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Chapt er 6

Ex c i t a t i o n a nd I o n i z a t i o n
Excitation and ionization of one-electron atoms by relativistic projectiles
are t reat ed simultaneously in this chapter and are not distinguished. Most
applications refer to K-shell ionization which is the i mport ant process at
high velocities. The theoretical methods used for relativistic collisions are
very similar to those applied at nonrelativistic bombarding energies.
In Sec. 6.1 we start with an outline of first-order pert urbat i on theory,
and in Sec. 6.2, for the sake of illustration, we discuss the simple cases of
the dipole approximation and of a quasirelativistic t reat ment of the mat ri x
elements. Some of the methods used to evaluate the necessary interaction
mat ri x elements more exactly are presented in Sec. 6.3, so t hat one is in
a position to derive theoretical results and to compare t hem with the cor-
responding experimental data. In Sec. 6.4 we discuss the finite-difference
met hod for solving the time-dependent Dirac equation of the collision sys-
tern in a nonpert urbat i ve way. As an alternative nonpert urbat i ve method,
we consider two-center coupled-channel methods in Sec. 6.5, and subse-
quently specialize to single-center coupled-channel calculations.
For definiteness, we assume in this chapter t hat a single target electron
is excited or ionized by the projectile. If the active electron is carried by the
projectile, excitation can occur by the target nucleus, and one has simply to
interchange the role of target and projectile. Excitation is then influenced
by the target electrons. These and other many-electron effects are discussed
in Chap. 7.
139
140 C H A P T E R 6. E X C I T A T I O N A N D I O N I Z A T I O N
6. 1 Fi rs t - order pert urbat i on t heory
For a fast collision and for impact parameters b comparable with, or larger
t han the atomic K-shell radius, the transient perturbation of the target
atom by the projectile is small enough that the first-order time-dependent
perturbation theory is expected to be a good approximation, even for a
high-Z projectile.
6. 1. 1 General expressi ons
In first-order perturbation theory, by combining Eqs. (5.76) and (4.32), the
transition amplitude for excitation and ionization of the target electron is
written as
e ~/ZPe2 / i (Ef E i ) t / 1
Aft(b) -- i h dt e ~ - d3rT r -- Zaz) D- ~ i(rT). (6.1)
rp
Here, 7 is the Lorentz factor, Zp the projectile charge number, and ~i
and ~f are the initial and final eigenfunctions of the target electron with
energies Ei and Ef. The coordinates are explained in Fig. 3.2, and r},, given
by Eq. (5.97), is the electron-projectile distance measured in the projectile
rest system. The cross section for excitation is directly given by Eq. (5.65),
while for the differential ionization cross section we have to replace aft by
d a f i / d E f , so t hat for each specified initial and final state (see below) we
have
d a _ 27r [A~ll 2 bdb. (6.2)
d E f
In this formula, it is assumed t hat the radial continuum wave function
for each final partial wave ~f or jf, If entering in the transition amplitude
is normalized per unit energy interval, see Eq. (4.117). Since the emit-
ted electron is not represented by a plane wave but a Coulomb wave, the
approaches discussed here belong to the class of distorted-wave Born ap-
proximations (DWBA). Introducing the minimum momentum transfer hq0
through Eq. (5.105), the integration in Eq. (6.1) over the time dependence
residing in the exponential factor and in the term 1 / r ~ can be directly
carried out to yield [BAH59, AmA81]
2 qo ~ / ( X T _ b ) 2 + y~ ) i> 2 (6.3)
[A~[ - 4~ ] / f l ( l - 3a z ) e i % z T K o ( - ~
Here and in the remaining part of this chapter, we use the bracket notation
for the space integral. Furthermore, ~p is given by Eq. (5.52), and K 0
denotes the modified Bessel function. It is seen t hat the range parameter
6.1. FI R S T - O R D E R P E R T UR BA T I O N T H E O R Y 141
- 1
of the effective interaction is q0 along the path, i.e., parallel to the z-axis,
but is ~ / qo 1 perpendicular to it, i.e., in the impact paramet er plane. Hence,
as 7 increases, the integrand falls off more slowly with b t han in the beam
direction. This reflects the properties of the Li~ nard-Wiechert potential
given by Eq. (3.34) and depicted in Fig. 3.3.
For mul at i on i n t e r ms o f the Four i er t r ansfor m
For an actual evaluation of the cross section, it is more convenient to return
to the expression (6.1) and to rewrite the retarded interaction in terms of
its Fourier transform. Using the relativistically generalized Bethe integral
(5.103), the electronic transition mat ri x element in Eq. (6.1) can be cast
into the form (5.104). By decomposing q as q = (qb, qz) and performing
the time integration, one obtains from Eq. (5.106) the transition amplitude
A~(b) - i T vup Mfi(b) - -Tri u,,_ f
d2 qb
q2 + ( 1 -/ 32)q~)
and from Eq. (6.2) the cross section
C -i qb' b Mfi (q) (6.4)
~0 ~176
d ~ _ 87rr,2 qb dqb [Mfi(q)l u (6.5)
dEf [q2 + ( 1 - 32)q~]2 ,
where
Mfi(q) = (fl(1 - ~ a z ) c i q r T [i ) . (6.6)
The advantage of this formulation is t hat the complicated time depen-
dence contained in the expression (5.97) for r~, is removed and replaced
with the more explicit wave number dependence (6.5) and (6.6). The ex-
pression (6.5), valid for each target electron and for specified initial and
final states, agrees with the corresponding expression derived in a wave
picture, in which certain simplifications, described in Sec. 5.2, are adopted
[DAM78, Anh79].
Speci fi cat i on of the i ni t i al and fi nal st at es
For exci t at i on, the initial and final bound states i and f are specified by
their quant um numbers i - {hi, ~i, Pji } and f - {nf, ~f, #jf}, respectively,
see Eqs. (4.84) and (4.85). In order to obtain the complete cross section,
one averages over the initial angular moment um projections PJi and sums
over the final angular moment um projections pjf.
For i oni z at i on, Eqs. (6.2) and (6.5), the initial bound state is charac-
terized in the same way. However, for the final state of a given continuum
142 C H A P T E R 6. E X C I T A T I ON A N D I ONI Z A T I ON
energy Ef, one has to distinguish two possible situations determined by the
experimental setup.
(a) The energy Ef and the direction fr of emission of the electron is
1
detected. Then the final state f} - I Ef , fr a) with spin projection c r - +2
is a coherent superposition of partial waves ~f, pjf given by Eq. (4.124).
By inserting into (6.2) or (6.5) and summing over the (undetected) spin
projections, one obtains the angle-differential cross section.
(b) The direction of emission of the electron is not detected. Then one
integrates Eqs. (6.2) and (6.5) over the direction 1r of the emitted electron
in Eqs. (4.124) or (4.123) and sums over the spin projection a (or ms).
Owing to the orthogonality of the rotation matrices in (4.124) [or of the
spherical harmonics in (4.123)] and of the Clebsch-Gordan coefficients, one
obtains an incoherent summation over the partial waves ~f, #jf.
The resulting total energy-differential cross section for ionization is then
written explicitly as
dEf total
1 f ~ qb dqb
87r@ 2ji + 1 E E J0 [q~ + ( 1- f12)q212
~Ji ~f ' ~Jf
<Ef,~ f,#jfl(1 - fl.~)e* qrTlni,~,~ji) ,
(6.7)
where fl = v/ c.
In the following, we keep the symbols i and f for fully specified states,
i.e., [i} -- Ini, Ni, PJi ) and f} -- IEf, Nf, pjf }. Only when calculating angular
distributions, do we identify f with a coherent superposition If} - ]Ef, 1r a>
of partial waves given by Eq. (4.124).
6. 1. 2 L ong- r a nge c oupl i ngs a nd Coul omb bounda r y
c ondi t i ons
In the preceding subsection, we have assumed that the initial and final
states are undistorted target eigenstates. However, according to the discus-
sion in Sec. 5.3.3, we should use the exact solutions 1 (5.61)
9 t ) - t ) (6.8)
of the asymptotic Dirac equation (5.49), that is, we should take into account
the asymptotic distortion caused by the residual interaction - S2 Z p e 2 / R ~.
Inserting the solution (6.8) into Eq. (5.82), one finds from Eqs. (5.82)
and (5.83) that, by construction, the residual interaction term proportional
1An irrelevant constant phase factor depending on the unit of length is discarded.
6. 1. F I R S T - O R D E R P E R T UR B A T I O N T H E O R Y 143
to 1 / R ~ has to be subt ract ed from the interaction occurring in Eq. (6.1),
see Eq. (6.9) below. The reason why one usually disregards the residual
interaction t erm derives from nonrelativistic collisions, where, according
to Eq. (5.47), R- R ~, so t hat a term proportional to 1 / R has vanishing
mat ri x elements between orthogonal states.
For relativistic collisions, the situation is somewhat different. Let us ex-
amine the modified transition amplitude A e calculated with phase-distorted
states ~ satisfying Coulomb boundary conditions [ToE90b]. Since the
state-independent phase factors in Eq. (6.8) for initial and final states can-
cel each other, one has
.A~ (b)
i ~ZPe2 /
h d t e ~ ( E f - E i ) t
t J
x/ f ( l - ~ a z ) ( l
1
R,)
i) ( 6.9 )
instead of (6.1). The additional term 1/ _R I in the pert urbat i on operator
with R ~ = v/ b 2 + v2 t ~2 depends on the laboratory space coordinates t hrough
t ~ = ~ / ( t - VZ T / C 2 ) . In contrast to the nonrelativistic case, the space inte-
gral of the 1 / R ~ term does no t vanish. However, we still have to perform
the time integration. Since the integration f d 4z over the complete four-
dimensional space is Lorentz invariant, we may as well evaluate this integral
in the projectile frame. In the moving coordinate system, the term 1 / R ~
is a constant, therefore does not contribute to the mat ri x element between
orthogonal (exact) eigenstates, and hence can be discarded. We may now
transform back to the l aborat ory frame to obtain a result wi t h o ut the 1/_R ~
term, t hat is, we recover Eq. (6.1). In other words, Eqs. (6.1) and (6.9) are
equivalent, and Coulomb boundary conditions are without any influence.
It should be emphasized here t hat the equality of the two t reat ment s is
valid only in first-order pert urbat i on theory and only if we consider the
occupation amplitude for the final state at time t ~ oc.
Obviously, the same reasoning is valid for any function f ( R ~) and the
corresponding phase distortion. This means t hat the first-order transition
amplitudes for excitation and ionization (and for pair production) are in-
variant with respect to gauge transformations. This has also been confirmed
in [RuS93] by a different method.
As an illustration, we show in Fig. 6.1 the time evolution of occupa-
tion probabilities calculated from Eqs. (6.1) and (6.9), respectively, with
the modification t hat the upper limit of the time integration is taken as
t rather t han as oc. In the upper part of the figure, calculated from the
finite-time version of Eq. (6.1), we notice the effect of the long-range cou-
plings which lead to a sizable population of 2P3/2 and 2Pl/ 2 states in the
144 C H A P T E R 6. E X C I T A T I O N A N D I O N I Z A T I O N
1.0
1 0 - 1
1 0 - 2
> , 1 0 - 3
. _
. _
10- ~
o
c..
,-, lO-S
r -
0
. _
-4-
o 1.0
o 10 -1
1 0 - 2
10- 3
1 0 - 4 "
1 0 - s
1 G e V / u l s ~ l z
U g z * + U 9 1 +
u n p e r t u r b e d B o r n , - v- - - - - 2 s ~'lz / , l s ~ l z
/ / ~ - I 2 p ; , ~
/ / I r _ t ~ - z p 3 / z
+ 2 P3-/z
l s ~ / 2
b o u n d a r y - c o r r e c t e d B o r n
2s~'~z
2 p
' - 6 . 2 o . o 0 . 2 o . +
v t ( a . u . )
{ 2 l s ~ / z
2 p ~ / z
p3+, ~
Fi gur e 6.1. Time evolution of the occupation probabilities of target states in
U 92+ -~- U91+(lSl/ 2) collisions at 1 GeV/ u. Calculations are performed in the
Born approximation at b = 0.01 a.u. (about one K-shell radius). Upper part:
unperturbed initial and final states, Eq. (6.1); lower part: boundary-corrected
states, Eq. (6.9). The abscissa is the projection of the projectile-target separation
on the beam direction. The projections of the angular momenta are indicated by
1 1 3 and 3
+ , - , + for mj - - +~ , - ~ , +5, - ~ , respectively. From [ToE90b].
ent rance channel for projectile-target separations as large as 0.4 a.u. ( about
37 K-shell radii). On the ot her hand, in the lower part of the figure, the
finite-time version of Eq. (6.9) has been used. Here, as would be expect ed
from the short -range pot ent i al in Eq. (6.9), the long-range couplings have
di sappeared. For large positive times, the occupat i on probabilities in the
unper t ur bed and in the boundary-correct ed Born approxi mat i on are ex-
actly the same, thus verifying the reasoning given above. In a numerical
evaluation of the time integrals, one expects t hat the boundary-correct ed
version converges much more rapidly.
6. 2. T WO S I MP L I F I E D T R E A T ME N T S 145
6.2 T w o sim plif ied treatm ents
The t r eat ment presented so far is exact wi t hi n the first-order semiclassical
approxi mat i on of Eq. (6.1). For the sake of an i nt roduct ory illustration,
we now present two different approxi mat i ons, one valid at low values of q0,
which means small excitation energies or high projectile velocities, the other
valid for C~ZT << 1. These met hods are called the dipole approxi mat i on and
the quasirelativistic t reat ment , respectively.
6. 2 . 1 D i pol e approxi m at i on
In Bet he' s dipole approxi mat i on [Bet30], one replaces in the mat ri x element
(6.6) the factor exp(i q- r T) by 1 + i q. r T. Unless the wave number q
becomes larger t han the inverse K-shell radius a K (for K-shell excitation
or ionization) it is justified to neglect higher-order t erms in the expansion
because t he exponential decay of the bound-st at e wave function cuts off
cont ri but i ons from larger r values.
If we rewrite the Dirac mat ri x a z with the aid of the identity (5.91),
valid for exact eigenstates, and with the definition (5.105) for q0 = qz , the
dipole approxi mat i on yields
Mfi ~ <fl(1 - 13a=)eiqrT li> ~ i ( q" <flrTli> - 32qo<flzTli>), (6.10)
where each t erm obeys a different selection rule. Int roduci ng spherical
coordinates rs wi t h the magnet i c quant um number s - 0 , +1, so t hat r 0 =
z w and r +l - T~ ( x T + i YT ) , and subsequent l y defining reduced mat ri x
elements [Ros57] t hrough
/
Ji
1
( J f P j f Irs Ji Pj i > - - [
k
P ji 8
i f )
P j f
(f ]] rw I] i>, (6.11)
where Ji, P ji and jf, pjf are the angular moment a and their projections
of initial and final states, and ( . . ]-) is a Cl ebsch-Gordan coefficient, see
Eq. (4.88), we get
_qo2( 1_/ 32) 2 ( Ji 1
\
P ji 0
2
Jf
\
] [ ( f [] rT ]] i} [ 2
#j i
/
IM~I 2
and
[2 _ 1 2 ( 1
- - 2 ( qx + q~) Ji
\
Pj i + 1
P j f -- P j i '
(6.12)
j f ) 2
Pji i 1 [(f ][ rT ]] i)[2
if P j f -- P ji -~- 1.
(6.13)
146 C H A P T E R 6. E X C I T A T I O N A N D I O N I Z A T I O N
Bot h types of terms contribute to the cross section after summat i on over
final angular moment um projections, provided initial and final states have
different parity and the dipole selection rules embodied in the Clebsch-
Gordan coefficients are satisfied. In writing down Eqs. (6.12) and (6.13) we
still mai nt ai n a relativistic description of the electronic states. Expressions
(6.12) and (6.13) have different q dependencies and cannot be combined
unless the squares of the Clebsch-Gordan coefficients are equal. For the
particular transition Sl/2 --+ P l/ 2 all ( . -I. ) 2 - 1/ 3, but in general, e.g., for
sl/ 2 ~ P3/ 2, this is not true.
In order to evaluate the cross sections for each of the two cases, we
write q2 _ qg + q~, where hqb is the transverse moment um transfer. Since
1 1 dq~ we get from Eq. (6.1)
q d q - -~ dq 2 - -~ ,
do' ~ (]~ji ~ P ji ) __-- 47r@ ( Ji 1
dEf Pji 0
'N]21( f II rw II i)l 2
Jf
Pji
/
and
jr0 ~
qo2(1 - ~2)2
[q~ + (1 -/ 32)qg]2 dq~
(6.14)
do' ~ (]-~ji ~ ~ji-JI- 1) = 27rup2 ( Ji 1
dEf #ji +1
j f ) 2
~[~ji -1[- 1 I(f II rT l i)l 2
foo ~ q~ dq~ (6.15) x [q~ + (1 -/ 39.)qg]2 "
According to Eq. (6.5), the integration over q~ extends from zero to infinity.
The dipole approximation breaks down for large values of q, giving rise to
a t erm in Eq. (6.15) which diverges logarithmically. If, in the divergent
term, we introduce a cut-off qmax as the upper integration limit, we have
do' ~ (~ ji ~ ~ ji ) = 471./.]2 ( Ji 1
dEf Pji 0
and
2
Jf
\
] ] ( f ]} rT I] i) ] 2 ( 1 --/ 3 2 ) ( 6. 16)
Pji
/
do' ~ (J[~ji ~ ~[~ji -It- 1)
dEf
_ 11 Jf ) 2
P ji P ji 1
x 2 In 7 + in qmax 1
q~ + -
I(f ]l rw II i)] 2
1] . (6.17)
6 . 2 . T WO S I MP L I F I E D T R E A T ME N T S 147
In Eq. (6.17) we may neglect the t erm 7 . 2 in the second logarithm. If,
somewhat arbitrarily, we choose 2 _ 2 mE i / h 2 qmax as the nonrelativistic
inverse K-shell radius and, moreover, neglect Ef in the definition (5.105)
for q0 , we may replace 2 qmax/%2 wi t h 2 my 2 / E i .
Equat i ons (6.16) and (6.17) illustrate a very i mpor t ant feature, namel y
t hat for #j i --+ #j i transitions, the cross section approaches a const ant value 2
as the projectile energy increases, while for #ji - + #ji--t- 1 it grows propor-
tional to In 7 for large values of 7. The increase of the cross section as In 7
in the ext reme relativistic limit can be underst ood by considering the ex-
tension in the transverse direction of the LiSnard-Wiechert pot ent i al (3.34)
shown in Fig. 3.3. As a consequence, larger and larger i mpact paramet ers
contribute, and the cross section keeps increasing wi t h energy [AmA81].
This unbounded increase wi t h energy is characteristic for all per t ur bat i on
t heory approaches, which do not conserve unitarity.
6. 2 . 2 Qu as i r e l at i v i s t i c t r e a t m e n t
The cross section (6.5) is exact in first-order per t ur bat i on t heory as far as
relativistic effects are concerned. Here, we present a t r eat ment which em-
ploys semirelativistic Darwi n bound wave functions (See. 4.3.3) and semirel-
ativistic plane waves to evaluate the mat ri x element (6.6) using a convenient
coordi nat e system. The advant age of this t r eat ment is t hat the final cross
section is a sum of a nonrelativistic expression plus a relativistic modifica-
tion. For the nonrelativistic part , many t abul at i ons exist, given below, and
for the relativistic part , approxi mat e expressions are available.
For calculating the t ot al cross section, we st art from Eq. (6.7), using
an i nt egrat i on over q from q0 to infinity rat her t han ove r qb from zero
to infinity. It is advant ageous to evaluate the mat ri x element in a ~, ,),
coordi nat e system, in which the ~.-axis lies along q and the 2-axis lies in
the plane formed by q and/ 3. Then
/ 3-ct =/ 3cos A ct~ +/ 3si n A ct~. (6.18)
Here, k is the angle between q and/ 3, so t hat cos k = q z / q = q o / q , where
the z-axis points al ong/ 3. Subst i t ut i ng this expression into Eq. (6.7), the
mat ri x element of
( ~ e i q' r T = OL~ e i q z T
2The cancel l at i on bet ween 1 and ~ 2 as 3' --+ cc is a resul t of t he di pol e appr oxi mat i on
( 6. 10) . Any devi at i on from it l eads t o a finite cons t ant val ue in t he ext r eme r el at i vi st i c
l i mi t .
148 CHA P T E R 6. E X CI T A T I ON AND I ONI Z AT I ON
can be evaluated with the help of Eqs. (5.105) and (5.107) as
(f[cts eiqsTli> _ ~qo ei
--~--(f] qSTli >.
(6.19)
This and Eq. (6.18) yield
(f](1 - / 3. c~ )eiqrTli > -- (1 --/ 32 q~/q2)F(q ) _ ~ i I _ q2/q2 G(q) , (6.20)
with
F(q) = <fleiqSTli>,
G(q) = <floz:~eiq2Tli > . (6.21)
These definitions imply t hat the wave functions for the initial and final
states are specified in the x, y, z coordinate system.
Since the wave functions ]i} and If) are characterized by definite values of
the magnetic quant um number #j, the mat ri x elements F(q) and G(q) obey
different selection rules: in G, the operator c~ changes the total angular
moment um component along the 2-axis, but not in F. For any specific
combination of the magnetic quant um numbers Pji and pjf, at most one of
t hem contributes, so t hat the terms containing F and G add up incoherently
in the total cross section (6.7). This equation now becomes
/ ~ dq ( ~ 2 ( 1 - q~/q 2) 2)
do-~ - 87r@ E ~-ff IF(q)12 + (1 -/ 32 q~/q2)2 IG(q)l ,
dEf t ot a l o
(6.22)
with the underst andi ng t hat the sum is taken over all partial continuum
waves, and t hat in Eq. (6.21) the wave function If) refers only to a single
partial wave.
The t erm proportional to ~ IFI 2 is identical to t hat obtained for non-
relativistic projectiles. The t erm proportional to ~ IGI 2 is the relativistic
modification, as suggested by the factor/ 32. As/ 3 ~ 1, the first t erm be-
comes independent of/ 3 (or 7), since q0 becomes constant, see Eq. (5.105).
To obtain t he/ 3 dependence of the second term, one notes t hat the main
/3 dependence arises near q _~ q0. Hence, one can perform the integration
over q assuming G(q) ~_ G(qo) . One then finds t hat the second t erm is
proportional to
1 ln(1 /32 ] 2
~-5 - ) - 1- ~ 1n3, - 1, (6.23)
which, as/ 3 ~ 1, has the asymptotic form of Eq. (1.11).
6. 2. T WO SI MP LI FI E D T R E A T ME N T S 149
The mat ri x elements F and G have been evaluated with ls semirela-
tivistic wave functions for the electron [DaM78,Anh79]. Averaging over the
initial and summi ng over the final angular moment um projections of the
electron, and integrating over the final electron energy, one obtains the cross
section for ionizing a single K-shell electron. The expression is simplified if
one makes the substitutions
W -- 2 Ef - Ei ( 6. 24)
Z?re2/ao
and
q2a2
Q- z~ "
One then finds [MeL58, KhC69, Anh79, AnG86] a
(6.25)
(YK --
47rag 2 ZP2 4 / i m
r/K ZT in
dQ
d W mi n Q2
where
and
(IFKI ~ +
( 3ZTa) 2 (1 -- (~min/ Q)
(1 - / 32Qmi n/ Q) 2
~K - ( 9/ ~ Z T ) ~
1 2
( I G K I ~ + - ~ Q IF K I )
, (6.26)
(6.27)
Qmi n = W 2 / 4 ~] K ,
2I K xp
Wmi n = OK - - Z2e2/a O.
(6.28)
Here, IK xp is the experimental K-shell ionization energy, and for a neutral
target atom, the target charge is taken as an effective charge ZT ~ Z bar e-
0.3 according to the Slater screening rules [Sla60].
The factors IFKI ~, laKI ~ in Eq. (6.26) are squares of quasirelativistic
mat ri x elements calculated with hydrogenic Darwin and free-electron wave
functions. They are given by
[FK[ 2 -- ( 3Q+ W) QA3,
[ ( ~ K 12 __ 1 WA 2 (6.29)
4
3Since quasirelativistic wave functions are accurat e only to order C~ZT, it is in-
consistent to introduce normal i zat i on factors for these wave functions of the form
[1 + (aZT/2)2] - 1/ 2 and [1 + (kaZT/2)2] - 1/ 2, respectively [DAM78, anh79] . For this
reason, these normal i zat i on factors are omi t t ed in Eq. (6.26), as is in fact done also in
[Anh85a, AnG86].
150 C H A P T E R 6. E X C I T A T I O N A N D I O N I Z A T I O N
wi t h
An ----
27 e xp{ - 2/ k a r c t a n[2 k / ( Q + 1 - k2)]}
311 - e xp ( - 2 7r / k ) ] [( Q + 1 - k2) 2 + 4k2] n'
k - v/ W- 1. (6.30)
The i nt egrat i on over q in Eq. (6.26) has to be performed wi t h some care
(see t he discussion preceding Eq. (6.22) and in [MeL58, Anh79, AnG86] ) .
The first t er m with ]FKI 2 arises from t he longitudinal cont ri but i on present
also in nonrelativistic collisions. The t erms proport i onal to IGK[ 2 and
1 12
~Q]FK are i nt erpret ed as t ransverse and spin-flip contributions, respec-
tively [Anh79]. The t ransverse and spin-flip t erms are most i mpor t ant for
hi gh-Z t arget s, for which t he quasirelativistic approxi mat i ons act ual l y lose
their justification. Tables for t he longitudinal part of the cross section are
available [KhC69, ChM73, RIB77, BeK78, JOB79], but rat her t han using
t he projectile energy entering in t he tables, for relativistic collisions one
must use t he ion velocity entering t hrough t he par amet er ~]K given in Eq.
(6.27). 4 Est i mat es for t he t ransverse and spin-flip cont ri but i ons are given
in [Anh79, AnB87].
In Fig. 6.2, t heoret i cal ur ani um K-vacancy product i on cross sections are
shown for bare projectiles of charge Zp. According to Eq. (6.26), t he t ot al
cross section is proport i onal to Z~ . Hence, t he cross section shown has
been divided by Z~ . For 7 >- 10, t he t ransverse and spin-flip cont ri but i ons
account for more t han one-half of t he t ot al cross section. Figure 6.9 shows
t hat these cont ri but i ons bring t he t heory into close agreement wi t h t he ex-
peri ment al dat a. Al t hough, as not ed previously, t he wave functions used to
eval uat e t he cross sections are valid only for c~ZT << 1, t he agreement ap-
pears to st ret ch to C~ZT ~-- 0.7. This may be because t he collision dynami cs
explores a part of t he bound and cont i nuum wave functions which is not
sensitively dependent on c~ZT.
For general orientation, Fig. 6.3 shows reduced 1s-vacancy product i on
cross sections by bare projectiles on one-electron t arget s as a function of
In 7 for various values of ZT, cal cul at ed from Eq. (6.26). 5
4 In the theoretical expression (6.22), the projectile velocity enters through the pa-
rameter q0 in the nonrelativistic term and through q0 and/ 3 in the relativistic term.
5One-electron (ls) loss cross sections for projectiles by bare targets are given by
[AnB87]. By interchanging ZT and Zp, the 1s-ionization cross section of a one-electron
target by a bare projectile can be obtained. Figure 6.2 is taken from [Anh79] and refers
to two electrons in the K-shell, whereas Fig. 6.3 is taken from [AnB87] and refers to a
single ls electron.
6.2. T WO SI MP LI FI E D T R E A T ME N T S 151
2 5
2O
o 1 5
. J~
I 0
_ I I / / / ~ _
I 0 I 0 0 I 0 0 0
Fi gur e 6. 2. Calculated cross sections for U K-vacancy production by bare pro-
jectiles of charge Zp, divided by Z~, as a function of the Lorentz factor 0', using
Eq. (6.26). The longitudinal, transverse, and spin-flip contributions are shown,
as well as the total cross section. From [Anh79].
1 4
12
A
. . Q
,q- 10
+o
~ 8
N
out.. 6
I %
2 [
0
I I J
10 102 103
-1
3
7
10
2 0
5 O
9 2
Fi gur e 6.3. Calculated cross sections for one-electron target (ls) ionization
by bare projectiles of charge Zp, multiplied by (Z T / Z p ) 2, as a function of the
projectile Lorentz factor y. The calculated curves are based on Eq. (6.26). The
units are b/ electron. Adapt ed from [AnB87].
152 C H A P T E R 6. E X C I T A T I O N A N D I O N I Z A T I O N
6.3 Mul ti pol e expansi on
For high-Z target atoms, it is mandat ory to use exact relativistic wave func-
tions for initial and final states. The factor r s- 1 in the Dirac l s bound and
continuum wave functions [see Eqs. (4.98), (4.103), and (4.114)] contracts
the radial electronic density distribution. The resulting decrease of the ra-
dial mat ri x elements leads to smaller cross sections [AnG86] compared to
the nonrelativistic t reat ment of electrons.
For calculating exact matrix elements, one may either use a multi-
pole decomposition of the interaction in coordinate space [MeS89], or one
may decouple the angular part of the electronic and projectile coordinates
[VaB84, BEG85, Bec86] by introducing a multipole expansion for the expo-
nential exp(i q. rT) occurring in Eq. (6.4). This amounts to an expansion
in moment um space. In the following, we discuss bot h types of expansion
in turn.
6. 3 . 1 Mul t i pol e expans i on in coordi nat e s pace
Ret urni ng to the starting equation (6.1), one may t ry to decouple the time
integration associated with the nuclear motion from the integration over
the electronic coordinates by performing a multipole decomposition of the
interaction term 1 / @. Such an expansion is applicable not only in the per-
t urbat i ve formula (6.1) but also in a more rigorous coupled-channel treat-
ment, see Sec. 6.5.
For a nonrelativistic interaction 1/ Ir 1 - r21 , the st andard multipole ex-
pansion leads to a complete decoupling of the angular dependence of the
vectors r 1 and r2, i.e., a decoupling of the unit vectors r l and f2. In a rela-
tivistic collision, the Lorentz contraction acts in the z-direction, so t hat the
Cartesian coordinates are not treated on equal footing in Eq. (5.97). Some
coupling in the polar angles will therefore remain. A partial decoupling
[RuS93] can be achieved by rewriting the interaction term in the form
1 1 1
r{~ V/(XT _ b)2 + y2 + ~/ 2(z T _ v t ) 2 I P e - - P P I ' ( 6. 31)
where we have formally introduced the vectors
Pe - (Xw, YT,~ZT) with pe -- IX 2w + y2 w + 72Z2 w (6.32)
and
pp = (b, 0, ~/ vt ) with p p = v/ b 2 + ~ 2 v2 t 2 . (6.33)
6.3. MUL T I P O L E E X P A N S I O N 153
zT !
I " T
( x . ~ + y m 2 ) 1 , 2
Fi gur e 6.4. Definition of the vector Pe"
These vectors are not physical position vectors for the electron and pro-
jectile, respectively, nevertheless t hey are formally useful in part l y separat-
ing the electron mot i on from the projectile motion. In Fig. 6.4, we show the
relation of the modified vector Pe to the position vector r T = (XT, YT, ZT)"
Int roduci ng the polar angles 0 of r T and 0' of Pc, we can rewrite
p~ - - rTu(O ) (6.34)
with
u(O) - V/1 + (7 2 - 1) cos 2 O, (6.35)
so t hat
COSO t - - 7 Z T _ _ 7 C O S 0
- - p~ - - u(O) " (6.36)
We now decompose the inverse distance 1 / I p ~ - p p [ of Eq. ( 6. 31) i nt o spher-
ical harmoni cs YLM, dependi ng on the directions ~ and ~ p, in the form
1
Ip~ - pp[
EL=O 2L 4- 1 pL+l E M- - - L Y; M( R P ) YLM( R e ) ,
if Pe ~- PP,
oo 471" p L L
}-~L=O 2L + 1 [rTU(O)]L+ 1 ~-~-M=-L Y; M( P P ) YLM( P ~ ) ,
if p~ _> pp,
(6.37)
154 C H A P T E R 6. E X C I T A T I O N A N D I O N I Z A T I O N
~ p
=pp l u ( O )
Fi gur e 6.5. Illustration of the inner and outer regions in which the angular and
the radial integration decouple and of the intermediate regions in which they do
not decouple.
or, equivalently,
IPe - - P P [
47t
= E 2 L + 1 v L ( r T ' O ' p P ) Y[ M( ~ P ) YL M( ~ )
L M
(6.38)
wi t h
[rTU(O)] L
pL+l ,
vL(r~ , e, pp) - p~
if r T ~ p p / U( O ) ,
if r T ~ pp/ u(O) .
(6.39)
The distinction, which one of Pe or pp is larger, is seen to depend on t he
angle 0, unlike for t he nonrel at i vi st i c case. Since, according to Eq. (6.35),
u(O) varies bet ween 1 and 7, t he separat i on bet ween t he radial and t he
angul ar i nt egrat i on is compl et e only in t he range r w < p p / ~ / a nd r w >__ pp.
The dividing surface bet ween t he inner and t he outer region is given by t he
ellipsoid pe = rwu(O ) = pp. The inner, outer, and i nt ermedi at e regions are
i l l ust rat ed in Fig. 6.5.
The first-order t ransi t i on ampl i t ude (6.1) is now expressed as
A~ (b) - i ~/ZPe2 f
.... h d t e i ( E e - E i ) t / h Mf i ( b , t ) .
(6.40)
6.3. MUL T I P O L E E X P A N S I O N 155
Here, the mat ri x element is
47r
M~ ( b , t ) - E 2 L + 1 (fl(1 - / 3a z )
L=0
VL( r T O, pp)YL,ttjf_pj i ( ~ ) l i } Y* '~ r~J --"Ji ( P P )
(6.41)
The quantities #ji and #if are the angular moment um projections of the
initial and final states, respectively. Formula (6.40) is a possible point of
depart ure for the accurate evaluation of excitation, ionization, and pair pro-
duction cross sections using Eqs. (5.64) and (5.65) within first-order pertur-
bation theory. The mat ri x elements (6.41) can, of course, also be employed
for detailed single-center coupled-channel calculations [RuS93].
In evaluating the mat ri x elements (6.41), one has to observe t hat , owing
to (6.39), not only the radial integration over r T but also the integration
over the polar angle 0 within the interval flp/ ~/ < r T <__ pp depends on
the particular value of b and t t hrough the relation tip -- v/ b 2 + "),2v2t2 of
Eq. (6.33). Only the integral over the azimuthal angle can be carried out
easily.
6. 3 . 2 Mu l t i po l e e xpans i on in m o m e n t u m s pace
Let us now t urn to the calculation of the transition ampl i t ude in momen-
t um space which allows for a more complete separation of the integrations
associated with the electron and the projectile coordinates.
If we st art from the right-hand side of Eq. (5.104) [which leads to
Eq. (6.4)] rat her t han from the left-hand side, a decoupling is achieved
by decomposing the exponential exp( i q- r T) . In terms of a spherical repre-
sentation ~ t - q / q - - (Oq, r wher e q2 _ q~ + q02, and rT -- r T/ r T -- (0, 0),
we can write the expansion of the plane wave as
oe L
C i q' rT -- 47I E E iL JL(q r T ) Y~ M((t ) YLM(~ T ) "
L=0 M=--L
(6.42)
While in each t erm of the sum, the angular dependencies factorize, the ra-
dial parts remain coupled by the spherical Bessel function j L( q r T ) . Using
q b " b = qx b = qbsin Oq cos Cq and the integral representation of the Bessel
function JM, one may carry out the Oq integration within the angular in-
tegral on the ri ght -hand side of the mat ri x element (5.104) to get
~027r / 1 e-iqb sin O q c os (r
dC~q i d cos Oq q2(1 - 32 cos 20q)
Y;M(Oq, Oq) =
156 CHAPTER 6. EXCI TATI ON AND I ONI ZATI ON
i t _ ( ~ ) 1 ( q z )
2 ~ i - " l d q~ _ 9~qz 2 y~ , ~ rccos-,q o J M( b v / q ~ - q~ ) .
(6.43)
By substituting Eq. (6.42) into (6.4) and employing Eq. (6.43), one obtains
the transition amplitude
A~(b) 8iTrup E i L- M ~0 cc q dq
q~ _ 9~ q~,
L , M
x (f[(1 - 3Ctz)jL(qrT)YLM(~T)[i ) BLM(b , qo, q),
(6.44)
where
( rccos ~ ,04 ,
is the straight-line path factor [AmA81, VaB84, BEG85] t hat already oc-
curs in the SCA for nonrelativistic collisions [BAH59]. The Heaviside step
function O( q- q0) assures t hat q is greater than its projection q0.
The total cross section is derived either from Eq. (6.44) using the or-
thogonality relation for the Bessel functions or, more directly, from Eq.
(6.5). The final result for the ionization cross section per electron can be
written as
dcr~ _ 87c@ q dq
dEf o (q2 _/ 32q~)2 IMfi(q)l 2, (6.46)
with
(2O
Mfi(q) - 47r E iL <f](1 -/ 3az) j L( qrT) YL, , j f_, j i (~T)li}
L = 0
ar ccos- - , 0 , (6.47)
X rL,#jf_#j i q
where ]_Lji and #jf are the angular momentum projections of the initial
and final state, respectively. This formula is the starting point for the
accurate evaluation of excitation and ionization cross sections within first-
order perturbation theory [VaB84, BEG85].
Before moving on to discuss some details and generalizations, a few
comments may be appropriate.
(a) First, we observe t hat in contrast to Eq. (6.15) in the dipole ap-
proximation, there is no convergence problem at the upper limit of the
q-integration in Eq. (6.46). The cross section is well-defined without am-
biguous cut-off procedures.
6. 3. MUL T I P O L E E X P A N S I O N 157
(b) The behavior of the cross section (6.46) in the extreme relativistic
limit ~/>> 1 can be investigated by expanding the integrand around q- q0.
In this way, it is shown by Becker [Bec86] t hat for #if - #j i (and also
for IPjf - #j i I >- 2), the integral tends to a constant value as ~/ increases.
However, for #j r - #j i + 1, the integral increases with ~/ as ln~ . This
is in accordance with the results (6.17) or (6.23), derived more simply in
the dipole approximation or the quasirelativistic treatment, and with the
asymptotic behavior given in Eqs. (1.10) and (1.11).
(c) The choice of the gauge for the electromagnetic potentials is dis-
cussed in some detail in [AmA81]. Here, we have used the Lorentz con-
dition (3.3) which is Lorentz invariant and hence allows us to derive the
electromagnetic potentials A and (I) by a Lorentz transformation from the
static Coulomb potential. This renders it possible to use Eq. (6.4) to de-
rive rather simple pat h factors (6.45) which actually are the same as for
nonrelativistic projectiles. On the other hand, the Coulomb gauge defined
by V- A C~ - 0 leads to more complicated pat h factors. A comparison of
numerical results for cross sections calculated in the Lorentz and Coulomb
gauges in the plane-wave Born approximation as well as in the SCA shows
agreement with one another on the 1% level.
(d) The electronic mat ri x elements in Eq. (6.47) have to be calculated
with relativistic wave functions. The use of nonrelativistic approximations
either leads to a violation of gauge invariance (since the electromagnetic
coupling j u A P / c , Eq. (5.31) is not compatible with the SchrSdinger equa-
tion) or leads to second-order terms in the potentials and hence to a spurious
projectile charge dependence as Z~. Only by a careful analysis lAmA81] is
it possible to remove these spurious terms.
In evaluating the mat ri x elements (6.47) rigorously, it is no longer useful
to reduce the terms containing the Dirac mat ri x C~z by employing Eq. (5.90).
Rather, with the definitions (4.86) and (4.87), one may decompose the
mat ri x elements as [VaB84, BEG85]
( f l( 1 - ~C ~z) j ~( q r T ) Y Zm( ~T ) l i } - -
A1 f (1) (q) + i ~ A 2 f ( 2 ) (q ) - i ~ A 3 f ( 3 ) (q ) (6.48)
where the angular integrals are defined by
~Jf Pj"
dl - {/ ~gf I YLMI ~ ai ' )
_ _ (~ PJf ~Ji
me , ) ~_~fl YLMOz I X~i }
A3 ~ ]~jf ~Ji
- I rL. zl _ l
(6.49)
and are evaluated with st andard techniques [Ros57, Edm57]. The radial
158 C H A P T E R 6. E X C I T A T I O N A N D I O N I Z A T I O N
integrals are defined as
f0 C~
FL (1) (q) -- j L( q r ) ( g i g f -Jr- f i f f ) r 2 dr
/0
Ft 2) (q) - - JL ( q r ) g i f f r 2 d r
Fi 3)(q) -- j L (q r ) f igf r 2 dr. (6.50)
The integrals can be rewri t t en in t erms of hypergeometric functions [JaZ57,
Amu78, JaA80, TrB83, VaB84] if exact Coulomb bound-st at e wave func-
tions (4.98) and continuum partial waves (4.114) are inserted. The actual
evaluation is performed numerically [BEG85].
The calculation of the t ot al and energy-differential ionization cross sec-
tion according to Eq. (6.7) requires an averaging over all #ji and a sum-
mat i on over all values of ~f and #if. In practice, the summat i on has to be
t runcat ed at a maxi mum value ~max because of computer limitations. For
the angle-differential cross section, one has to use the wave functions (4.123)
or (4.124) with well-defined asympt ot i c moment a instead of the spherical
partial waves.
6. 3. 3 P e r t ur ba t i ve r e s ul t s a nd c ompa r i s on wi t h e xpe r -
i me nt
In an experiment, we usually have a solid or gas target, t hat is, we have
to take into account many-electron effects. Deferring a more detailed
discussion to Chap. 7, we assume for the present purpose t hat the K-
shell wave function of a complex t arget at om can be approxi mat ed by an
effective hydrogenic wave function. The generally accepted met hod uses
an effective Slater-screened t arget charge Z~ = Z bar e- 0.3 in conjunction
with experimental K-shell binding energies. These binding energies are not
consistent with the wave functions used. One may expect, however, t hat
mai nl y the inner part of the wave function is responsible for the mat ri x
elements. This part is well described by the effective nuclear charge Z~ .
The outer part is related to the binding energy but does not enter sensitively
into the results. Nevertheless, it is not clear whether the inconsistency may
lead to sizable effects in some cases. In most results to be discussed in this
chapter, it is justified to neglect the effective-charge correction.
The first step in calculating differential (in electron energy and angle)
and t ot al cross sections consists in studying the i mpact -paramet er depen-
dence of the ionization probability P (b ) . The weighted K-shell ionization
probability 27rb P (b ) usually has a maxi mum in the vicinity of the K-shell
6.3. MULTI POLE EXPANSI ON 159
radius a K. This is similar as for the excitation probabilities in Fig. 6.13 for
coupled-channel calculations.
Figures 6.6 and 6.7 show calculated double-differential ionization cross
sections d2cr/dEe df~e for fixed electron energies and fixed electron emission
angles, respectively, for the system Zp + U [MoG89]. In Fig. 6.6, we
can see t hat electron emission occurs mainly at smaller electron energies.
As Fig. 6.7 demonstrates, the angular anisotropy of the emitted electrons
becomes peaked in the forward direction as their kinetic energy increases.
Since, owing to limitations in computing power, I~1 _< 10 has been used,
the convergence of the partial-wave contributions in Eq. (4.123) becomes
unsatisfactory at backward angles, so t hat this angular range is not included
in Fig. 6.7.
In Figure 6.8, the total K-shell ionization cross section for p + U
collisions is plotted as a function of the Lorentz factor -y. As already seen
explicitly in the dipole approximation of Eq. (6.17), the cross section in-
creases monotonically with "y. The quasirelativistic calculation of Anholt
[Anh79] and the multipole expansion calculation of Becker et al. [BeG85]
show the same qualitative behavior as the collision energy increases. For
-y > 2, the absolute difference between the calculations increases slowly
with ~,. For large values of -y, Becker et al. have the problem t hat a grow-
ing number of terms contribute in the multipole expansion (calculations
have been carried up to 1 = 6); however, the authors estimate the resulting
inaccuracy to be less t han 5 %. On the other hand, differences in the wave
function will affect the matrix elements changing the magnetic quant um
number by one unit and hence will increase as ln' y for large energies. It
is therefore quite natural t hat discrepancies slowly build up as the energy
increases.
Numerical calculations have established an approximate scaling rule
lAmAS1, Bee86] for the ionization probability at high relativistic energies
(3' > 5) and fixed impact parameters. For b = 0, the ionization probability
P ( b - O) - 1.8 x lO-4Z~ (6.51)
is independent (within +10%) of the target charge up to the heaviest el-
ements. This empirical finding shows t hat for Zp _> 75 the ionization
probability exceeds unity, and hence pert urbat i on theory breaks down.
There are few experimental dat a to compare with theoretical results.
At present, only measurements for total cross sections of K-shell ioniza-
tion in various target atoms are available. In Fig. 6.9, the total K-shell
ionization cross section is shown for 4.88 GeV protons impinging on target
atoms with charge numbers ZT. For the calculations of [DAM78, Anh79],
quasirelativistic wave functions are used. For high-Z targets, the deviation
160 C H A P T E R 6. E X C I T A T I O N A N D I O N I Z A T I O N
lO
10 ! 1
u ' l
9 T 1
>~
~E
, Z3
~ 10-3
10-6
" I
I
I I i I I 1
2 S l l 2
e ( d e g )
9O
9 0 "
I
2 4. 6 8
E, (MeV)
1 0 - 3
1 0 - 6
. 1 1 0 - 6
Fi gur e 6. 6. Double-differential cross section for t he ionization of t he lSl/ 2 and
2Sl/ 2 t ar get st at es in Zp + U collisions at Elab -- 1 GeV/ u as a funct i on of t he
energy of t he ionized electron. The par amet er at each curve gives t he l abor at or y
emission angle 0. From [MoG89].
1 0 - z
~" 1 0 - 3
f -
U e l
"T
>
( l J
1 0 - ~ '
~." I0 - s
- o 0 - 6
uYl
~ 1 0 - 7
3me 2
0 2 0 / , 0 6 0 80
e { d e g)
Fi gur e 6. 7. Double-differential cross section for t ar get K-shell ionization in Zp
+ U collisions at Elab -- 1 GeV/ u as a function of t he el ect ron l abor at or y emission
angle 0 for various el ect ron energies Ee. From [MoG89].
6.3. MUL T I P O L E E X P A N S I O N 161
1/., . r~
12 " . ' "
1 0 , o . . ~ ~ S S ' ' ' ' ~
1 1 0
Y
Fi gure 6. 8. K-shell ionization cross section for p + U collisions as a function
of the Lorentz factor ~. Dashed curve: [Anh79]; solid curve: [BeG85]. In both
curves, experimental binding energies have been used.
from exact relativistic wave functions (used in [BEG85]) should be most
significant. In fact, the results for the two types of calculations differ by
only 10%. Unfortunately, the calculations using more accurat e electronic
wave functions lie farther away from the experi ment al data. Considering
the experi ment al errors, it certainly would not be justified to prefer any
of the calculations j ust on the basis of a comparison wi t h the data. For
furt her discussion see [Eic90].
In view of the scarcity of ionization dat a for relativistic at omi c projec-
tiles, it is t empt i ng to t ur n to ot her projectiles. Ionization measurement s
have been made wi t h electrons up to 23 GeV, corresponding to 3' = 4.4 x 104
[SpM94]. At these ext remel y high values of 3', the relevant i mpact parame-
ters are so large t hat t hey lie in the medi um surroundi ng the t arget at om. 6
This leads to a shielding of the projectile' s electromagnetic field [Fer40],
which causes the cross section to sat urat e [Sor87, ChE89]. Such " many-
body" effects lie outside the scope of this book. Below the onset of the
sat urat i on, though, typically for "y _< 103, one can expect t hat high-energy
electrons have ionization cross sections similar to those of protons. This is
true, as long as the t raj ect ory of the electron projectile can be approxi mat ed
by a st rai ght line for the relevant collisions. Calculations by Davidovid et
al. [DAM78], based on a relativistic first-order wave theory, show t hat even
6At these high values of -y, the de Broglie wavelength h/ (~meC ) is small enough
( ~ 10 -2 fm) t hat the concept of impact paramet er is applicable even to electrons.
162 C H A P T E R 6. E X C I T A T I O N A N D I O N I Z A T I O N
I I
2 0 \
r-,
, 4
10
0 i
7 0 80 90
ZT
Fi gur e 6. 9. K-shell ionization cross section for 4.88 GeV protons versus t he
t arget charge. Experi ment al dat a and dashed curve: Anholt et al. [Anh79], see
also Davidovid et al. [DAM78]; solid curve: Becket et al . [BEG85].
A
JQ
z 1 6 0
O
I -
U
LO
o o
1 2 0
0
k)
z
o 8 O
I - -
<
N
z
_o 4 o
_ J
. _ i
w
--r
!
,- 0
1 . 0 2 1 . 2 3 2 1 2 0 0 2 0 0 0
. . . . I . . . . . . . . I . . . . . . . . 1 . . . . . . . . I . . . . . . . . 1 . . . . . . . . I ' ' '
4 7 Ag
- - f . - -
~ , ~ ? . - i ~ ' y .."
- f . . ~ . , ~ , . . . ' " o -
~ ,;, . . "
_ - . . . . . . . . . . . . ; , . . : : : . . . . . . . . . . . . . . . . . . . . -
.
. . . . I , I l , ' " ' l . . . . - - , " " , , , I . . . . . . . . I . . . . . . . . I . . . . . . . . I , , ,
1 0 - 2 1 0 -1 1 0 ~ 1 0 1 1 0 2 1 0 3
I NCI DE NT KI NET I C ENERG Y ( Me V )
F i g u r e 6 . 1 0 . K-shell ionization cross section for Ag bombarded by electrons.
The dash-dot t ed curve gives t he result of a semiclassical calculation [Ko175], the
dashed curve a fully quant um-mechani cal calculation [Sco78], and the solid line
a calculation based on st ruct ure functions with one-phot on exchange [EsM82],
t oget her with a decomposition into longitudinal (a l) and transverse plus spin-
flip (a t) contributions. Note t hat the abscissa is not linear in ln-7. From [Gen84].
6.4. N O N P E R T UR BA T I VE A P P R O A C H E S 163
for ~ as low as 5 (2-MeV electrons), electron and proton cross sections dif-
fer by less t han 5% up to Z p = 50. Therefore, we show in Fig. 6.10 the
K-shell ionization cross section for electrons on Ag. A comparison is made
with various theories. One of these, by Eschwey and Manakos [EsM82],
allows a decomposition into longitudinal (a z) and transverse plus spin-flip
(a t ) components, shown in dot t ed lines on Fig. 6.10. The former goes to
a constant, and the latter increases as in ~, as ~ increases to high values,
illustrating the expected behavior of these cross section components. Com-
parisons of other relativistic electron dat a with Eq. (6.26) can be found in
[Anh79].
6.4 Nonpert urbat i ve approaches
The empirical scaling rule Eq. (6.51) of the ionization probability at im-
pact paramet er b - 0 shows t hat pert urbat i on theory breaks down at large
projectile charges. Already for Zp _> 75 the probability P (b - 0) >_ 1.0,
so t hat for medi um-Z projectiles, the met hod will st art to become ques-
tionable. Although this conclusion is weakened for the more i mport ant
larger impact parameters, it is nevertheless mandat ory to examine nonper-
t urbat i ve approaches. We first consider the finite difference met hod and in
Secs. 6.5 and 6.6 proceed to coupled-channel methods.
We would like to mention another relativistic nonpert urbat i ve approach,
namely the classical-trajectory Monte-Carlo ( CTMC) met hod [TeTS0,
HoH92]. The nonrelativistic CTMC version, while difficult to justify theo-
retically, is known to be successful in low-velocity collisions. The relativistic
version t reat s the nuclear as well as the electronic motion by solving the
classical relativistic equations of motion for the t hree-body system assuming
a relativistic microcanonical distribution of initial positions and moment a
and ignoring the electron spin.
6. 4 . 1 F i n i t e - d i f f e r e n c e m e t h o d s
Let us now t urn to finite-difference calculations. Here, the time-dependent
Dirac equation in its Hami l t oni an form (5.40) is solved numerically. Writ-
ing, for a small time step At,
9 (rT, t + At) = U(t , t + At ) ~ ( r T, t), (6.52)
the time evolution operator is evaluated as
( ) - 1( i 1 )
i 1At ) 1 - At H( t + At)
U(t , t + At) - 1 + ~-~ At H ( t + -2 ~-h
(6.53)
164 C H A P T E R 6. E X C I T A T I O N A N D I O N I Z A T I O N
Fi gur e 6. 11 Ti me evol ut i on of t he el ect r on densi t y di s t r i but i on in t he z T - - p-
pl ane [ p- (x 2 + y2) 1/ 2] for a U 92+ + V 91+ col l i si on at 10.0 Ge V/ u. The t ar get
r emai ns fixed at Zw = p = 0 whi l e t he pr oj ect i l e moves at b = 0 from ri ght t o
left al ong t he Zw-axis in t he posi t i ve z-di rect i on. It is l ocat ed at Zp - - 3. 1 x 103
fm for t = - 8 . 0 [in uni t s of h/ / ( m~ c 2) -- 1.28 x 10 -2~ s], at Zp = 0 for t = 0, at
Zp = 2.3 x 103 fm for t = 6, and at Zp = 4.2 x 103 fm for t - 11. The densi t i es
are gi ven in uni t s of ao 3 (a0 = 5.3 x 104 fm). Fr om [ ThB92] .
6. 4. N O N P E R T UR BA T I VE A P P R OA C HE S 165
up to second order in At. After discretizing the wave function in space as
well, one may follow its time development starting from a suitable initial
condition. The numerical technique is described in detail by Becker et al.
[BeCS3].
In order to render the numerical procedure manageable, one has to con-
fine oneself to an impact paramet er b = 0, thus enforcing cylindrical sym-
met ry about the beam direction and keeping the problem at two dimensions
in space [BEG83, ThB92]. While this choice of the impact paramet er carries
zero weight for the cross section, it is instructive to study this particular
case.
Since the t raj ect ory passes right t hrough the singular points of the
Coulomb potentials, it is necessary to replace the Coulomb potentials in
Eq. (5.40) by nonsingular potentials produced by a finite-size nucleus. The
simplest choice for the nuclear charge distribution is a homogeneously
charged sphere with radius R0, separately fixed for the target and the pro-
jectile nucleus. In other words, one has to substitute in Eq. (5.40) for bot h
collision partners
1 / r for r _> R0
1 fo(r) (6.54)
P 1( 3- r2/ R~))/ Ro for r < Ro
Figure 6.11 conveys a vivid picture of the time development of the prob-
ability distribution for U 92+ + U 91+ collisions at 10 GeV/ u [ThB92]. In
the calculations leading to these results, a grid of 600 300 meshes with
a spacing of 4.6 -2 a K = 26.5 fm (where a K is the urani um K-shell
radius) is used. The nuclear radius R0 is arbitrarily chosen to be twice
this amount in order to guarantee the stability of the numerical procedure.
The calculations are initialized at the time t = - 8 . 5 [in nat ural relativistic
units to = h/ (rnec 2) = 1.28 x 10-21s], when the projectile has a distance of
about 5.7 a K = 3.3 x 10 -~ ~ cm from the target. At to, the density of the
electron distribution is assumed to be determined by the unperturbed ls
1/2
ground state of U 91+. Figure 6.11 shows the electron density at t - - 8 . 0
and separation 5.4 a K. At the next stage, t = 0, when the nuclear charge
distributions completely overlap, the density distribution still is almost un-
altered. The main change takes place while the projectile recedes and leaves
the target at om behind, at a separation of about 4a K at t = 6 and of about
7.3a K at t = 1-1. The numerically calculated wave functions can be pro-
jected onto exact target eigenstates and thus be analyzed with respect to
their content of various excited and continuum states.
While these calculations are very instructive in permi t t i ng one to visu-
alize the collision process, they are not sufficient to calculate cross sections.
166 C H A P T E R 6. E X C I T A T I O N A N D I O N I Z A T I O N
In Sec. 6.1 it is also shown t hat it is not realistic to assume t hat in the en-
trance channel the target wave function is still unpert urbed at a projectile
separation of 5.7 a K. In reality, owing to the long range of the Coulomb in-
teraction, changes in the target wave function start to accumulate when the
projectile is still a distance of (500-2000)a K away [ToE88b], see Fig. 6.12.
Unfortunately, numerical calculations on a discretized grid within such a
large time span are presently hardly possible.
Following the arguments outlined in Sec. 6.1.2, one may expect a much
bet t er convergence if one uses a phase-distorted wave function (5.62) for the
initialization of the time evolution and, correspondingly, the short-range
interaction occurring in Eq. (6.9).
6. 5 T w o - c e n t e r c o u pl e d- c ha nne l m e t h o d s
The direct solution of the time-dependent Dirac equation (5.39, 5.40) in
the l aborat ory frame on a discrete space-time grid is still not feasible with
sufficient accuracy for a general collision geometry. However, one may solve
the problem within a limited space of basis functions. For this purpose, one
expands the wave function ff~(rT, t) in terms of a suitable set of basis states
r t). The degree of approximation then is essentially determined by
the choice and the t runcat i on of the basis set. A basis set embracing the
most i mport ant reaction channels should not only allow for excitation and
ionization but also for charge transfer.
In this section, we discuss two-center coupled-channel calculations, and
proceed to single-center coupled-channel methods in Sec. 6.6. Both methods
are based on the same idea, namely an expansion of the time-dependent
wave function in terms of atomic orbitals. In the former, more symmetrical
approach, one uses a subset of basis functions centered around the target
and another subset centered around the projectile nucleus. In the latter
method, which is computationally simpler, the basis functions are attached
only to the target nucleus, with the projectile merely acting as a source of
perturbation.
6. 5. 1 Coupl ed- channel e qua t i ons
A t reat ment of the time-dependent Dirac equation (5.39, 5.40) for relativis-
tic ion-atom collisions requires the expansion of the time-dependent wave
function ~ ( r T, t) in terms of target and projectile eigenstates Ck(rT, t) and
~Pk,(r~, t' ), respectively, as
9 (rT, t) -- E ak( t ) ~ k( rT' t) + E ak, (t ) S-l~Pk, (r~ , t' ), (6.55)
k k'
6. 5. T WO - C E N T E R C O UP L E D - C H A N N E L ME T H O D S 167
where we have referred the total wave function to the laboratory system.
The first sum represents an expansion in terms of target states; the second
sum is an expansion in terms of projectile states originally defined in the
projectile system and subsequently transformed to the laboratory system
with the aid of the operator S -1 defined in Eqs. (4.29) and (4.31).
The use of two centers for the expansion of the wave function 9 (r, t) has
three i mport ant implications: (a) In the interaction region, linear combina-
tions of atomic orbitals around the target and around the projectile nucleus
provide flexibility to approximate transient molecular orbitals which may
play a role during the collision. (b) Charge transfer is explicitly included as
a reaction channel. This not only renders charge exchange at all possible,
but also will affect other reactions by entering as an intermediate state. (c)
Specifically, ionization of an electron may occur as a direct ionization of the
target at om as well as capture into the continuum of the projectile. In this
way, one will get a better representation of the true continuum by a finite
set of basis states.
In fact, the only approximation within the met hod consists in the re-
striction to a finite set of atomic basis states. Since each of the atomic
basis sets is truncated, there is no problem with overcompleteness t hat
would arise from two complete (or nearly complete) sets. In practical cal-
culations [ToE88a, ToE88b], basis sets have been confined to 20 or 36 sub-
states, namely those of the lsl/ 2, 2Sl/ 2, 2Pl/ 2 , 2P3/2 , 3Sl/ 2, 3Pl/ 2 , and
3p3/ 2 shells. The use of exact hydrogenic eigenstates calculated from Eqs.
(4.86) and (4.98) guarantees t hat the atomic basis functions attached to
the s a me center are orthogonal in b ot h the target frame and the projectile
frame according to Eqs. (4.41) and (4.44). This would no longer be true for
variational wave functions or basis states obtained by diagonalization in o ne
of the two frames. The difficulties associated with pseudostate calculations
are discussed in Sec. 6.5.3.
In Eq. (6.55) the Lorentz transformation of the time factor [Eq. (4.45)1
included in the projectile states automatically implies the relativistic court-
t erpart s of the nonrelativistic translation factors, see Eq. (1.6).
C o up l e d e q ua t i o ns
In order to determine the time-dependent expansion coefficients ak and ak,
in Eq. (6.55), we have to insert ~ ( rT, t ) into the Dirac equation (5.39).
Observing t hat the atomic eigenfunctions satisfy
H - i h 0 ) _ _ S 2 Z p e 2
a t ~?k , ~ k , ( 6 . 5 6 )
r p
168 C H A P T E R 6. E X C I T A T I O N A N D I O N I Z A T I O N
and using Eq. (5.42), we get
0 ) ZTe2 s- l ~ ) k ,. (6.57)
H - i h - ~ s- l ~ 2 k , - -
With these two relations, the time-dependent two-center Dirac equation can
be rewritten as a set of coupled differential equations for the occupation
amplitudes ak(t ) and ak, (t ) . Combining the amplitudes into a column vec-
tor a = ( a k , ' ' ' ; ak , , ' " "), we may write the coupled equations in a compact
matrix form as
i h N 5. = V a (6.58)
or
i N -1 (6.59)
5_- ~ Va.
The overlap matrix N and the interaction matrix V are each built from four
submatrices corresponding to target-target, target-projectile, projectile-
target, and projectile-projectile transitions.
The overlap matrices are
N~k
N~k,
Ni,k
Ni' k'
' - ~ i k
= i ~ (r w) S- - l ~ k ' (r ~ p ) e i ~ E k ' (~ / h ~ 2 ) z T d3rw e- i (~Ek' - E~) t / h
v . J
= [~ ,(r}' )s-lqDk(rT)e--i~ E~ ' (' / h~ 2)zT d3rw e--i(Ek--~E~')t/h
, J
= 5i, k,. (6.60)
The last equation, valid for exact atomic eigenstates only, is derived in
Eq. (4.44). The single-center overlap matrix elements (target-target and
projectile-projectile) are time independent while the two-center matrix el-
ements (target-projectile and projectile-target) are time dependent owing
to the relative motion of the collision partners.
In analogy to the overlap, we have four types of interaction matrix
elements, namely
V~k
/ r (rT) ( - $2 ZPe2 ) . ~k (rT) d 3r T e - i (E k - E i ) t / h
rp
V~k,
/ qp~ ( rT) ( S - 1 Z T e 2 ) (v/h~2)ZT
-- ~k, ( r~ ) e i~Ek' d3rw
?~T
X e - i ( ~ / E k ' - E i ) t / h
6.5. TWO- CENTER COUPLED-CHANNEL METHODS 169
V~,k
J p ~ , ( r 1 p ) ( - S ZPe2 )
, 99k(rw) e - i ' T E i ' ( v/ h c 2 ) z w d 3 r w
r p
e - - i ( E k - - y E i , ) t / h
Vi' k'
f f ~ , (r p) ( - S -2Zwe2 )
' r (r~ ) e - i ~ / ( E k ' - E i ' ) ( v/ h c 2 ) z w d3rT
?~T
X e - i ~ / ( E k ' - E i ' ) t / h . (6.61)
One verifies t hat in the nonrelativistic limit, all matrix elements merge into
the corresponding nonrelativistic expressions including translation factors.
As long as the expansion (6.55) is not truncated, the set of coupled equa-
tions (6.59) is equivalent to the original two-center Dirac equation (5.39).
The choice and the t runcat i on of the basis set constitutes the only approxi-
mation made in solving the problem. Of course the t runcat i on implies t hat
some of the symmet ry properties of the original Dirac equation get lost in
the coupled-channel equations. Wi t h an incomplete basis set, Eq. (6.59)
is neither Lorentz invariant nor gauge invariant. An explicit numerical
example for the loss of gauge invariance is given in Sec. 6.5.4.
Initial conditions
In order to actually solve the coupled equations (6.59), one has to specify
the initial conditions. If we assume t hat the target electron is initially in
the state k0, we have
ako(t ~ - oc) = 1
ak(t - - - , - oc) = 0
ak, (t - - ~- ec) = 0
for k C ko
(6.62)
Equat i on (6.60) shows t hat an expansion in terms of atomic eigenfunc-
tions has the advantage t hat at asymptotic separations, i.e., for t ~ +oc,
all basis states are mutually orthogonal. This means t hat the expansion
coefficients ak, ak, can be interpreted unambiguously as occupation ampli-
tudes in this limit. In particular, there is no overlap with the negative-
energy continuum which might lead to spurious results if there were a finite
overlap. In the interaction region, where target and projectile states are
nonorthogonal, and where each bound state of one center has some overlap
with bound states and positive- as well as negative-energy continuum states
of the other center, an interpretation in terms of probability amplitudes is
170 C H A P T E R 6. E X C I T A T I O N A N D I O N I Z A T I O N
not needed. It suffices t hat the overlap mat ri x (6.60) is rigorously taken
into account.
C r o ss se c t i o ns
The final probabilities are
P k (b ) = ]ak(t --* ~ ) ] 2 for excitation (6.63)
and
P k , ( b ) = l a k , ( t ~ oc)l 2 for charge transfer. (6.64)
The integrated cross section for exciting state k from the initial state k0
according to Eq. (5.65) is given by
~k - 2~ P ~( V) b db ( 6.65)
while for transfer, k is replaced with k ~.
N ume r i c a l p r o c e d ur e
The main numerical task consists in evaluating the mat ri x elements defined
in Eqs. (6.60) and (6.61). In contrast to the analogous nonrelativistic
problem, there is no symmet ry about the internuclear axis because of the
Lorentz contraction in the beam direction. A fully numerical integration is
required.
The details of the numerical procedure are discussed in [ToE88b]. The
task is facilitated by a symmet ry relation
N ~ z ( t ) - ( - 1) z~ +l~ +"~ +"~ +l N ~ z ( - t ) (6.66)
for the overlap mat ri x and a corresponding relation for the potential ma-
trix elements, where a,/ ~ denote any of the labels i, k, i ~, k ~ and l~ ' z are
the orbital angular moment a for the large components of the states c~,/3,
c~,/3 1
while #j are the projections of the total angular moment a j - 1A 4- -~.
Est i mat i ng the radius of the interaction region by 4 = 4a o / ( Z w + Zp), the
limits of time integration are extended to Ivtl < 250 4, and, when needed
for convergence, to 500 4 or 1000 4. Beyond Ivtl = 20 4, the two-center
mat ri x elements are negligibly small, so t hat only single-center mat ri x ele-
ments have to be calculated. Since the calculation of the mat ri x elements
takes the overwhelming part of the computing time, it is convenient to solve
the coupled time-dependent equations simultaneously with all the different
initial conditions t hat might be of interest.
6. 5. T WO - C E N T E R C O UP L E D - C H A N N E L ME T H O D S 171
6 . 5 . 2 Ap p l i c a t i o n t o U 9 2+ -+- U 9 1+ c o l l i s i o n s
For the collision of U 92+ ions with U 91+ t arget s at 0.5 and 1.0 GeV/ u,
experimental dat a are not available but, on the other hand, the collision is
well suited to serve as a model case for which effects of relativistic electron
and relativistic projectile motion can be studied. According to Fig. 5.1,
the mat chi ng energy for lSl/ 2 electrons is 240 MeV/ u, so t hat at least for
500 MeV/ u we still have rat her "slow" relativistic collisions for which the
two-center coupled-channel met hod is most appropriate.
Figure 6.12 shows some results for the time evolution of the occupation
probabilities for t arget states (excitation) and projectile states (charge
transfer) for the impact energy of 500 MeV/ u using 36 atomic basis states
up to the 3p3/ 2 shell of t arget and projectile and assuming an impact pa-
ramet er of 0.01 a.u. This distance is approxi mat el y equal to the K-shell
radius a N and roughly corresponds to the region of maxi mum contribution
to the excitation cross section, see Fig. 6.13. The interval I vtl <<_40 aK,
displayed in Fig. 6.12, represents a narrow window out of the total time
range I vtl < ( 50 0 - 2000)aN actually t reat ed in the calculation.
In conjunction with the time developments shown, it should be noted
t hat the i nt erpret at i on of the expansion coefficients as probability ampli-
tudes near t = 0 is only approxi mat el y valid because of the nonorthogo-
nality in the reaction zone of basis states belonging to different centers.
Therefore a transient " probability" exceeding unity occurs in Fig. 6.12(a).
All figures reveal certain qualitative features: (a) The i mport ance of
multistep processes is shown by the rapid fluctuations of some of the occu-
pation probabilities. (b) Electron transfer, bot h during the collision as well
as in the exit channel, is comparable to excitation and cannot be neglected.
(c) Wi t h increasing shell size, the interaction region extends much farther
out, see Fig. 6.12(b). (d) In this t reat ment , certain target states are af-
fected by the projectile long before and long after it reaches its distance of
closest approach at t = 0. In Sec. 6.5.4, we come back to these long-range
couplings, also observed for first-order pert urbat i on theory in Fig. 6.1.
Figure 6.13 shows weighted excitation and transfer probabilities P ( b ) b
for the leading transitions as a function of the impact paramet er b. As
already apparent from Fig. 6.12, the probabilities for excitation reach out
to much larger impact paramet ers t han for transfer. A particular role is
1 1
played by the spin-flip transition ls 1/2 (~ ) --~1Sl/2 ( - ~)" Being degenerate
within the coupled-channel t reat ment , the two states are strongly coupled
even at large impact paramet ers so t hat the total cross section diverges
logarithmically. This divergence is spurious and can be remedied by in-
cluding higher-order QED corrections or hyperfine interactions removing
the degeneracy.
172 C H A P T E R 6. E X C I T A T I O N A N D I O N I Z A T I O N
1 . 0
10-1
10- 2
10- 3
10 -~,
1 0 - s
-,- 1 . 0
o 1 0 - I
..l=l
0
1 ..
10- 2
t -
O
:E. 1 0 - 3
0
~, 10- l,
o
1 0 - s
1 . 0
+ ( a )
l S l / 2 ,
U 9 2 * + U 9 1 +
2Si+/2 l s ~2
e x c i t a t i o n ,i/
3 +
U 92 ++U 91+ ( b )

2 S l / 2
2P31
4 -
]PI12
4-
/3 s~12
c h a r g e t r a n s f e r ( c )
1 0 - ' I. ls1"~2
[ 2S~/2 / S l/ 2
10 -2
10- 3
10- ~
1 0 - s
-0.1+ -0.2 0.0 0.2 0.~
vt(a.u.}
Fi gur e 6. 12. Time evolution of the occupation probabilities of target states in
excitation and of projectile states in charge transfer in U 92+ + U 91+ collisions at
500 MeV/ u laboratory energy and impact paramet er b - 0.01 a.u. ~ a K. The
abscissa plotted is the projection of the projectile-target separation on the beam
direction. The projection of the angular moment um is indicated by + , - , and + +
for pj ---- 2'1 2' 1 and ~,3 respectively. (a) Excitation from an initial lSl/ 2 state;
(b) excitation from an initial 2Sl/2 state; (c) charge transfer from an initial lSl/ 2
state. Adapted from [ToE88b].
6 . 5. T WO - C E N T E R C O UP LE D - C H A N N E L ME T H O D S 173
d
o
1.0
0.5
I 1 I I i I I
- 2 S l l 2 U 9 2 " + U 9 1 -
/ ' X 500MeV/ omu
/ \ exci tati on
lS l/2(-1/2)
.c_
C L
1.0
0.5
0.0
I I I I I I
/ " ~ t o t al
/ \ charge transf er
_ / / ~ S l j z ( 1 1 2 )
I
0.05
i mpact parameter b (a.u.)
Fi gur e 6.13. Weighted excitation and capture probabilities P(b) b for U 92+ ql_
U 91+ (lSl/ 2) collisions at 500/ u MeV laboratory energy as a function of the impact
parameter b. Only the leading probabilities into specific final states nlj(#3) are
plotted. From [ToE88b].
For detailed st at e-t o-st at e cross sections wi t hi n a 36-state fully rela-
tivistic coupled-channel t r eat ment of 500 MeV/ u U 92+ + U 91+ collisions
see [ToE88b, Eic90].
6. 5. 3 P s e udos t a t e s f or t he c ont i nuum
The coupled-channel t r eat ment discussed in the preceding subsections uses
a basis of bound states in the t arget and the projectile at om and hence is
confined to excitation and charge transfer into bound states. However, in
order to describe ionization processes on the same footing as excitation and
capture, it is mandat or y to include t arget and projectile cont i nuum states
in the basis set. It is known from nonrelativistic collisions [FrL91] t hat by
174 C H A P T E R 6. E X C I T A T I O N A N D I O N I Z A T I O N
augment i ng the atomic orbital expansion by appropriate " pseudostates"
at t ached to target and projectile, one may simulate intermediate and fi-
hal continuum states and at the same time improve the representation of
molecular states at small internuclear separations. P seudost at es are arbi-
t rary basis functions chosen so as to improve the flexibility of the basis set
in approxi mat i ng the true two-center wave function t hroughout the colli-
sion. Not being eigenstates of the unpert urbed atomic Hamiltonian, pseu-
dostates, if properly chosen, have an overlap (a) with bound highly excited
atomic orbitals not explicitly included in the basis set, (b) with atomic or
molecular continuum states, and (c) with uni t ed-at om wave functions (for
R = 0 and Z = ZT + Zp) needed to improve the representation of molecular
orbitals. This met hod is a powerful tool for simultaneously describing exci-
tation, ionization, and charge transfer in nonrelativistic collisions [FrL91].
For relativistic collisions, see [ToE89].
The use of approxi mat e wave functions such as pseudostates to describe
relativistic collisions entails two problems t hat are absent in the nonrela-
tivistic situation. One of t hem is the occurrence of negative-energy states
arising from the Dirac theory for the relativistic electron motion. The other
one is the loss of the orthogonality propert y of approxi mat e eigenfunctions
under Lorentz transformations.
Negative-energy components
We first address the problem of negative-energy components in pseu-
dostates. The Dirae equation, while formally appearing as a single-particle
equation, is fully interpretable only if considered as an equation for the
field operator, see Sees. 4.2.2 and 5.1. As a consequence, many-el ect ron-
many-posi t ron systems are equally represented by the same equation. For
most applications in atomic and molecular physics, however, we wish to
confine ourselves to a system with a fi z ed number of electrons. Therefore,
one wants to avoid " negative-energy solutions" of the Dirae equation, t hat
is solutions with eigenvalues E < - r nec 2 (defining E = rnec 2 for a free
electron at rest). Indeed, for variational problems, negative-energy solu-
tions may always occur since the Dirac Hami l t oni an is not bounded from
below. In spite of these problems, techniques have been developed to avoid
negative-energy states and to perform reliable relativistic many-electron
calculations for atoms and molecules. The most i mport ant feature com-
mon to many of the recipes appears to be t hat the ratio between upper and
lower Dirae components has to be fixed to a reasonable value and is not left
open to variation. It is thus a pragmat i c procedure to augment the set of
exact Dirae eigenstates as basis functions in a linear variational procedure
by hydrogenie wave functions in Eq. (6.55) generated by effective charges
6. 5. T WO - C E N T E R COUPLED- CHANNEL ME T HODS 175
Z* , see e.g. [TOE89, Eic90].
Loss of orthogonality
When pseudostates are included in the basis set, a difficulty arises in the
calculation of overlap and potential matrix elements t hat is peculiar to
relativistic projectile motion. As discussed in See. 4.1.4, the operator S
represents a Lorentz transformation only for rigorous eigenstates and rep-
resents an approximate Lorentz transformation for approximate eigenstates
such as those obtained by diagonalizing the single-center Hamiltonian ap-
pearing in Eqs. (5.53) and (5.54) in a basis containing pseudostates. For
example, approximate projectile eigenstates which, by construction, are or-
thogonal in the projectile system are no longer orthogonal in the target
frame, in which the collision is described. This means t hat the last of Eqs.
(6.60) is no longer valid, and instead, we have in the target system
- ~i' k' if i/, k / are bot h real states (6.67)
Ni,k, ~: ~i' k' if at least one of i ~, k ~ is a pseudostate
A similar relation holds for the Hamiltonian matrices. For example, if
the projectile Hamiltonian has been diagonalized in the projectile frame,
only the submat ri x spanned by real states remains diagonal under Lorentz
transformations.
The loss of the diagonal property of overlap and Hamiltonian matrices
under Lorentz transformations poses serious problems to calculation and in-
t erpret at i on within a framework of coupled channels involving pseudostates.
Then, no mat t er whether the projectile Hamiltonian is diagonalized in the
projectile or in the target frame, an observer in the target frame will always
find t hat for t -+ oc the coupling matrix ( H ~ - i h o Nv) in the projectile frame
is nondiagonal and hence the occupation amplitudes keep oscillating among
the various projectile basis states. Such a behavior is physically meaning-
less. Several approximate ways to treat these problems are discussed in
[TOES9]
The loss of orthogonality is generally unavoidable if basis states are used
t hat are not eigenstates of target or projectile Hamiltonian. Discretized
wave packets for the continuum, see See. 6.6.1, are expected to give rise to
similar problems.
6. 5. 4 Long- range coupl i ngs and Coul om b boundary
condi ti ons
In Figs. 6.12(a) and (b) we present calculated results for U 92+ + g 91-k col-
lisions which exhibit long-range couplings among the excited target states.
176 C H A P T E R 6. E X C I T A T I O N A N D I O N I Z A T I O N
In this subsection, we analyze this effect and show how to remove it. The
anomalous long-range couplings are of relativistic origin and are absent in
nonrelativistic coupled-channel calculations.
According to Eqs. (6.56) and (5.97), the interaction leading to target
excitation is
s2zP e2 [ 1 bxT+ 2v zT l
r~ =' YZPe2(1 - / 3az) ~oo + (R;) 3 + " " (6.68)
where R~o - (b 2 +~/2v2t2)l/2 and higher multipole terms have been omitted.
The main term in (6.68) giving rise to long-range couplings between initial
and final states is the term proportional to ~ a z / R ~ o , which is of magnetic
origin; for a more detailed analysis, see [ToE886, ToE88b].
Ba si s st a t e s sa t i sf yi ng C o ul o mb b o und a r y c o nd i t i o ns
In coupled-channel calculations, the choice of the basis states is a matter
of convenience, both for the desired interpretation of the results and for
the ease of calculations. In Eq. (6.55), we have chosen the conventional
view t hat the basis states are stationary atomic orbitals. In light of the
discussion above, it appears more appropriate to use a set of basis states
t hat satisfy Coulomb boundary conditions (5.61) and (5.62). We therefore
replace Eq. (6.55) with the expansion [ToE90b]
~ ( r T' t ) -- E a k ( t ) e - i up l n( R ' - vt ' ) ~ ) k ( r T ' t )
k
+ E a k , ( t ) e i UT l n ( R + v t ) s - l c k , ( r t p , t ' ) . (6.69)
k~
The first term represents an expansion in terms of target states asymptoti-
cally phase-distorted by the projectile, while the second sum is an expansion
in terms of projectile states asymptotically phase-distorted by the target.
When writing down the equations corresponding to (6.56) and (6.57), we
find t hat on the right-hand side, the time differentiation of the logarithmic
phase factors yields additional terms so that we get the replacement
Z p e 2 Z p e 2 Z p e 2
.._.+
' R ' r ~ r p
Z T e 2 Z T e 2 Z T e 2
- - . (6.70)
r T r T R
The phase factors themselves drop out in the one-center integrals since they
are state independent, but they remain in the two-center integrals. Wi t h
6.5. T WO - C E N T E R C O UP LE D - C H A N N E L ME T H O D S 177
these substitutions it is obvious how to modify the overlap matrix elements
(6.60) and the potential matrix elements (6.61). We emphasize t hat the
multiplication of the basis states with a phase factor and the simultaneous
replacement (6.70) of the interaction simply constitute a gauge transforma-
tion.
It becomes apparent t hat with the basis expansion of (6.70), the long
range of the Coulomb interaction is explicitly taken into account and hence
the long-range couplings discussed in See. 6.5.2 disappear. Indeed, if the
replacement (6.70) is inserted into the left-hand side of Eq. (6.68) the term
1/R~o in the square brackets responsible for these couplings is cancelled.
E l i mi nat i on of long-range couplings
The elimination of the long-range couplings by a suitable gauge transfor-
mation is illustrated in Fig. 6.14. Here, the time evolution during a U 92+
+ U 91+ collision at 1 GeV/ u is shown for the occupation probabilities of
the target states. The impact parameter is 0.01 a.u. or about one uranium
K-shell radius. Unpert urbed basis states (6.55) are used in the upper part
of the figure, while the lower part is obtained for boundary-corrected basis
states (6.69). Here, the long-range couplings visible for unpert urbed basis
1 1
states have disappeared. The 2P3/2( 89 2Pl/2(~), 3P3/ 2(~), and 3P1/2(89 )
states t hat are excited for unpert urbed states already long before the dis-
tance of closest approach is reached begin to be populated for boundary-
corrected basis states only at about vt = - 10 a K. Similarly, after the col-
lision, the boundary-corrected basis states attain their asymptotic occupa-
tion probabilities at much smaller values of vt t han the unpert urbed basis
states. Most importantly, the asymptotic values themselves are changed, in
sharp contrast to the Born approximation discussed in See. 6.1.2. A similar
behavior has been confirmed for single-center calculations [ToE90b]. Gen-
erally speaking, Fig. 6.14 explicitly illustrates t hat for an incomplete basis
set the coupled-channel equations (6.59) are not invariant with respect to
gauge transformations.
One can conclude t hat for relativistic single-center and two-center coupl-
ed-channel calculations with unpert urbed basis states, the coupling among
states is of long range and acts long before and long after the encounter
takes place, while for basis states satisfying Coulomb boundary conditions,
the couplings are localized around the distance of closest approach. How-
ever, in contrast to the Born approximation, Sec. 6.1.2, where there is no
backcoupling, the multiple couplings occurring in a coupled-channel calcu-
lation eventually lead to transition probabilities and cross sections t hat are
distinctly different for unpert urbed and boundary-corrected basis states.
This shows t hat it is mandat ory for a description of direct reactions to take
17 8 C H A P T E R 6. E X C I T A T I O N A N D I O N I Z A T I O N
1 . 0
10 -1
1 0 - 2
> , 1 0 - 3
o 10 -4
o
c. .
o . l O - S
t -
O
o 1.0
C3.
L.J
1 0 -1
1 0 - 2
1 0 - 3
1 0 - 4

1 G e V l u l s l l 2
u ? Z + + u 9 1 +
u n p e r f u r b e d
+
3 s v
2 s L , \
2 s 1+1z 2 P ; / 2
- / -
~ c l s t / z
" 3 s ~ ' /2
l s *
1 1 2
J
lo-' -o.2 o.o o.2 o'.,
b 0 u n d a r y - c 0 r r e c f e d
3 P ~ / z
, 2 ~ 3 / z - - - ~ , / R I I , ,
v t ( a . u . )
" 2 p~ '/2
F i g u r e 6. 14 . T i m e evol uti on of the occupati on probabilities of target states
in U 9 2+ + U9 1+( 1s1/ 2 ) collisions at 1 Ge V/ u l aboratory energy. Cal cul ati ons
are perf orm ed w i th 18 hydrogenic basis states at each of target and proj ectile
and f or an im pact param eter b - 0. 01a. u. T he upper set of curves represents
results obtai ned f rom unperturbed basis states ( 6. 55) , w hile the low er set of curves
corresponds to boundary-corrected basis states, Eq. ( 6. 69 ) . For the notati on, see
Fig. 6.1. From [ T oE9 0b] .
care of the long-range Coulomb interaction from the beginning. It is to be
expected t hat this al so i m proves the convergence behavior with res pect t o
the number of bas i s s t at es .
6 . 6 S i n g l e - c e n t e r c o u p l e d - c h a n n e l m e t h o d s
While two-center coupled-channel calculations have the merit of allowing
f or charge exchange, one obt ai ns great simplifications in a single-center
coupled-channel calculation, where one regards the projectile merely as the
s ource of a time-dependent electromagnetic field. In this way, one di s cards
6. 6. SI N GLE - C E N T E R C OUP LE D- C HA N N E L ME T H O D S 179
charge exchange not only as a final but also as an intermediate channel
and moreover does not permi t the formation of transient quasimolecular
states. On the other hand, by renouncing a second set of basis states and
the associated complications, one may handle larger sets centered around
the t arget and carry the calculations to higher energies.
By dropping the projectile-centered expansion in Eq. (6.55), we may
write
9 (rT, t) -- Z ak(t)~ bk(rT' t), (6.71)
k
where the Ok(rT, t) = pk( r T) e xp( - i Ekt / h) are mut ual l y orthogonal and
normalized bound-st at e and continuum ( E > rnec 2) wave functions. This
means t hat in each of Eqs. (6.60) and (6.61) only the first lines apply, in
particular one gets rid of the unpleasant t i me-dependent overlap terms.
Dropping the primed terms, the initial conditions (6.62), the expressions
for the probability (6.63), and the cross section (6.65) are valid in exactly
the same way.
6. 6. 1 Wa ve pa c ke t s f or t he c ont i nuum
The main problem of all coupled-channel calculations consists in t reat i ng
the continuum. In Sec. 6.5.3, we discuss pseudostates. Another met hod
which allows one to underst and bet t er which part of the continuum is
included is provided by the use of discretized continuum wave functions
constructed as superpositions of continuous eigenstates.
Weyl wave packets
One first segments a certain energy range of the continuum into finite in-
tervals centered around Ek and with the width AEk. By integrating the
exact continuum wave function 7) E e xp ( - i E t / h ) over the energy interval
A E k , one obtains Weyl wave packets in the form
~ Ek ( rT, t) -- 1 fEk+/XEk/2
v/ A E k JEk--/XEk/2 FE (r T ) e - i (E - E k ) t / h dE. (6.72)
These wave packets travel radially into the reaction region for t < 0 and
- - 2C4) 89 [HeG81,
outwards for t > 0 with a peak moment um Pk (E~ - rn e
MeR85]. Since the continuum wave functions are normalized on the energy
scale, see Eq. (4.117), and the energy intervals AEk belonging to different
discretized states do not overlap, the Weyl wave packets are orthonormal,
t hat is
/ ~ k ( rT' t)~ Et ( rT' t) ~k,1.
d3rT (6.73)
180 C H A P T E R 6. E X C I T A T I O N A N D I O N I Z A T I O N
go
E
0
o ~
(D
E
~ L
0 . 2
0 . 0
- 6 - 0 . 2
- 0
0
r Y
- 0 . 4
E0 = 2 . 5
lil lililil liflil:
Nl l U v :
0 2 0 4 0 6 0
R( ]d i ( ]l c o o r d i n a t e r
Fi gur e 6.15. The radial components G(r) = r g(r) and F(r ) = r f ( r ) of rel-
ativistic wave packets in relativistic units (h = c = me - 1) versus the radial
coordinate r. The s-state (a -- - 1) with the total energy E0 = 2.5 for Z = 82
is considered. The integration over continuum states is performed assuming a
width of AE = 0.3.
On t he ot her hand, t hey are no exact solutions of t he t ar get Dirac equat i on.
St a t i o na r y wave pac k e t s
If one superi mposes not t i me- dependent but st at i onar y cont i nuum solutions
of t he Dirac equat i on, one obt ai ns st at i onar y wave packets, see e.g. [BaS85],
~Ek (rT, t ) = ~Ek e x p ( - i E k t / l i ) , where
1 f E k + A E k / 2
~Ek (rw) -- v/ AE k J Ek-AEk/ 2 ~ P E( rT) dE. (6.74)
Owi ng to t he superposi t i on of adj acent cont i nuum functions, t he fall-off of
t he radi al wave funct i ons g (r ) and f ( r ) is much faster t han t he decrease 1 / r
of t he funct i ons g (r ) and f ( r ) themselves, see Fig. 6.15. In t he eval uat i on
of mat r i x el ement s cont ai ni ng t hese wave packets, it is somet i mes necessary
to t ake slowly varyi ng quant i t i es out si de of t he energy integrals.
Ga ussi a n wave pac k e t s
As is known from quant um chemistry, it is often advant ageous to expand
6.6. S I N G L E - C E N T E R C O UP L E D - C H A N N E L ME T H O D S 181
atomic or molecular orbitals in terms of Gaussian-type orbitals ( GTO)
(~z) e-~"~2 rZYl.~ (~), (6.75)
99n/rn(r) = E cu
v
where the solid harmonics rIYlm(~) are written in Cartesian coordinates,
and the Gaussian width parameters are chosen in a suitable (e.g., geometric
progression). It is the merit of this expansion t hat the single-center and
multi-center matrix elements entering in the Hamiltonian matrix can be
evaluated analytically. Collision problems, however, demand the accurate
numerical calculation of a complex auxiliary function defined as a one-
dimensional integral, which arises from the complex oscillatory factors in
Eqs. (6.60) and (6.61). It has been shown [TOE91, TOE92] t hat the method
of GTO wave packets is very powerful in nonrelativistic coupled-channel
calculations, even for energetic collisions when high-lying continuum states
are needed. The Cartesian decomposition, which comes naturally with
the GTO method, should be particularly appropriate for relativistic colli-
sions, where, because of the Lorentz contraction, the z-coordinate has to
be treated separately. Actual calculations have not yet been performed.
6. 6. 2 Nu m e r i c a l r e s ul t s
In order to solve the coupled equations (6.59), where N is the unit matrix
for a single center with orthogonal basis states, one evaluates the cou-
pling matrix elements (6.61) (first line only). Instead of a direct numerical
quadrature, one may use the multipole decomposition discussed in See. 6.3.
Adopting the multipole expansion in momentum space, See. 6.3.2, and
Weyl wave packets (6.72), Becker [Bec86] considered collisions of Zp + U
at 1 GeV/ u and b = 0. The calculated differential cross sections for K-shell
ionization are very close to the corresponding cross sections calculated in
first-order perturbation theory (see See. 6.3.3). However, for higher pro-
jectile charges (see Fig. 6.16), the calculations show t hat the cross sections
do not scale anymore with Z~ as they do in perturbation theory and hence
do not coincide in the diagram. All these calculations require considerable
computer time and cannot be easily extended to arbitrary impact parame-
ters in order to provide complete cross sections.
More extended calculations of excitation and ionization cross sections
in collisions of Zp + U 9~ at 430 MeV/ u and of Zp + X e 52+ at 82 MeV/ u
are performed by Momberger et al. [MoG90] within a one-center coupled-
channel formalism. While there is good qualitative agreement with the
experimental data, discrepancies at small values of Zp/ ZT still remain, see
Fig. 7.6 for projectile ionization. Differential ionization cross sections are
calculated in [MoG89].
182 C H A P T E R 6. E X C I T A T I O N A N D I O N I Z A T I O N
10 -31 Zp+U I
- I
10-s
e , , i
u
i =
e ~
N I O_ L , _
1.0 1.S 2 .0 2 .5
Ef (m c z )
Fi gure 6.16. Differential K-shell ionization probabilities in Zp + U collisions,
divided by Z~, at 1.0 GeV/ u and b - 0 versus the energy of the ionized elec-
tron. The curves are obtained from coupled-channel calculations by Becker et al.
[BeG87b].
N o np e r t ur b a t i ve b eh avi or at ve r y sma l l i mp a c t p a r a me t e r s
Figure 6.16 and the earlier discussions reveal t hat single-center and two-
center coupled-channel calculations yield significant deviations from the
results of pert urbat i on theory, Sec. 6.1. These deviations are expected to
be largest if the interaction is extremely strong, t hat is, for high-Z colli-
sion partners at very small impact parameters close to the limit of grazing
collisions between the nuclei.
In order to investigate this interesting behavior, Rumrich et al. [RUM91,
RuS93] have performed single-center coupled-channel calculations using sta-
tionary wave packets (6.74) for describing electronic continuum states (and
also positron states, see Sec. 10.2.3) and a multipole decomposition of the
interaction in coordinate space, see Sec. 6.3.1. Since they start from the
expansion (6.71) without boundary corrections (Sec. 6.5.4), they introduce
a damping procedure to avoid the time oscillations of the occupation ampli-
tudes at the internuclear separation where the initial conditions are speci-
fled.
In part of their calculations, they include negative-energy basis states.
The basis includes continuum states between 1.1 and 3.5 me c 2 and angular
moment um quant um numbers ~ bet ween- 2 and +2. It is found t hat for
the system Zp + P b sl+ at the bombarding energy of 1.2 GeV/ u and impact
6. 6. S I N G L E - C E N T E R C O UP L E D - C H A N N E L ME T H O D S 183
1 . 5
' 1 . 0
O

S
' - ' 0 5 ~
0.0
' I ' I ~ I '
: . . . - - ' " " ' - - . . . . . ~
-. . .
.~
' I
l , l , I l I J I i I
2 0 40 6 0 8 0 1 0 0 1 2 0
Zp
Fi gur e 6.17. lSl/ 2 and 2Sl/2 ionization rates versus Zp for the system Zp
P b 81+ at an impact parameter of b - 20 fm. The notation is: D, lSl/ 2 ionization
for 0.5 GeV/ u ; O, lSl/ 2 ionization for 1.2 GeV/ u; and / k, 2Sl/2 ionization for
1.2 GeV/ u. Full line: unitarity limit. From [RuS93].
par amet er b = 20 fro, t he ionization rat e is reduced by up to 30% if negative-
energy st at es are included.
Fi gure 6.17 shows lSl/ 2 and 2Sl/ 2 ionization rates divided by Zp 2 as a
function of the projectile charge Zp for t he i mpact par amet er b = 20 fm.
If per t ur bat i on t heory were valid one would have horizontal st rai ght lines.
The calculations show t hat t he 2Sl/ 2 ionization rat e is lower t han t he lSl/ 2
ionization rat e by a factor of 3.
In accordance wi t h t he previous remarks regardi ng t he influence of
boundar y conditions, it has been poi nt ed out by Bal t z et al. [BaR93b]
t hat t he nonper t ur bat i ve behavior seen in coupled-channel calculations is
st rongl y gauge dependent , in part i cul ar for small basis sizes. Insofar, such
results have to be viewed wi t h some caution.
In Chap. 10, in t he cont ext of el ect ron-posi t ron pair product i on, we
ret urn to the probl em of discrepancies bet ween cal cul at ed per t ur bat i ve and
nonper t ur bat i ve cross sections. In this case, the est i mat ed effects are by
far larger.