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Introdu tion
Xw
M
=1
ilk
(a)wi l k (a)
0 0
Ek
+ ii ll RilB
0
(1)
where wilk (a) is the amplitude of partial wave l asso
iated with target state i in
eigenve
tor k at a. E is the s
attering energy and RilB is the Buttle
orre
tion
whi
h
an be introdu
ed to
orre
t for the in
ompleteness of the
ontinuum
basis in the inner region [1.
A serious
omputational drawba
k of this pro
edure is that the
onstru
tion
of Ril;i l (a; E ) requires all M solutions of the M -dimensional se
ular matrix.
Sin
e
omputer time for diagonalising a matrix in
rease as M 3 and the memory
requirement in
reases as M 2 , this puts a signi
ant
onstraint on problems that
an be addressed.
In pra
ti
e many of the inner region solutions lie at energies whi
h are very
signi
antly higher than the s
attering energy of interest. This is parti
ularly
true for problems involving ele
tron
ollisions with mole
ules where the region
of interest is usually for ele
tron
ollision energies below 20 eV.
0 0
2
Berrington and Ballan
e (BB) [3 derived a \partitioned R-matrix method"
whi
h only expli
itly uses the lowest P inner region solutions and then
approximated the higher solutions. Unfortunately the pra
ti
al test given by BB
required P to be about half M to give good results. This is too many solutions
to provide any signi
ant
omputational saving. This method was subsequently
re-analysed and an alternative formulation of the partitioned R-matrix method
was given by Tennyson [4. These methods are dis
ussed below.
Partitioned R-matrix theory
X
P
=1
+ ii ll
sil
E0
1
Ek
E0
+ RilB + RilC
1
E
(2)
where RilC is an error
orre
tion term dis
ussed below. E0 is an average or
ee
tive energy for the poles omitted when only the lowest P solutions are
expli
itly
onsidered; it is dened as:
E0
=1 H
=1 E ) ;
I ;I
(3)
where the rst sum is simply the tra
e of the Hamiltonian matrix. In (2), sil is
the total probability distribution of a given
hannel on the R-matrix boundary
sil
X
nil
=1
(uilj (a))2 ;
(4)
where uilj (a) is the amplitude of the j th fun
tion used to represent the
ontinuum ele
tron inside the R-matrix box, see [5 for example. BB's error
orre
tion term was also expressed as a fun
tion of these quantities:
C
Ril
X
nil
Ji
(uilj (a))2
1
Eilj
E0
1
E
(5)
where BB dened Eilj as the energy of the
ontinuum fun
tion uilj (x) and the
sum runs over those states for whi
h Eilj > EP , the energy of the highest pole
expli
itly
onsidered.
3
Tennyson [4 identied two problems with this formulation. The rst was
that the denition of E0 was su
h that it in
reases as more L2 terms are added
to the inner region wavefun
tion expansion as most of these tend to be high
in energy. However su
h terms have zero amplitude at a and therefore do not
ontribute to the R-matrix. Se
ondly BB's error
orre
tion term over-
orre
ted
sin
e sil summed all the probability for a
hannel even if some of this probability
had already been a
ounted for in the P terms expli
itly
onsidered in the sum.
Finally for mole
ular problems he observed that the energy of a
ontinuum basis
fun
tion is not really well dened. This latter problem was solved by using the
appropriate diagonal element of the Hamiltonian matrix instead.
Tennyson redened the ee
tive energy, E0 , as the average of those diagonal
elements of the Hamiltonian matrix between
ontinuum orbitals, Hilj;ilj , whi
h
are not among the lowest P diagonal elements, ie for Hilj;ilj > EP . This
denition leaves E0 unae
ted by in
reasing the number of purely L2 fun
tions
used. Se
ondly, he estimated the
ontribution of the
ontinuum orbitals to the
states not expli
itly in
luded in the sum (2) as:
Xilj
X 2
P
=1
=1
iljk
(6)
where
iljk is the
oe
ient of
ontinuum orbital uilj in the k th eigenve
tor.
This fa
tor is then used to dene a new error
orre
tion formula:
R
C
il
X
nil
Ji
(uilj
(a))2 X
ilj
1
Hilj;ilj
E0
1
E
(7)
Test al ulations
4
1
g symmetry
Eigenphase sum
-5
-10
-15
-20
0
3
Energy (eV)
FIG. 1: Eigenphase sums for ele
tron s
attering from C2 for a full
al
ulation (solid
urve) and a partitioned R-matrix
al
ulation (dashed
urve).
appli
ations of the MRMPS pro
edure were only to two ele
tron targets (H+
3
and H2 ). Attempts to use the pro
edure for many ele
tron targets have proved
di
ult be
ause of the very large number of
ongurations that need to be
treated as a result of trying to treat the double
ontinuum even if it is dis
retised
by being lo
alised inside a box.
We have therefore
ombined the MRMPS method with the partitioned Rmatrix method to treat the problem of ele
tron
ollisions with C2 . Figure 1
shows some test results for one of the smaller wavefun
tions that we
onsidered.
Eigenphases are shown
al
ulated using the full, M = 6575, solutions and with
less than 10 % of that number, P = 650. It
an be seen that the results are very
similar. Indeed the resonan
e feature just below 5 eV is essentially unmoved
between the two
al
ulations. This result is typi
al of the more extensive (in
both energy range and number of states P ) tests that we have performed.
Con
lusions
5
ele
tron impa
t deta
hment of C2 using mole
ular R-matrix with pseudo states
models whi
h give Hamiltonian matri
es of dimension M 100; 000. For su
h
al
ulations the partitioned R-matrix method represents a major saving. This
is parti
ularly true be
ause the proportion of solutions required drops well
below 10 %, indeed we anti
ipate obtaining good results with
al
ulations whi
h
expli
itly
onsider only about 1 % of the solutions of inner region Hamiltonian
matrix.
P , the number of solutions expli
itly obtained, is
riti
al for the
omputational
performan
e of the method but is perhaps the wrong parameter to fo
us on
physi
ally. Physi
ally the important parameter is probably the energy span of
the solutions whi
h are expli
itly
al
ulated, as to get a good
al
ulation it is
learly important to span the energy regime of the
olliding ele
tron. In this
sense the key parameter should therefore be the eigen energy of solution P , EP .
Our
al
ulations on the C22 system show that to get stable results for
ollisions
energies of 15 eV, EP should be at least 40 eV.
Finally we note one
omputational issue with implementing the partitioned Rmatrix method. The outer region of the UK R-matrix
odes is written in a highly
modular fashion [10. Communi
ation between the various modules, whi
h
perform tasks su
h as R-matrix propagation [11, 12 or resonan
e tting [13, is
a
hieved via a series of small input/output subroutines [10. The partitioned Rmatrix method requires signi
ant extra information to be passed between these
modules so that the error-
orre
ted partitioned R-matrix
an be
onstru
ted.
The re-write of the
ommuni
ations routines makes it di
ult for the new
odes
to be ba
kwards
ompatible. There is no su
h problem with the only inner
region
ode that needs amending, SCATCI [2.
A
knowledgement
The UK mole
ular R-matrix
ode has been supported over many years by UK
Collaborative Computational Proje
t 2 (CCP2).
[1 P. G. Burke and K. A. Berrington, eds., Atomi
and Mole
ular Pro
esses, an
R-matrix Approa
h (Institute of Physi
s Publishing, Bristol, 1993).
[2 J. Tennyson, J. Phys. B: At. Mol. Opt. Phys. 29, 1817 (1996).
[3 K. A. Berrington and C. P. Ballan
e, J. Phys. B: At. Mol. Opt. Phys. 35, 2275
(2002).
[4 J. Tennyson, J. Phys. B: At. Mol. Opt. Phys. 37, 1061 (2004).
[5 A. Faure, J. D. Gornkiel, L. A. Morgan, and J. Tennyson, Computer Phys.
Comms. 144, 224 (2002).
6
[6 J. D. Gornkiel, L. A. Morgan, and J. Tennyson, J. Phys. B: At. Mol. Opt. Phys.
35, 543 (2002).
[7 I. Rozum, N. J. Mason, and J. Tennyson, J. Phys. B: At. Mol. Opt. Phys. 35,
1583 (2002).
[8 J. D. Gornkiel and J. Tennyson, J. Phys. B: At. Mol. Opt. Phys. 37, L343 (2004).
[9 J. D. Gornkiel and J. Tennyson, J. Phys. B: At. Mol. Opt. Phys. 38, 1607 (2005).
[10 L. A. Morgan, J. Tennyson, and C. J. Gillan, Computer Phys. Comms. 114, 120
(1998).
[11 K. L. Baluja, P. G. Burke, and L. A. Morgan, Comput. Phys. Commun. 27, 299
(1982).
[12 L. A. Morgan, Comput. Phys. Commun. 31, 419 (1984).
[13 J. Tennyson and C. J. Noble, Computer Phys. Comms. 33, 421 (1984).