8 TRIPLE DIFFERENTIAL CROSS SECTIONS

8.0 Introduction

In this chapter, we discuss the evaluation of the triple differential cross sections (TDCS), also
denoted as  e, 2e  cross sections, for electron impact ionization of hydrogen atom using the first-
order distorted wave Born approximation.

8.1 Differential Cross Section for Ionization

In the case of ionization of the target atom by the projectile electron, the triple differential cross
section (TDCS) or the (e, 2e) cross section is given by

d 3 4 ki k
 
2
  2  Ti 0 k 0 , k i , k  (8.1)
dEi d i d  k0

which is triply differential with respect to the kinetic energy Ei  ki2 2 of the scattered electron
and the solid angle d i  d   of the scattered (ejected) electron and where k0 and k  is the
momentum of the incident and ejected electron respectively. From the conservation of energy
principle, we have

E0  Ei  E  I (8.2)

where E0  k02 2 and E  k2 2 is the kinetic energy of the incident (ejected) electron, while I is
the ionization potential of the atom. For hydrogen atom, the DWBA T-matrix element in
equation (8.1) takes the form

Ti 0DWBA  i    0      1 V  Ui  
ˆ  1      0 
 
0 (8.3)

The distorted waves 0  ,  i   and      satisfy the general equation

 

 k 2j 
 Kˆ j  U j   j    0

 j  0,  , i (8.4)
 2 
 

In equation (8.4), Kˆ j   2 2 is the kinetic energy operator, U 0   V  is a short-range static

distorting potential in which the incident electron moves as a result of interaction with the neutral
target atom, while U i and U  is the long-range Coulomb potential experienced by the scattered
and ejected electron respectively due to interaction with the nucleus. For more complex targets,
such as helium atom, U i and U  are modified Coulomb potentials.

1
In equation (8.3), V is the electron-hydrogen atom interaction potential

1 1 1 1
V     (8.5)
r r  r r r01

Also, in equation (8.3),  is the wavefunction of the target atom

1
  r,   Pnl  r  Ylm  ,   sms   (8.6)
r

while ̂ is the antisymmetrization operator given in terms of the exchange operator̂01 (which
interchanges the spin and spatial coordinates of the target electron with those of the projectile) by

ˆ  ˆ 
 ˆ 01 (8.7)

Equation (8.3) then becomes

Ti 0DWBA  i    0      1 V  Ui   1 0   0   i    0      1 V  U i    0  0  1

     

(8.8)
Now, for the hydrogen residue ion
1
Ui   (8.9)
r

Equation (8.8) therefore becomes

Ti 0DWBA  i    0      1  1  0    0   i     0       1   0   0   1

  1 1
(8.10)
r01 r01

The first term is the direct T-matrix element, while the second term in the exchange T-matrix
element in the distorted-wave first Born approximation.

8.2 Evaluation of the T-matrix Elements

The T-matrix element in equation (8.10) is evaluated using the partial wave expansion of the
distorted waves  i and   thus

12  m l
2
i ,     r ,    
 
 kr 1  
l 0 ml
 
i l ei l Fl  n, kr  Ylm  rˆ  Ylm kˆ  sm
†
s
  (8.11)

2
where Fl  n, x  is the regular Coulomb function,  l  arg   l  1  in  is the Coulomb phase shift,
n   Z k is the Coulomb-Sommerfeld parameter and  sm
†
s
is the spin wavefunction of the
scattered (ejected) electron. The distorted wave of the incident electron is expanded similarly
12
 2
r ,   0      kr 1  il eil l  k , r Ylm  rˆ Y lm  kˆ   sms   (8.12)
  lm

where  l is the phase shift. The radial distorted/partial waves  l satisfy the Schrodinger equation

 d 2 l  l  1 
 2  2  E  U 0   l  k , r   0 (8.13)
 dr r 

Equation (8.13) is solved subject to the boundary condition

lim l  k , r   cos  l fl  k , r   sin  l gl  k , r  , where f l and g l are regular and irregular Ricatti-
r 
Bessel functions respectively. The Ricatti-Bessel functions fl  x  and gl  x  are obtained from
the Coulomb functions Fl  n, x  and Gl  n, x  by setting n  0 for a neutral target. Further, in
equation (8.10) we use the multipole expansion of the electron-electron interaction potential


1  4  r
  Y   rˆ  Y  rˆ  (8.14a)
r  r   2  1  r 1

which may be written as

1 r 
   1  1 C   rˆ  C  rˆ  (8.14b)
r  r  r

where the renormalized spherical harmonics C  are defined by

12
 4 
C  rˆ     Y  rˆ  (8.15a)
 2  1 
and are such that
12
4 
 1 C  rˆ     Y   rˆ  (8.15b)
 2  1 


since Y   rˆ    1 Y ,   rˆ  .

3
8.2.1 Direct T-matrix Element

Substituting equations (8.6), (8.11), (8.12) and (8.14b) in the first (direct) term in equation (8.10)
gives

Ti 0D  i    0      1  1  0    0 
  1
r01

l0 li l ei li  l l0 

32
2 1 1
   r 2 drdrˆ  r 2 dr drˆ  2 2   i
  ki k k0 r r  li mi l m l0m0

   
Fli  ki r  Ylimi  rˆ  Yli mi kˆ i Fl k  r Yl m  rˆ   Yl m kˆ   
r
  1  1 C   rˆ C  rˆ  Pnl  r Ylm  rˆ  l0  k0 , r Yl0m0  rˆ Yl0m0  kˆ 0  msi ms ms0 ms
 r

l l l  i l  l l 
32
2
 
 
1
   
ki k k0 li mi l m l0m0 

 
i 0 i  e i  0  1 Yli mi kˆ i Yl m kˆ  Y l0m0 kˆ 0    

   drˆY li mi  rˆ  C  rˆ  Yl0m0  rˆ  drˆ1Y l m  rˆ   C  rˆ   Ylm  rˆ   Dlil ll0 msi ms ms0 ms (8.16)
 

where Dlil ll0 is the direct Slater-type integral defined as

 
r

Dlil ll0   dr  dr Fli  ki , r  Fl k , r   r  1 Pnl (r)l  k0 , r 
0
(8.17)
0 0 

From the orthonormality of the spin wavefunctions, we then have in equation (8.16)

msi ms ms0 ms   ms ms  ms ms (8.18)

i 0 

since si  s0  s  s  1 2 , which ensures conservation of the total spin S of the interacting

electrons. Further applying the Wigner-Eckart theorem to evaluate the angular integrals in
equation (8.16) gives

 l  l0   li  l0 
 drˆY

 rˆ  C  rˆ Yl0m0  rˆ    1mi li , l0 1 2  i   (8.19a)
 0 0 0  mi  m0 
li mi

4
and

 m 1 2  l  l   l  l 
 drˆ Y l m  rˆ  C   rˆ  Ylm  rˆ     1 l , l 
 
    (8.19b)
 0 0 0   m   m 

In equations (8.19a, b), l    2l  1 . Equation (8.16) then gives the direct T-matrix element for
electron-impact ionization of hydrogen atom as

l l l  i l  l l 
32
2
Ti 0D   
 
1
   
ki k k0 li mi l m l0m0 

 
i 0 i  e i  0  1 Yli mi kˆ i Yl m kˆ  Y l0m0 kˆ 0    
 1 2  l  l   l  l   li  l0   l  l  
  1  i   li , l0  l , l   i 0  
 m m 12  
     Dlil ll0 (8.20)
  0 0 0   0 0 0   mi  m0   m   m  

For momentum k 0 of the incident electron along the z-axis, we have 0  0,0  0 and
consequently

 2l  1 12
Y l0m0  
kˆ 0  Y l0m0  0,0   0
4
 m0 0 (8.21)

Equation (8.20) then reduces to

l l l  i l  l l 
32
2
Ti 0D   
 
1 1
  
4 ki k k0 li mi l m l0 
i 0 i  e i  0 Yli mi kˆ i Yl m kˆ     
 1 2  l  l   l  l   li  l0   l  l   
  1  i   l0 li  l , l   i 0  
 m m  12
     Dlil ll0 (8.22)
  0 0 0   0 0 0   mi  0   m   m  

Applying the properties of the 3-j symbols

 l  l   l  l   l  l
      m   ,m    (8.23a)
m  m m
 m   m   m   m   m  

and

 li  l0   li  l0   li  l0   li  l0 
    mi ,       m  m m  m  (8.23b)
 mi  0   mi  0     0     0 

Equation (8.22) then becomes (McCarthy and Weigold, 2005)

2
32
1 l 
12  i  l   l 1 2 

i  l   l  2  l 12
 e
2
Ti 0D   
  4 ki k k0 li 0
e li i i   
l  0

5
 l l l 
 l  l   l l
  1  Yli ,mm kˆ i Yl m kˆ   
m
    
m l   l l  0 0 0   m m  m m 

li 

i  l0 l0 2  l  li  l0   li  l0  
  e 0    m  m m  m
 Dl l ll
0  i  0
(8.24)
l0  li   0 0 0  

where we have used i  0 i    e  0 i    ein 2 .

l l l i l  l  l 2

In evaluating equation (8.24), the momentum k i of the scattered electron is taken to be in the
xz  plane while the momentum k  of the ejected electron is measured from this plane. In the
coplanar asymmetric kinematics, the relative azimuthal angle   i   is set equal to either to
0 or 180 , Ei  E , i  30 and   is varied. Non-coplanar symmetric kinematics corresponds to
Ei  E and i   . In this case, the relative azimuthal angle  is varied.

The spherical harmonics Yli ,m  m i ,0  and Yl m   ,  are then determined from the general
equation

  2l  1  m !
12
Y m  ,    1 P m  cos  eim
m
  m0 (8.25)
 4   m ! 

For negative values of m , the spherical harmonics are obtained using the equation

Y ,m  ,    1 Y m  ,  .
m
m0 (8.26)

where Y m denotes the complex conjugate of Y m .

8.2.2 Exchange T-matrix Element

Substituting equations (8.6), (8.11), (8.12) and (8.14b) in the second (exchange) term in equation
(8.10) gives

Ti 0E  i    0      1   0   0   1
  1
r01

l0 li l ei li  l l0 

32
2 1 1
   r 2 drdrˆ  r 2 dr drˆ  2 2   i
  ki k k0 r r  li mi l m l0m0

6
    
Fli  ki r  Ylimi  rˆ  Yli mi kˆ i Fl k  r Yl m  rˆ   Yl m kˆ   
r
  1  1 C   rˆ C  rˆ  Pnl  r Ylm  rˆ  l0  k0 , r Yl0m0  rˆ Yl0m0  kˆ 0 
 r

l l l  i l  l l 
32
2
 
 
1
   
ki k k0 li mi l m l0m0 

i 0 i  e i  0  1 Yli mi kˆ i Yl m kˆ  Y l0m0 kˆ 0      

   drˆY li mi  rˆ  C  rˆ  Ylm  rˆ  drˆ1Y l m  rˆ   C  rˆ   Yl0m0  rˆ    Elil l0l msi ms ms ms0 (8.27)
 

where Elil l0l is the exchange Slater-type integral defined as

 
r

Elil l0l   dr  dr Fli  ki , r  Fl k , r    r  1 l  k0 , r Pnl (r )
0
(8.28)
0 0 

Using the expansion

m1m2   j3m3 C jj3jmm

3
m
1 2 1 2
(8.29)
j3m3

In terms of the Clebsch-Gordan coefficients C jj3jmm3 m . The using equations (7.13) and (7.15) in
1 2 1 2

equation (8.27) yields

msi ms ms ms0   CssSMm m 0

S
s s0
CsSM S
s m
i  si ms
SM S

S   si
s ss0 S 
   2S  1  ms 
M S   ms ms ms

MS 
SM S  0  i   (8.30)
s s S s s0 S   s si S 
   1 i   2 S  1   
 ms ms M S   ms msi MS 
SM S  0   
   1
S

since si  s0  s  s  1 2 , and where S is the total spin of the two electrons. Note that S  0 and
S  1 corresponds to singlet and triplet scattering respectively. Also applying the Wigner-Eckart
theorem to evaluate the angular integrals in equation (8.27) gives

 l  l   li  l 
 drˆY

 rˆ  C  rˆ  Ylm  rˆ    1mi li , l 1 2  i   (8.31a)
 0 0 0  mi  m 
li mi

7
and

 m 1 2  l  l0   l  l0 
 drˆ Y l m  rˆ  C   rˆ  Yl0m0  rˆ    1 l , l0 
 
    (8.31b)
 0 0 0   m   m0 

Equation (8.27) then gives the exchange T-matrix element for electron-impact ionization of
hydrogen atom as

l l l  i l  l l 
32
Ti 0E
2
   1  
S

 
1
   
ki k k0 li mi l m l0m0 

i 0 i  e i  0  1 Yli mi kˆ i Yl m kˆ  Y l0m0 kˆ 0     
 1 2  l  l   l  l0   li  l   l  l0  
  1  i   li , l  l , l0   i
 m m 12  
      Elil l0l (8.32)
  0 0 0   0 0 0   mi  m   m   m0  

For an incident electron beam along the z-axis, we have   0,  0 and consequently

 2l  1 12
Y l0m0  
kˆ 0  Y l0m0  0,0   0
4
 m0 0 (8.33)

Equation (8.19) then reduces to

l l l  i l  l l 
32
S2
Ti 0E    1  
 
1 1
  
4 ki k k0 li mi l m l0 
i 0 i  e i  0 Yli mi kˆ i Yl m kˆ     
 1 2  l  l   l  l0   li  l   l  l0  
  1  i   l0  li , l , l   i
 m m   
      Elil l0l (8.34)
  0 0 0   0 0 0   mi  m   m   0  

Applying the properties of the 3-j symbols

 l  l0   l  l0   l  l0 
      m ,     (8.35a)
 m   0   m   0    m  0 
m

and

 li  l   li  l   li  l  li  l
    mi , m       ,m   m  m m
 (8.35b)
 mi  m   mi  m     m  m    m

Equation (8.34) then becomes

2
   1  
32
1 l   1
12 m 

i  li li 2  l 1 2 

i  l  l  2  l 12
 e   
S
Ti 0E e
 
i
4 ki k k0 li 0 l  0

8
 l li l 
 li  l   li l
   1m Yli ,mm  kˆ i Yl m  kˆ      
m l   li l  0 0 0   m  m m m

l   

i l0 l0 2  l  l  l0   l l0  
  e 0   E
0  lil l0l
(8.36)
l0  l   0 0 0   m m

Applying equations (8.24) and (8.36) in (8.10) gives

Ti 0DWBA 
4

1 D 3
 
Ti 0  Ti 0E  Ti 0D  Ti 0E
4
 (8.37)

where the first and second terms on the RHS of equation (8.37) correspond to singlet and triplet
scattering, where S  0 and S  1 respectively, and where the result is averaged over the sum
S 1

 (2S  1) of spin multiplicities.

S 0

8.3 Hermann-Skillman Mesh

In order to solve a differential equation or evaluate an integral numerically, a numerical grid or

mesh is needed in the form of values of the independent variable r of the differential equation or
the integration variable of the integral. A linear mesh consists of values of the variable which are
equally spaced that is

ri 1  ri  h , i  1, 2,...,  M  1 (8.38)

where ri 1 and ri are two adjacent values of the variable while h is the step size. Small values of the
step size lead to a reduction in the truncation error. This type of error is due to the
algorithm/numerical method used by the programmer. There is however a limit to how small the
step size can be made since a decrease in h leads to an increase in the mesh points resulting in an
increase in the round off error, due to inaccurate storage of values by the computer. To evaluate
atomic radial wavefunctions Pnl  r  numerically, for example in the Hartree-Fock method, a
combination of a linear mesh and a logarithmic mesh may be used (Fischer et al., 1997).

The use of the logarithmic mesh enables accurate evaluation of the atomic radial wavefunctions
near the origin where the wavefunctions vary rapidly. On the other hand in the evaluation of
radial distorted wavefunctions in scattering theory for large orbital angular momentum values l ,
the value of the wavefunction is small near the origin (in the vicinity of the atom) but varies
sinusoidally in the asymptotic region. An adaptation of the Hermann-Skillman mesh (Bartschat
et al., 1996), which is a linear approximation to a logarithmic grid, is preferred in which the
initial step size set at

h1  aZ 1 3 (8.40)

9
and the maximum radius at
r  bh1 (8.41)

where a  2.2133535 103 and b  81880 . The modified HS mesh is then subdivided into 6
intervals having a total of 2720 grid points. The step size hi used in each of these intervals is
double that of the previous interval. That is
hi 1  2hi i  1,....,5 (8.42)

The first 5 intervals each consist of 40 equally-spaced points making a total of 200 grid points.
The last interval has 2520 grid points.

8.4 Radial Wavefunctions

The reduced radial wavefunctions for the hydrogen atom can be expressed as

k
Pnl (r )   c jn f jnl (r ) , (8.43)
j 1

where f jnl (r ) are normalized Slater-type orbitals (STOs) of the form

 2 jnl 
I jn  12

f jnl (r )  r
I jn
 
exp  jnl r . (8.44)
 2I jn !
The summation in (8.43) is over k basis functions f jnl (r ) . In equations (8.43) and (8.44), c jn , I jn
and  jnl denote the coefficients, integers and exponents. For the 1s 1S0 ground state of hydrogen
atom, whose atomic number Z  1 , these parameters are listed in table 8.1 with k  1 .

Table 8.1: 1s radial atomic wavefunction for the ground state of hydrogen (McCarthy and
Weigold, 2005)

I js c jn  j1s
1 1 Z

These values are obtained from solving the radial Schrödinger equation for the hydrogen atom.
Subsequently, we have

P1s  r   2Z 3 2 re Zr (8.45)

For the 1s 2 1S0 ground state of helium atom, whose atomic number Z  2 , these parameters are
listed in table 4.1 with k  4 .

10
Table 8.2: 1s radial atomic wavefunction for the ground state of helium (Bunge et al., 1993)

I js c jn  j1s
1 1.4595 1.347900
3 5.3244 -0.001613
2 2.6298 -0.100506
2 1.7504 -0.270779

These values are obtained from calculations based on the Hartree-Fock theory of atoms (Cowan,
1981; Fischer et al., 1997; McCarthy and Weigold, 1995).

8.5 Optical Potential

To a first approximation, the optical potential Vopt in which the incident electron moves may be
taken to equal to the static potential which has the general form (Cowan, 1981)

Z  Pn l  r  
2
Vst  r      va  dr  a a , (8.46)
r nala 0 r

where va  2la   2  2la  1 is the occupation number of the n a l a target subshell, where the
multipole integral in (8.46) can be expanded thus

 Pn2ala  r   1r 
' na la  
P2 r
I   dr   
r 0
 dr P 2
r    dr , (8.47)
r
na la
0
r r

The first integral in (8.47) is the forward integral which is evaluated starting from the origin r  0
while the second integral is the backward integral evaluated from r  r . The integrals are
calculated using the five-point quadrature rule (Fischer et al., 1997)
x j 2

 y  x  dx  90 34  y j 2  y j    y j 3  y j 1   114 y j 1  O  h 

h 7
(8.48)
xj

At the ends of the integration range, where use of equation (8.48) is not possible, the less
accurate three-point Simpson’s 1 3 rule (Press et al., 1992) may be used
x j 2

 y  x  dx  3  y j  4 y j 1  y j 2   O  h 
h 5
(8.49)
xj

as well as Simpson’s 3 8 rule

11
 x j 3

 y  x  dx  8 3 y j  9 y j 1  9 y j 2  3 y j 4   O  h 
h 5
(8.50)
xj

 
Note the order of the truncation errors [denoted by O hn ] in these expressions.

8.6 Radial Equation

In potential/elastic scattering which describes the motion of the incident electron, the radial
Schrödinger equation

 d 2 l  l  1 
 2 2  
 2 E  Vopt  l  k , r   0 (8.51)
 dr r 

where  l is a radial distorted wavefunction, is solved subject to the boundary conditions

l  k ,0   0 (8.52a)

lim l  k , r   cos  l fl  k , r   sin  l gl  k , r  (8.52b)

r 

where Vopt  U opt 2 is the optical potential ( U opt is the reduced potential), E  k 2 2 is the energy
of the incident electron with respect to the ground state of the atom,  l is the phase shift
corresponding to  l , while f l and gl are regular and irregular Ricatti-Bessel functions
respectively. For a complex optical potential both the phase shift  l and radial distorted
wavefunction  l are also complex. To solve equation (8.51), Numerov method (Cowan, 1981)
may be used. In general for an ODE of the form

d2y
 F r  y  G r  (8.53)
dr 2

where G  r  is and inhomogeneous term, if y is known at points ri 1 and ri , then y at point ri 1 is

given by
 1 
Yi 1  2Yi  Yi 1  h2  Fi yi   Gi 1  10Gi  Gi 1   i  1,2,3,.. (8.54)
 12 
where
 h2 
Y  y 1 
 12 
F (8.55)
 

Comparing equations (8.51) and (8.53), we see that y  l and

12
  l  l  1 

F  r   2  E  Vopt   2r 2 
 (8.56)


The phase shifts  l are then determined by equating the logarithmic derivative  of the numerical
solution to that of the asymptotic form of  l , given by equation (8.52b), to obtain the K-matrix
elements
 k f   f 
K L  tan l    l l  (8.57)
 k g   g 
 l l 

where   y 1  dy dr  , fl  dfl d  , gl  dgl d  and   kr . Once the radial distorted waves and
associated phase shifts are obtained for the incident electron, they are then applied in
determining the direct and exchange T-matrix elements in equation (8.24) and (8.36). The
Coulomb functions and phase shifts, spherical harmonics, and 3j-symbols are obtained as
described in the COULFUNC, CGAMMAFUNC, ALPOLY, SPHARMONICS, and 3JSYMBOL
programs discussed earlier.

The sample input:

E0  eV  Ei  eV  E  eV   E0  Ei  I i  deg     deg  i  deg    deg 

100 84.4 2 8 0 0 0

with maximum values of li and l set to LMAX  20 , should yield a value comparable with the
value TDCS  0.9078 in McCarthy and Xixiang (1996) program. Note that I  13.6eV is the
ionization potential of hydrogen atom.

References

1. Cowan, R.D. (1981). In The Theory of Atomic Structure and Spectra.(University of

California Press, Berkeley). Pg. 178.

2. Fischer, C.F., Brange, T. and Jonsson, P. (1997). In Computational Atomic Structure,

(IoP, London). Pp. 1 – 63.

3. McCarthy I.E. and Weigold E. (2005). In Electron-Atom Collisions. (Cambridge

University Press, Cambridge).

4. McCarthy I. E. and Zhang Xixiang (1996). Distorted-Wave Methods for Ionization. In

Computational Atomic Physics: Electron and Positron Collisions with Atoms and Ions.
(Springer, Berlin). Ed. Bartschat K. Pg. 87 - 100

13