 and one
obtains:
derived from Fig. 1. Rewriting the integral Z from

J(1(f2"Jr" e cos9+X sin 29cos2</>cosO sinOdOd(3dcp

Eq. (3), one obtains
0 0 0 P

M
Z = 211"e- xi" ePcos9sin{!a2'lfi1T eX cos2,ysinxdxdcp JdO. (5) (9)
M. 21Tf". eP cos9+X sin 9cos </>sin0d8d(3dcp
ff
2"
2 2

The double integral in brackets can be shown to be o I) 0

independent of 0 because the axes of easy magnetization

It is quite difficult to derive an explicit expression
are orientated in the way of thermal equilibrium with
from Eq. (9), which is valid for all values of p and A.
respect to every single 1-'. This consideration is confinued
Expanding the exponential tenu into a power series of
mathematically in the Appendix.
A or p, and integrating straightforwardly, one finally
Transfonuing the x,1/> coordinate system to one based
gets the following equations for small A or small p
on if; and 1/>', where 1/>' is located in the plane perpendic-
values:
ular to t' (Fig. 1), the integral changes to
M/M. = L(p)[l- AX (Da/D 1 - D2/Do)],
A = i for A«l (lOa)
and

= -211" L -
'" An! . cos2"if;d(cosif;)
'"
L
An
.-
2n
n=On! 0 M p n~n!(2n+1) 2n+3
1--------------- for p«l. (lOb)
00 An M. 3 '" An
=411"L . (6) L---
n~on!(2n+1) n~on!(2n+l)

The exact proof of Eq. (6) is outlined in the Appendix. Equation (lOa) simplifies to
Substituting Eq. (6) into Eq. (3) one obtains
M/M.= (p/3) (l-BX), B=2/15
L'" An f" e P cos9COSO sinOdO for p«1 and X«l (lla)
M n~ n!(2n+1) 0 Dl and
-=L(p) (7)
M/M.= 1- (l/p)- (CAjp2) C= 1
M. '"
L An f1T e Do
P cos9sinOdO for p» 1 and X«1. (llb)
n~ n!(2n+l) 0

All values of magnetization are lower than those given

where by the corresponding Langevin functions. Equation
(8) (lOb) suggests that the relative magnetization
approaches zero for extremely large values of A.

Downloaded 06 May 2012 to 139.184.30.132. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions
3546 YASUMORI, REINEN, AND SELWOOD

Case (Ie): Knappwost and Rust Treatment H

These authors assumed that every JJ. is located in the
plane fonned by the direction of the field H and one
z
-
A FIG. 1. Geometrical
relationships used in
formulation. A, axis of
axis of easy magnetization A. Their basic equation is easy magneti7.ation; 0,
angle between Hand p,;
obtained from Eq. (3) putting Q>=O and x-y.,=e fAx, angle between Hand
therefore: A; .p, angle between A
and p,; a, angle between
x axis and the projection
, "1211'1011' e P 0088-A sin 2 (x- 6 lcos6 sine sinxdedadx ~::::+--+-+--fI of }.into the xy plane;,6,
angle between x axis
M 1o o. 0 and the projection of A
into the xy plane; and
M.
rt'r e
) 0 ) 0 ) 0 P 00s6-, sin 2 (x- 8l sinO sinxdOdadx
<f>=a-,6, angle between
the projections of p, and
A into the xy plane,
(12) respectively.

Taking a similar way of evaluation to that in the case

(lb), one obtains an expression analogous to Eq. (lOa) where
for A«I, the coefficient A being 1 however. This result
also yields two limiting fonns which are slightly differ-
ent from Eqs. (lla) and (llb) in the numerical coeffi-
cients, i.e., B=4/45 for p«1 and C=j for p»1. In this
modified three-dimensional model, one also obtains a and X= cosO and Z= cosx.
decrease of magnetization in the presence of uniaxial Equation (14) is still too complicated to evaluate for
anisotropy. The difference between our value of the general case. For small A values, however, it can be
coefficient Band Knappwost and Rust's value (8/15) simplified to
is due to their erroneous neglect of the contribution
from the A tenn in the denominator function Z.

MAGNETIZATION OF ASSEMBLIES OF FINE

PARTICLES WITH FIXED ORIENTATION
OF SYMMETRY AXES =L(P)[1- 2A~(~D2 _1)(D3 _D2)] (16)
Case (2a): Three-Dimensional Random 15 Do Dl Do
Distribution of Axes
because, as follows from Eqs. (6) and (7) and the
One has to use the following equation: Appendix,

rfh111' eP COS6-A sin2>i'cosO SinOdedaj

Mlt'r _0_ _
0 _ _ _ _ __

M.= 47r)0)0 (IC

) 0
re
) 0 P cos8,·-' sin 2,psin6dOda Equation (16) has the following limiting fom1s
M/M8 = (P/3)- (p3/45)- (16p3A2/10125).··
Xsinxdxd(3 (13) for p«1 (l8a)
and
as the starting formula. The magnetization of a sub-
assembly of particles with its symmetry axes restricted M/M.=1-(1/p)-(8A2/15 p2) ••• for p»1. (18b)
to the directions between X and x+dx and f3 and f3+d(3
is described by the expression in brackets in Eq. (13). Equations (16), (18a), and (18b) do not contain any
The total magnetization is now obtained by the inte- linear A term; consequently the initial slope of the
gration over all angles X and (3. Expanding the expo- magnetization curve is not influenced by A and obeys
nential term e- x sin2 >i' into the simpler equation (2a). The latter result is valid not
only for small anisotropies, but for every A value,
'" An because the integral Fo in Eq. (14) is independent of z
e-' L - cos2 ""v= e-'[l + j(A,Q>,O,X)]' for p«1. It is readily seen from the above expression
n=O n!
that the relative magnetization takes values, depending
Eq. (13) can be rewritten as on the values of p and A, between the Langevin value
and the following limit,
M
-=L(p) [11FI-Fo
1+ - - d z], (14) M/ M.= (p/3)- (p:l/15)+ (lp3/lOS)· ..
M. 0 l+F o for p«1 (19a)

Downloaded 06 May 2012 to 139.184.30.132. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions
 A N ISO T R 0 PIC BE H A V lOR INS U PER PAR A MAG NET Ie S Y S T EMS 3547

which can be derived from the formula given by Bean by the free rotation of the particles for example-the
for the case of infinitely large A. 3 The above results also magnetization is not influenced at all by the magnetic
support the considerations by Bean and Livingston,! anisotropy. In the case of fixed random orientation of
that the initial magnetization is p/3 for all values of A the axes the anisotropy causes a decrease in the relative
and that the dominant term in the high field approach magnetization, but the Langevin low- and high-field
is still the Langevin expression 1-1/p except for the approximation [Eqs. (2a) and (2b)] are still valid. It
case of infinitely large A, where Bean's approximation is further shown that the magnetization curve may be
gives lowered below or raised above the Langevin values,
depending on the kind of distribution and orientation of
the axes of easy magnetization in other cases.
In order to apply these results to the behavior of
Case (2b): The Axes of Easy Magnetization actual systems it seems reasonable to assume that the
Are Lined Up Parallel to the Field symmetry axes have fixed orientations under the normal
With x=O and if;=(), Eq. (13) is changed to conditions of the magnetization measurements, at room
temperature and lower, dealing with fine cobalt particles
Jt'rr
0 J 2
0 eP cos8-X sin 8cos() sin()dfJda
imbedded in or fixed to a solid matrix for example. It is
possible then to classify assemblies of ferromagnetic
M
(20) particles of this kind under the following aspects:
Ms (a) If the particles are extremely small, one can neglect
Jt"r
0 J 2
0 eP cos8-X sin 8sin()d()da the contribution of anisotropy to the magnetization.
The system shows a good superposition of magnetiza-
tion data at different temperatures, when plotting
In the case of small anisotropies, one obtains similar
MMo/Isp vs HIspjTMo and no hysteresis, Mo being the
equations to Eqs. (lOa), (lla), and (l1b), but with
saturation magnetization at 0°K.1,6
negative coefficients: A=-l, B=-4/15, and C=-2,
(b) The particles are larger and the anisotropy has
corresponding to an increase of magnetization. The
already appreciable influence on the magnetization
analogous expression to Eq. (lOb), the low-field
curve in the temperature range considered. The super-
approximation for every value of which is given by
position is not good, mainly at low H/T values, but
00 An 4n the system is still in thermal equilibrium because it
L: .- does not show hysteresis.
n~O n!(2n+1) 2n+3 (c) Though particles are single domain, they are so
1 + - - - - - - - . (21) large that the anisotropy barrier cannot be overwhelmed
00An
L:--- by thermal agitation within the time of a single meas-
n~on!(2n+1) urement. The magnetic moments are fixed to the
regions of the symmetry axes, at least for some time,
For extremely large value of A, the equation approaches and the magnetization becomes time-dependent. The
p. formulations in the second part of this paper are
concerned with systems described under (b).
Case (2c): The Axes Are Uniformly Distributed Considering the results in case (1), which deal with
in the Plane Perpendicular to the Field systems with mobile symmetry axes, the calculation of
Obviously the following equation: Knappwost and Rust 5 does not cover the general
behavior of a distribution of this kind. A comparison of
the coefficient Band C in Eqs.(lla) and (l1b) with
those in the case (lc) shows clearly that their formula-
tions correspond to a distribution which is between the
two-dimensional one of case (lb) and the three-
dimensional one of case (la). A factor of f changes the
coefficients in Eqs. (lla) and (llb) into those of
(22) case (1c).
yields the same results as Eq. (9). Besides, this model of mobile symmetry axes does not
likely suit their actual system, which consists of cobalt
DISCUSSION AND CONCLUSION particles produced by a precipitation from a cobalt-
copper alloy at 475°C. It is difficult to believe that the
The relative magnetization of assemblies of fine, directions of the symmetry axes are restricted so as to
ferromagnetic, single-domain particles which exhibit give a special distribution at this temperature on the
anisotropy of uniaxial symmetry has been formulated one hand, and that the axes can move freely at the
under various assumptions. If the symmetry axes are
involved in a three-dimensional thermal equilibrium- 6 D. Reinen and P. W. Selwood, J. Catalysis 2, 109 (1963).

Downloaded 06 May 2012 to 139.184.30.132. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions
3548 YASUMORI, REINEN, AND SELWOOD

lower temperatures where the magnetic measurements The adsorption of hydrogen can sometimes cause an
were performed, on the other hand. It seems to us that increase of magnetization at low fields instead of the
the assumption of fixed, but randomly orientated, axes expected decrease in such systems. 6,10,11 These results
of easy magnetization may possibly be a better model. suggest that these assemblies contain certain fractions
Equations (18a) and (18b) show, that the magnetiza- of particles which belong to the class (c). This is also
tion would be decreased in this case too as needed for verified by another example of a 6% cobalt-on-silica
the explanation. catalyst which was sintered in vacuum at 500°C for
It is still left, however, to explain the abnormal several hours after reduction at the same temperaturel3 :
maximum in the magnetic susceptibility or the inflection the catalyst shows an increase of magnetization with
point in the magnetization curve, which was found by temperature in a low ac field, deviating from the true
Knappwost and Rust for their cobalt system. Their superparamagnetic behavior. High dc field measure-
explanation about the maximum is not correct, because ments on the same sample show a remanence of several
they neglected the 1/p term in the high-field approxima- percent at room temperature, which increased with
tion, considering only the smaller 1/p2 term in the decreasing temperature.
calculation. The suitable maximum cannot be obtained In the equations derived in this paper only systems
if one takes this term into consideration. The introduc- containing particles of uniform size are considered. Real
tion of a particle-size distribution does not improve the systems, however, show a distribution of particle size,
situation so long as the limitations (a) and (b) about which depends on the method of preparation, the nature
the particle size hold. The possible explanation may be of the support, the heat treatment, and the reduction
that a fraction of cobalt particles belong to the class of conditions of the samples. The total relative magnetiza-
size (c). They are not able to surmount the potential tion of the system in thermal equilibrium is given by
barrier of the anisotropic energy, which is lowered by
the applied field to some extent, within a reasonably
( M) = r(M) I.pvn(v)dv / r I.pvn(v)dv, (23)
short time at lower H values in order to follow the M. 0 J0 M. v J0
magnetic field. It is necessary, however, to find other
sources of anisotropy such as shape anisotropyl or sur- where (M/M.). is the relative magnetization of those
face anisotropy,7 because the magneto crystalline aniso- particles having volumes between v and v+dv, and n(v)
tropy K1v is not large enough to give a reasonably high is the particle distribution function, defined by the
barrier in this rate process. relation to the total number of particles N,
There are several examples of cobalt and nickel
particles supported by various carriers,6,8-1O which show
deviations from true superparamagnetic behavior, as
N= n(v)dv. 1'"
indicated by an incomplete superposition-especially
The spontaneous magnetization Isp may also be a
at lower field-or even by the presence of hysteresis, if
function of temperature and particle size. 14 Every
the particles are relatively large. The magnetization
formula which was derived in previous sections for
curve shows an inflection point in the latter case, which
is observed to shift to higher fields the larger the
M/M.
can be available in the above equation. If the
systems contain larger particles having the relaxation
particles are. 6In these systems the particles should have
time T, which is comparable to or longer than the time
their axes of easy magnetization distributed at ran-
of a single measurement t, for example, 102 sec in dc
dom-the manner of preparation and the nature of the
field method,! only those particles below a certain
carriers have no structural effects which may cause a
critical or blocking volume Vc are still in thermal
preferred orientation of these axes and the equations of
equilibrium, while all particles with v~ Vc will contribute
case (2a) are applicable, if one additionally considers
only little to the total magnetization. The observed
the particle-size distribution.
magnetization in such a case is essentially described by
In the measurements using the ac permeameterll in

(M) JVC(M)
which the equilibrium condition is more serious because 1
of the alternating field, a decrease of magnetization is - = - 18pvn(v)dv
often observed by the sintering of the particles or by M. obs (M.)total 0 M. v
the increase in the frequency of the alternating field. 12
= 1 I.pVn(T)dT~(M) , (24)
(C(M)
7 L. Neel, Compt. Rend. 237, 1468 (1953); J. Phys. Radium 15, (M.)total 0 M. V J
M. 0
225 (1954).
8 W. Romanowski, Chem. Stosowana 2, 225 (1961).
where
9 C. R. Abeledo and P. W. Selwood, J. Chem. Phys. 37, 2709
(1962). (25)
10 R. E. Dietz and P. W. Selwood, J. Chem. Phys. 35, 270 (1961).
11 R. J. Leak and P. W. Selwood, J. Phys. Chem. 64, 1114
(1960). 13 I. Yasumori and P. W. Selwood (to be published).
12 J. W. Geus, A. P. P. Nobel, and P. Zwietering, J. Catalysis 1, C. R. Abeledo and P. W. Selwood,
14 J. App!. Phys. 32, 229S
8 (1962). (1961).

Downloaded 06 May 2012 to 139.184.30.132. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions
 A N ISO T R 0 PIC B E H A V lOR INS U PER PAR A MAG NET I C S Y S T EMS 3549

and Tc is a critical relaxation time related to Vc and equationl5 may be used.

characterized by the condition t»T c. Since the relaxa-
tion time is an exponential function of the parameter A,
T= constx exp(X), for zero field, and gradually decreases
with increasing field,! it is understandable that the
deviation from the equilibrium value becomes more

{
appreciable in lower field and at lower temperatures. ~yp(O'O) (p=q)
To obtain a more nearly quantitative understanding = 2p+l
of the situation discussed above it would be necessary
to have a detailed knowledge about the relaxation time o (p~q), (26)
as a function of particle size and about the particle size
distribution. 6 where Yp is the spherical harnlonic of pth order and pq
the Legendre polynomial of qth order. (cosx)2n in Z'
APPENDIX may be expanded in a series of pq in the following way:
Evaluation of the integral n
(cost/t)2n= L A 2mP2m(COSt/t), (27)
t"(
Z' = J J (cost/t )2n sinxdxdcjJ.
0 0
m=0

where the A 2m are expansion coefficients of the general

In order to evaluate the above integral, the following form:

(4n+l)(4n-l)· .. {4n+1-2(n-m-1)}· (4m+l)· (2n)!

A2m =-------------------------------------------
2 ·4· 6· .. 2(n-m) ·1·3·5· .. (4n+ 1)

for m(n, and

(2n) ! ACKNOWLEDGMENTS
A2m
1·3·5··· (4n-l) It is a pleasure to acknowledge that this work was
for m=n. Substituting Eg. (27) into Z' one obtains done under grants from the U. S. Army Research Office
Z'= tA 2m t' r P m(cos1/;) sinxdxdc/J.
2 (28) (Durham) and the National Science Foundation. Sup-
m=O io io port is also gratefully acknowledged from The Advanced
The comparison of Eg. (28) with Eg. (26) shows Research Projects Agency of the Department of De-
Yp(x,cjJ) = 1= Yo(x,cjJ) fense, through the Northwestern University Materials
and Research Center.
Z'=AOJ~2"i'lf" Po (cost/t) sinxdxdc/J
15 G. Sansone, Orthogonal, Functions, Pure and Applied Mathe-
= 41I-A oYo(0,0) = 47rAo= 411-/ (2n+ 1). (29)
matics, edited by R. Courant, L. Bers, and J. J. Stoker (Inter-
Thus one obtains the previously cited results. science Publishers, Inc., New York, 1959), Vol. IX, p. 266.

Downloaded 06 May 2012 to 139.184.30.132. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions