Invited article in DST-SERC-School publication (Narosa, November 2011); collection of articles based on

lecture course given at the DST-SERC School at the Birla Institute of Technology, Pilani, January 9-28, 2011.

Atomic Photoionization in the Born
Approximation and Angular
Distribution of Photoelectrons
Pranawa C. Deshmukh
1*
, Alak Banik
2
and Dilip Angom
3
1
Indian Institute of Technology Madras, Chennai
2
Space Applications Centre, Ahmadabad;
3
Physical Research Laboratory, Ahmadabad;

*pcd@physics.iitm.ac.in


ABSTRACT

The aim of this article is to provide basic introduction for readers who are new to
the field of photoionization spectroscopy so that they can appreciate the
developments in this field wherein much more rigorous formulations have been
developed well-beyond the approximations introduced in this article.
Expressions for the differential and total cross-section for atomic photoionization
are developed from first principles. Explicit formula for the total cross-section in
the Born approximation is obtained. Based on this, the primary expression for
the angular distribution of photoelectrons is developed, following the original
elucidation by Cooper and Zare. A few select leads to the current state of
understanding of the phenomenology of atomic photoionization are included to
illustrate current interest in the field of atomic photoionization.

I. INTRODUCTION

The atomic photo-effect has a fascinating history [1]. Other than the
photoionization cross-sections which provide a measure of the transition
probability, a physicist would of course wish to measure other physical
properties related to the photoionization process. Any additional measurement is
nevertheless constrained by the principle of uncertainty, which is the hallmark of
quantum mechanics, since simultaneous measurements of certain physical
properties, such as position and its conjugate momentum, are incompatible. A
complete experiment aims at carrying our all possible measurements that are
compatible. In the case of atomic photo-effect, a complete experiment consists
of measurements of the integrated and differential cross sections, angular
2 Theoretical Techniques in Atomic and Molecular Collision Physics

distribution of the photoelectrons, and spin-polarization parameters for the
photoelectrons [2].
The angular distribution of the photoelectrons gives us information about the
photoelectron yield in different directions, with respect to the direction of
incidence of the electromagnetic radiation that is absorbed by the atom, and its
direction of polarization.
In this article, we provide a pedagogical formulation of the interaction between
electromagnetic radiation and an atomic electron in a bound state with the energy
of the radiation above the ionization threshold. In Section II, we develop the
basic expression for differential and total photoionization cross-section in the
IPA (independent particle approximation) using the Born (high-energy)
approximation. Essential elements are easily found in standard text-books [3-5],
but are included in this article for completeness, and to provide the basis for the
development of the expression for the angular distribution of the photoelectrons
based on the famous exposition of this topic in the Cooper-Zare paper [6]. The
aim of this article is to provide basic introduction for readers who are new to the
field of photoionization spectroscopy so that they can appreciate the
developments in this field wherein much more rigorous formulations have been
developed well-beyond the approximations introduced in this article.

II. THE DIFFERENTIAL AND TOTAL PHOTOIONIZATION
CROSS-SECTION

We shall consider the electromagnetic radiation to be polarized along the X-axis
and incident along the Z-axis of a Cartesian frame of reference. As is found in
standard text books on quantum mechanics and atomic physics, such as [3-5], we
shall describe an electron in an atom interacting with the electromagnetic scalar
and vector potentials
{ }
( , ), ( , ) r t A r t | by the Hamiltonian:
2
1
- ( , ) - ( , ) ( , ) -
2
q q Zq
H p A r t p A r t qf r t
m c c r
(
| | | |
( = +
| |
\ . \ . (

(1)
Ignoring the quadratic term in the vector potential, an approximation that is valid
for weak field, and employing the Coulomb gauge, we can express the electron-
field interaction term in above Hamiltonian perturbatively as:
'
0
H H H = +
, (2a)
with

' ( , ) ( , )
iq q
H A r t A r t p
mc mc
= -V = -
(2b)
where is the perturbation order parameter which we shall use to consider
terms up to first order in perturbation theory, q e = is the electrons charge,
mis the electrons mass, c is the speed of light, and p i = Vis the
momentum operator. First order perturbation theory gives us, using the famous
golden rule attributed to Fermi, the following expression for the transition rate
(i.e. transition probability per unit time) for photoabsorption resulting in a
Atomic Photoionization in the Born approximation..3

transition from an initial bound state i to a final continuum state f effected
by the transition perturbation operator:
2
2
0
( )
| | 2 ( )
ik r
fi
qA
W f e i
mc
e
c to e
-
| |
= -V
|
\ .
. (3)
The physical quantity of interest that gives us information about the
photoionization cross-section is given by the ratio:

Energy absorbed per unit time in
flux of the EM radiation

Energy absorbed per unit time in
per unit area per unit time of the EM radiation
i f
Energy
i f
Energy

. (4)
We shall use the geometry shown in Fig.1 to describe the photoionization
process. The electromagnetic radiation that is absorbed is considered to be
incident along the direction Z of a Cartesian frame of reference, and is polarized
along e
x
c =
. The ratio according to Eq.4 which gives us a measure of the
differential cross-section for photoionization in an elemental solid angle dO
resulting in a photoelectrons escape with momentum k along a direction given
by the unit vector

f
k is then given by:

( )
W
fi
k
d f
d I
k
f
c
e
c
o
e
(

(

(
=
(
O

, (5)
Wherein
fi
e e e = , and ( ) I e is the intensity of the electromagnetic radiation
at the circular frequency e .

Fig.1: Geometry employed to describe the photoelectron angular distribution
From the magnetic vector potential given by:
4 Theoretical Techniques in Atomic and Molecular Collision Physics

( ) ( )
( , ) ( )
0
i k r t i k r t
A r t A e e
e e
e c
(

= +
(

(6a)
we obtain (in the Gaussian-CGS system of units):
1
( , )
A
E r t
c t
|
c
= V
c
in Coulomb Gauge (
0; 0 A | = V- =
) (6b)
and
( , ) H r t A = V
, (6c)
from which we can find the intensity of the electromagnetic field as the average
value of the Poynting vector as:
2
2
0
( ) ( )
4 2
c
I S E H A
c
e
e e
t t
= = =
. (7)
Form Eq.5 and 7 we get:
2
2
0

2
0
( )
| | 2 ( )
( )
2
f
ik r
k
qA
f e i
d mc
d
A
c
c
e
e c to e
o
e
e
t
-
| |
-V
|
(
\ .
=
(
O

(8a)
Hence,

2 3
2
2

4
| | ( )
f
ik r
fi
k
d
f e i E E
d m
c
o t o
c o
e
-
(
= -V
(
O

. (8b)
We urge the student-reader to verify, by considering the physical dimensions of
each term on the right hand side that the dimension of the ratio described by Eq.8
is
2
L , justifying the name cross-section. It is usually measured in terms of the
unit Mb (Mega-Barn) with
18 2
1 Mb=10 cm

.

Transitions to a number of degenerate states are possible, and we must therefore
estimate the number of such states that must be considered. We shall use box
normalization over a cubical box of length L (Fig.2), but our final result will be
independent of L.

Fig.2: Box normalization

The number of states in the volume element is then given by (Fig.3):
Atomic Photoionization in the Born approximation..5

2 2
2
2
2
3
2
2
4
2
dn
n dnd n dEd
dE
dk L
n dEd
dE L
L mk
dEd
t
t
t
O = O
= O
| | | |
= O
| |
\ . \ .
, (9)
Thus, integrating over the possible energy states (Eq.9), we get from Eq.8:

2 3 2 3
4
| | ( )
2 2
2
d L mk
ik r
f e i E E dE
fi
d
m k
f
c
o t o
c o
t
e
| |
( | |
-
= -V
} | |
(
O
\ .
\ .

(10a)

Carrying out the Dirac o function integration over energy, we get:
2 3 2 3
4
| |
2 2
2
d L mk
ik r
f e i
d
m k
fi f
c
o t o
c
t
e
| |
( | |
-
= -V
|
|
(
O
\ .
\ .
. (10b)
The transition matrix element in Eq.10 is:

| |
| |
1
( )
3
( )
3
cos ( )
3
ik r
M f e i
ik r
f
ik r
e e r dV
i
L
i k k r
i f
k r e dV
f i
L
i k k r ik
f f
r e dV
i
L
c
c
c

-
= -V
| |
-
(
-
|
= -V
}
(
|

\ .
(
| |
-
|
(

( \ .
= -
} (
(

(

(
| |
-
|
(
\ .
=
} (
(

(11)
6 Theoretical Techniques in Atomic and Molecular Collision Physics




Fig.3: Estimation of the number of states to which the photoionization transition can
result in. Each of these states can contribute to the transition from an initial bound
state i to a final continuum state f .
Since it is the absolute square of the matrix element that is involved in Eq.10, we
see how the result is independent of the length L used in the box normalization.
The integral in Eq.11 can be easily determined; it is proportional to the Fourier
transform of the initial state wavefunction. If this state function is the 1s
wavefunction
0
3
2
0
1
Zr
a
Z
e
a t

(
| |
(
|
(
\ .
(


of the electron in atomic hydrogen, the integral becomes:
( )
i k - k r
f
I = dV (r)e
i
}
, (12a)
i.e.
{ }
3
2
0
2
2 0
2 2
0 f 2
0
Z
8
a
1 Z
I
a
1
Z a k k
a
| |
t
|
| |
\ .
=
|
t
( \ .
+
` (
)


(12b)

Using Eq.11 andEq.12 in Eq.10, we get:
( )
{ }
5 3 2 3
0
4
2

2 2
0
cos
32
f
f
k fi
f
Z a
k
d
d m
Z a k k
c

o
o
e
(
=
(
O

(
+
(

. (13)
We now make the high-energy (Born) approximation [4]:

2 2 2 2
f f
High Energy Approximation
k k
I.P.
2m 2m
e= + ~ ~
, (14a)
Atomic Photoionization in the Born approximation..7


whence

2
. This gives 1
2 2 2 2
f f f f
f
k k p v
k
kc
m k cm cm c
= = (((
. (14b)
Thus, in the Born approximation,
( )
5
2 2
4

0
sin cos
32
v
1 cos
f
k fi f
f
d Z
d m a k
c
c
u |
o o
e
u
| |
(
=
|
(
|
O

| |
\ .

|
\ .
. (15)
For unpolarized light, we use the average value
2
2 2
0
1 1
cos cos
2 2
d
t
| | |
t
= =
}
,
which gives
( )
5
2

0
v
16
sin 1 4 cos
f
unpolarized
f
k fi f
d Z
d m a k c
o o
u u
e
| |
| |
(
~ +
|
|
(
|
O

\ .
\ .
(16a)
The total photoionization cross-section is then obtained by integrating the
differential cross-section over all the anglesu :
2

0 0
5
5
0
sin
128 1
3
Total
f
unpolarized
unpolarized
k
f
d
d d
d
Z
m a k
t t
u |
o
o u u |
t o
e
= =
(
=
(
O

| |
=
|
\ .
} }
(16b)
( )
2 2
5/ 2
5/ 2
5 2 5/ 2
, since ,
2
2
,
f
f f
k
Now
m
m
k k
e
e
~
| |
= =
|
\ .

giving:
5
5/ 2 7/ 2
0
128 1
3
2
Total
unpolarized
Z
m a
m
t o
o
e
| |
=
|
| | \ .
|
\ .
. (16c)
We thus obtain the well-known result that in the Born approximation, the
photoionization cross-section goes as
7
5
2
, Z E o

. If one carries out similar

analysis with other hydrogenic wavefunctions for higher principal quantum
numbers n, we find that the photoionization cross-section goes as
-3
n
. The Born
approximation is very useful, but it does have limitations and strictly speaking it
provides more of an exception than a rule [7,8].
8 Theoretical Techniques in Atomic and Molecular Collision Physics


III. THE ANGULAR DISTRIBUTION OF PHOTOELECTRONS

The presence of angle dependent terms in the differential cross-section (Eq.15,
16) tells us that the photoelectric effect would not generally generate an isotropic
yield. To examine the angular dependence of the photoelectron yield, we
examine the transition matrix element:
| |
0
| | | |
| | ; (in the 'dipole approximation' 1)
| , |
ik r ik r
ik r
x
i
M f e i f e p i
i
f p i e
i m
f x H i
i
c c
-
= -V =
= ~
=

(17)
Since
2
0
[ , ] [ , ]
2
k k k
p i
r H r p
m m
= =
(18)
for k=x,y,x.
Using the fact that the states i and f are eigenstates of the unperturbed
Hamiltonian H
0
, we get, using Eq.8, Eq.17 and Eq.18:
( )
2
2 2
2 2

4
| | ( )
f
i f
k
d m
E E f x i
d m
c
o t o
o e
e
(
=
(
O

(19a)
i.e.,
( )
2
2 2
2 2

4
| | ( )
f
i f f i
k
d m
E E T
d m
c
o t o
o e
e
(
= ( )
(
O

. (19b)
From the form of the transition matrix element in Equations 17 and 19, we see
that it can be obtained by taking the matrix element of either the momentum
operator, as in Eq.17, or equivalently if the position/length operator, as long as
the commutation property described in Eq.18 holds. Thus, alternative forms of
the matrix elements can be used for their calculations [9]. Computationally, the
matrix elements are then evaluated either or both forms, and accordingly known
as the momentum or the length form of the matrix element. Eq.18, however,
holds only as long as the potential term in the Hamiltonian is local. The
exchange density term in the electron-electron interaction is however non-local,
as in the Hartree-Fock Self Consistent Field potential [10], and when such a
potential is employed the equality of the length and the momentum forms breaks
down. Note that we have written
| | | |
f i
f x i T = ( )
so that we can follow
the formulation in the Cooper-Zare paper [6] with the provision that Cooper-
Atomic Photoionization in the Born approximation..9

Zare paper [6] has the operator T z = whereas we have T x = , the difference
being only on account of the fact that in the Cooper-Zare paper, the incident
electromagnetic radiation is considered to be polarized along the Cartesian Z-
axis, whereas in the present article, it is considered to be polarized along the X-
axis.
The matrix element in Eq.19 is an integral over the radial and angular variables
and can be written as a product of the two:
( ) ( )
'
,
1 '
| | ( , ) 1 1
0 '
l m g
f i ll
l m
l l
T a l m l
m m


>

| |
( ) =
`
|

\ .
)

, (20)
where
2
' ' '
0
( ) ( )
ll kl n l
r drR r rR r

=
}
,
' 1
2
l l
g
+
=
, and l
>
is the greater of l and
' l .
It is important to note that the final state wavefunction used in Eq.20 must have
the correct boundary condition, known as the ingoing wave boundary condition
[11] which describe the photoionization process as time-reversed electron-ion
collision.
By taking the modulus square of Eq.20 and averaging over all states with
azimuthal quantum numbers m assumed to be equally populated, we thus see
that the differential cross-section for photoionization,
( ) ( )
( ) ( )
1 1
1
1
2 2
2
2

1
1 '
'
2 *
2
thus proportional to:
1 '
1
( , ') 1 1
' 0 ' 2 ' 1
1 '
( , ') 1 1
' 0 '
f
k
l g
l l
m l
l g
l l'
l
d
is
d
l l
a l m l
m m l
l l
a l m l
m m
c
o

>
>
(
(
O


| |

`
|
+
\ .
)

| |

`
|

\ .
)

(21)
in which
*

( , ) 4 ( )
l
i l m
l f
a l m i e Y k
o
t

= , (22)
using the notation in Ref.[6].
The summation over the orbital angular momentum quantum numbers is
restricted to be over no more than 4 terms, since under the dipole selection rules
( = 1 l o ), transitions to two possible values of l
1
can be reached at from a
given value of the orbital angular momentum l' of the initial bound state
10 Theoretical Techniques in Atomic and Molecular Collision Physics

function, and similarly transitions to two possible values of l
2
are possible. The
resulting four possible terms are explicitly treated below.
Now, the Wigner 3j symbols are well-known and can be obtained readily even
from the internet and the following two relations can now be used:
( )
( )
( )( )( )
1/ 2
2
2
1
1 1 1
1
0 2 1 2 3 1
l m
l l l m
m m l l l

(
+ + | |
= (
|
+ + +
\ . (

(23a)
and
( )
( )( )( )
1/ 2
2 2
1 1
1
0 2 1 2 1
l m
l l
l m
m m l l l

(
| |
=
(
|
+
\ .

. (23b)
Using Eq.22 and 23, the proportionality in the relation 22 becomes:
( )( )
( )
( )( )
( )( )
( )
( )( )
( )
( )( )
( )
( )( )
l-1,l'
l+1,l'
l 1 l 1

2 2
2
2
l 1,
2
2
2
2
l 1,
2
2
2
2 2
*
l 1 l 1 l 1, l 1,
2
2
2 2
l 1 l 1 l 1, l 1,

l
2l 1 2l 1
l 1
2l 1 2l 3
16
2l 1 l 1
l

2l 1 2l 1 2l 1 2l 3
l 1
l

2l 1 2l 1 2l 1 2l 3
f
k
m
m
i
m m
m
d
d
m
Y
m
Y
m
m
Y Y e
m
m
Y Y
c
o o
o
o

t


+

+

+ +
+ +
(
(
O

+
+
+
+ +
+ +

+
+ + +
+

+
+ + +
( )
l 1 l 1
*
m
i
m
e
o o
+
+
(
(
(
(
(
(
(
(
(
(
(
(
(
(

(24)
The spherical harmonics are functions of the polar angles O(and the azimuthal
angles u) defined with respect to the polar axis taken along the direction of
polarization of the incident electromagnetic radiation. The form of the relation
(24) is such that the u-dependence drops out. The angular dependence of the
photoelectron yield is then determined by the polar angle O which is the angle
between the direction of polarization of the incident electromagnetic radiation,
and the direction along which the photoelectron escapes. The angular
distribution of the photoelectrons is determined, as can be seen from the above
expression, also by the difference in the phase-shifts
( )
l l 1 1 +
o o
in the
dipole-dipole channels. The interference term between the dipole channels has
important consequences on the photoelectron angular distributions. Using a few
Atomic Photoionization in the Born approximation..11

identities with regard to the spherical harmonics and angular momentum
coupling coefficients which are explicitly spelled out in Ref.[6], the differential
cross-section (Eq.19) can be put in the following, very compact, form using the
relation 24:
| |

1 cos
4
f
Total
k
d
P
d
c
o o
|
t
(
= + O
(
O

(25)
in which the parameter | that is introduced is the famously known dipole
angular distribution asymmetry parameter:
( ) ( ) ( )
( ) ( )
2 2
1 1 1 1 1 1
2 2
1 1
( 1) 1 ( 2) 6 1 cos
2 1 1
l l l l l l
l l
l l l l l l
l l l
o o
|

+ + +
+
+ + + +
=
( + + +

(26a)
In Eq.25
( )
2
2
1
cos 3cos 1
2
P O = O
(26b)
This result provides a quantitative relation that describes the angular distribution
of the photoelectron yield resulting from absorption electromagnetic radiation
incident along the Z-axis and polarized along the X-axis. Since the cross-section
cannot go negative, the term in the Legendre polynomial in the Cooper-Zare
formula (Eq.25) restricts the angular distribution asymmetry parameter to the
range 1 2 | s s which keeps| |
2
1 P cos 0. +| O > .

IV. BEYOND THE BORN APPROXIMATION, AND BEYOND
THE COOPER-ZARE FORMULA

We have already mentioned above that the Born approximation used in Section
II breaks down [7,8], and the dipole approximation also breaks down [12-15].
The dipole approximation discussed above results from truncating the
expansion of the exponent in
ik r
e
powers of
r

| |
|
\ .
, and is a long-wavelength
or low-energy approximation. It is considered to be an excellent approximation
for photon energies up to ~5 keV above the ionization threshold. Terms beyond
the dipole approximation are often needed, and there is considerable interest both
in theory and experiment in examining non-dipole effects [12-15] in atomic
photoionization.

V. CONCLUSIONS

The formulation of the photoionization cross-section and the angular distribution
of the photoelectrons presented in this article is based on standard text-book [3-
12 Theoretical Techniques in Atomic and Molecular Collision Physics

5] and/or well-known papers [6]. It is hoped that this formulation is useful to
introduce a student-reader who is new to the literature on atomic
photoionization. The two major approximations used in the present formulation,
namely the Born approximation and the dipole approximation are both useful for
very many applications in atomic physics, but most studies of current interests
require one to go well beyond these approximations [3-5, 12-15]. An
introduction to problems of current interest requires familiarity with the
vocabulary and results described above, and it is hoped that it will be useful to
some young readers. It was felt necessary to include a discussion on
experimental aspects of atomic photoionization measurements of cross-sections,
angular distribution of the photoelectrons etc., but we finally decided,
considering the length of the article, to leave it out. Ref. [2, 12] can provide a
useful introduction for the beginner.

References:

[1] P.C.Deshmukh and Shyamala Venkataraman 100 years
ofEinstein'sPhotoelectric Effect Bulletin of the Indian Association of
Physics Teachers, Vol. 23, 320-327 (2006)
[2] Volker Schmidt, Photoionizatio of Atoms using Synchrotron
Radiation
Rep. on Progress in Phys. 55 1483-1659 (1992).
[3] H.A.Bethe and E.E. Salpeter Quantum Mechanics of One and Two
Electron Atoms
[4] Bransden and Joachain Physics of Atoms and Molecules, Prentice
Hall 2003.
[5] J.J.Sakurai, Modern Quantum Mechanics, Pearson Education Inc,
1994
[6] J. Cooper and R.N. Zare, Angular distribution of photoelectrons J
Chem Phys 48:942943 (1968); and in Lectures in Theoretical Physics,
edited by S. Geltman, K. T. Mahanthappa, and W. E. Brittin (Gordon
and Breach, New York,1969), Vol. XI-C, pp. 317337.
[7] E.W.B.Dias, H. S. Chakraborty, P. C. Deshmukh, S. T. Manson,
O.Hemmers, G.Fisher, P.Glans, D.L.Hansen, H.Wang, S.B.Whitfield,
D.W.Lindle, R.Wehlitz, J.C.Levin, I.A.Sellin, R.C.C.Perera.
Breakdown of the Independent Particle Approximation in High-Energy
Photoionization, Physical Review Letters 78:24 p.4553-4556 (1997)
[8] D.L.Hansen, O.Hemmers, H.Wang, D.W.Lindle, P.Focke, I.A.Sellin,
C.Heske, H. S. Chakraborty, P. C. Deshmukh and S. T. Manson
Validity of the independent particle approximation: The exception, not
the rule, Phys.Rev. A 60, R2641-2644 (1999).
[9] S.Chandrasekhar On the Continuous Absorption Coefficient of the
Negative Hydrogen Ion in Astrophysics Journal, Vol. 102, Page 223
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Atomic Photoionization in the Born approximation..13

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[14] Tanima Banerjee, P. C. Deshmukh and S. T. Manson Dipole and
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