Phaseshifts and total cross sections for the elastic scattering of low-energy (0-13.6 eV) electrons by molecular fluorine are presented. The phaseshifts are obtained by an approximate technique based on the weak asymptotic coupling of orbital angular momenta and are calculated solely from the results of a discrete basis set diagonalization of the molecular Hamiltonian. Correlation and polarization effects are not treated. The elastic cross section is dominated by a Sigma u+ shape resonance at about 2.2 eV in the static-exchange model

Bender, C. F.

McCurdy, C. W.

McKoy, V.

Rescigno, T. N.

English

Caltech Authors - Main

J. Phys. B: Atom. Molec. Phys., Vol. 9, No. 12. 1976. Printed in Great Britain. @ 1976 
Cross sections for the elastic scattering of low-energy 
electrons by molecular fluorine : an approximate 
theoretical treatment using discrete basis functions-f 
T N Rescignol, C F Bender$, C W McCurdygII and V McKoySY 
$ Lawrence Livermore Laboratory. University of California, Livermore, California 94550, 
USA 
5 Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology, 
Pasadena, California 91 125, USA 
Received 12 January 1976, in final form 1 April 1976 
Abstract. We present phaseshifts and total cross sections for the elastic scattering of 
low-energy (0- 13.6 eV) electrons by molecular fluorine. The phaseshifts are obtained by 
an approximate technique based on the weak asymptotic coupling of orbital angular 
momenta and are calculated solely from the results of a discrete basis set diagonalization 
of the molecular Hamiltonian. Correlation and polarization effects are not treated. The 
elastic cross section is dominated by a CJ shape resonance at about 2.2 eV in the static- 
exchange model. 
1. Introduction 
In a previous paper (McCurdy et a1 1976, hereafter referred to as I) we outlined 
a method for obtaining approximate low-energy electron-diatomic-molecule elastic 
scattering cross sections solely from the results of a basis set Hartree-Fock calculation 
on the closed-shell molecular target. The method was based on the assumed validity 
of the so-called ‘low 2-spoiling’ approximation (Fano 1970) of low-energy electron- 
molecule scattering, as well as the fact that the eigenfunctions at scattering energies 
obtained by diagonalizing the Hamiltonian in a sufficiently large set of square- 
integrable basis functions are, apart from an overall normalization, equal to the true 
wavefunctions over the region spanned by the basis set (Hazi and Taylor 1970, Hazi 
and Fels 1971). These assumptions were tested by calculations on e--H, and e--N2 
and the results obtained were found to be in reasonably good agreement with more 
elaborate theoretical treatments. In this paper, the method of I is applied to a study 
of low-energy e--F, elastic scattering. 
Very little is known about the scattering of electrons by F2, either experimentally 
or theoretically. To our knowledge, no previous theoretical studies of elastic e--F2 
scattering have been performed. A rigorous treatment would be complicated by the 
?This work was performed under the auspices of the US Energy Research and Development Adminis- 
tration under contract No W-7405-ENG-48. 
11 Present address: Department of Chemistry, University of California, Berkeley, California 94720, USA. 
7 Supported by a grant from the National Science Foundation. 
2141 
2142 T N Rescigno, C F Bender, C W McCurdy and V McKoy  
fact that the ground state of F2 is more difficult to describe accurately than the 
ground states of other first-row diatomics. The calculations presented here make 
use of the static-exchange approximation in which the F2 target is frozen in its 
Hartree-Fock ground-state wavefunction. The well known failure of the Hartree- 
Fock wavefunction to predict F2 to be bound relative to two fluorine atoms (Wahl 
1964) raises some doubt as to the adequacy of a Hartree-Fock description for con- 
structing a scattering potential. Thus, until more accurate calculations are performed, 
the present results should be considered preliminary. 
Our calculations on this system incorporate a number of simplifying approxima- 
tions. As in the computations reported in I, we have ignored correlation and polariza- 
tion effects in restricting ourselves to a study of the static-exchange approximation 
with a Hartree-Fock target wavefunction. The dominant feature we find in the total 
elastic cross section is a 1; shape resonance coming from the PO phaseshift at about 
2.2 eV. Before presenting our results, we give a brief summary of the procedure used 
in this work, 
2. Theory 
The method used to obtain electron-diatomic-molecule phaseshifts, as well as the 
nature and validity of the assumptions underlying the method, have been discussed 
fully in I and only a brief summary will be given here. Simply stated, the low /-spoiling 
assumption states that at  low electron energies orbital angular momentum is approxi- 
mately conserved in the body-fixed molecular frame. This conservation comes about 
from the repulsive centrifugal barrier of the effective potential which effectively pre- 
vents slow electrons from penetrating the highly non-spherical molecular core (Fano 
1970). It was further argued that this approximation should hold particularly well 
for a homonuclear diatomic molecule, since in this case the centre of symmetry causes 
even values of 1 to uncouple from odd values. 
We stress that the low l-spoiling approximation does not imply that the continuum 
wavefunction is proportional to a particular spherical harmonic at small radial dis- 
tances nor that a single-centre expansion of the molecular potential or the scattering 
wavefunction is rapidly convergent. It merely states that at  low energies it should 
be possible to find continuum solutions asymptotically proportional to a particular 
partial wave. 
To  this end, we diagonalize the molecular Hamiltonian in a discrete set of Gaus- 
sian basis functions that give a non-vanishing contribution to the particular symmetry 
(labelled by 1 and Iml values) under consideration. This set is chosen to give a good 
description of the occupied Hartree-Fock molecular orbitals and is then augmented 
with additional diffuse functions of one particular symmetry, most of which are placed 
at  the centre of the molecule. The molecular Hamiltonian is then diagonalized in 
this basis. For each positive energy eigenfunction, YE(v), a radial wavefunction R&(r) 
is obtained by projection with the appropriate spherical harmonic: 
Rfm(r) = dRYFm(R)YE(u). s 
For the particular case of a diatomic molecule with Gaussian basis functions chosen 
along the axis of symmetry the projection integral of equation (1) can be done analyti- 
cally. 
Elastic eC-F, scattering 2143 
On the assumption that the basis set representation of Rk(r) is valid over the 
region spanned by the basis (Hazi and Taylor 1970, Hazi and Fels 19711, and that 
this region is sufficiently large to reach a point where the potential has become 
vanishingly small, the tangent of the phaseshift may be obtained by plotting 
as a function of r and extracting a value for the phaseshift from the region where 
this function levels off to a constant value. This part of the procedure can be thought 
of as a basis set approach to the familiar variable-phase method of potential scattering 
(Calogero 1967). In contrast to the latter procedure, however, the value of tan dLm(r) 
obtained from equation (2) will again vary as a function of r when the basis is 
no longer capable of representing Rfm(r) accurately. 
The assumption of angular momentum decoupling simplifies the problem con- 
siderably since we do not have to face the prospect of dealing with more than one 
linearly independent regular solution at one energy for a particular choice of 1 and 
m. Relaxation of this assumption would complicate the problem considerably (Hazi 
1973). 
3. Results 
All of our calculations were carried out at the equilibrium internuclear separation 
of F,, 2.68 a,,. Correlation and polarization effects have not been considered in these 
computations; that is, the continuum wavefunctions were obtained as the positive 
energy eigenfunctions of the Hartree-Fock Hamiltonian of Fa. The HF occupied 
orbitals for F, were computed using a basis of [6s/5p] Gaussians on each fluorine 
contracted from a (10s/6p) set of primitives similar to that suggested by Dunning 
(1970), plus two do and two dn polarization functions (Dunning 1971) on each fluorine. 
The results of the self-consistent field (SCF) computation are summarized in table 1. 
Five separate diagonalizations were performed to obtain virtual Hartree-Fock 
eigenfunctions of C i ,  C:, nu, Il, and A, symmetry. For the C+ orbitals, the previous 
basis was augmented by two s-type and two z-type Gaussians on each fluorine and 
eight more s functions at the midpoint. The C,' calculations were done by adding 
Table 1. SCF molecular orbital eigenvalues for F2t.  (Energies are given in au.) 
- 198'73201 
- 26.4 129 
- 1.7523 
-0.7383 
-26.4126 
- 1.4890 
- 0.7984 
- 06563 
t In a 6s/5p basis of contracted Gaussian functions. This basis was only used to represent 
the occupied orbitals. 
2144 T AT Rescigno, C F Bender, C W McCurdy and V McKoy 
Table 2. e--F2 phaseshifts 
0.0216 
0.0461 9 
0,07738 
0.1199 
0.1806 
0.2695 
0.4021 
0.5973 
0.903 
1.086 
3,1005 
3,054 
2,994 
2,914 
2,798 
2.644 
2.40 
2.10 
1.75 
1.69 
0,0258 0~00001 
0.0480 0.0001 
0,0736 0,002 
0.1147 0,004 
0.1684 0,044 
0,2430 0.09 
0.3380 0.32 
0,4210 1.73 
0.572 2.32 
0.749 2.49 
1.170 2.25 
'0.0376 
0,0699 
0.1 110 
0.1671 
0.2469 
0.3636 
0,5394 
0.8039 
1.139 
3,14143 0,0460 
3.14078 0,0804 
3,1377 0.1239 
3,1308 0.1838 
3.105 0.2692 
3.054 0.3922 
2.895 0,5714 
2.78 0.8358 
2.5 1.1236 
3.1415917 0,3880 0.07 
3.141589 03639 0.20 
3.141534 0.8155 0.22 
3.14135 1,138 0.38 
3.1395 1,614 0.49 
3,132 
3.090 
2,976 
2.75 
two s and one z function on the fluorines and nine more z functions at the midpoint 
to the H F  basis. For the nu calculations, one x-type Gaussian on each fluorine 
and eight more at the midpoint were added to the HF basis; one additional x function 
on the fluorines and twelve more xz-type Gaussians at the midpoint were used in 
the IIg diagonalization. The Ag basis consisted of the H F  basis plus six xy Gaussians 
on each fluorine plus eight more at the midpoint. 
Table 2 lists the s, pa, pn, dn and d6 phaseshifts and corresponding eigenvalues. 
The number of digits given in the phaseshifts represents the number of significant 
digits that could be deduced from a region over which the phaseshift had stabilized. 
These figures merely reflect the stability of the extraction procedure and do not 
indicate the possible convergence of the phaseshift with respect to basis functions. 
Since the eigenvalues corresponding to different symmetries cannot be made to 
coincide by a simple diagonalization of the Hamiltonian, the computed phaseshifts 
must be interpolated before cross sections can be calculated. These interpolated values 
were used to compute a total elastic cross section which satisfies the equation 
4n 
a,,, = -1 sin2 dLm. 
k 2  1,m (3) 
The total cross section is depicted in figure 1. 
The cross section is seen to be dominated by a Xi-po resonance at about 
2.2 eV and rises from a background value of approximately 40 u t  to almost 120 u t  
over an energy range of about 04  eV. Unfortunately, there were only five computed 
eigenvalues in the interesting region over which the pa phaseshift rises through 
2.4 rad. and thus the resonant cross section will be somewhat sensitive to the way 
in which the phaseshifts are interpolated. 
4. Discussion 
We have applied a simple, but approximate, method to calculate low-energy e--F, 
elastic cross sections. The calculations were carried out under the assumption of 
low l-spoiling and correlation and polarization effects were also ignored. Since the 
method is based solely on the diagonalization of the molecular Hamiltonian over 
Elastic e- -F2 scattering 2145 
1 2 0 1 -  
i ’ - I i -  
0 D L  0.8 
Momentum ( a u l  
Figure 1. e--F, total elastic cross sections obtained from interpolated phaseshifts 
a discrete set of Gaussian basis functions and asymptotic boundary conditions are 
not explicity imposed, the entire procedure was implemented with standard bound- 
state molecular programs. Total cross sections were found by interpolation of phase- 
shifts obtained at discrete energy eigenvalues. The dominant feature we find in the 
elastic cross section is a 2.2eV C: shape resonance coming from the PO partial 
wave. 
However, it is entirely possible that this resonance is an artifact of the static- 
exchange approximation and would disappear if correlation effects were included. 
It is interesting to note that a comparison of the Hartree-Fock potential energy 
curves for the ground states of F2 (Das and Wahl 1966) and F; (Gilbert and Wahl 
1971) suggests that F; is stable with respect to F, and a free electron at the equilib- 
rium internuclear distance of F,. If that were the case, the shape resonance found 
in the present static-exchange calculation would be of doubtful validity. However, 
if a multiconfiguration, self-consistent field (MCSCF) potential energy curve for F2 
(Das and Wahl 1972) is used in the above comparison, F; is predicted to be unstable 
at the equilibrium internuclear distance of FZ. Experimental evidence for the 
resonance may be inferred from studies on the dissociative attachment of low-energy 
electrons to F,; this work is summarized in a review by Caledonia (1975). The 
measured rate constants for DA to FZ are quite large, indicating that the reaction 
may well proceed through resonance excitation to an unbound F; ion. In any event, 
the possibility of a stable negative ion suggests that the static-exchange approximation 
may be less valid for electron-F, scattering than for the previously studied cases 
of e--H, and e--N, (McCurdy et al 1976). Since there are no other calculations 
or experiments with which to compare these results directly, confirmation of our 
findings must await further study. One important question that must be answered 
is whether, in view of the poor H F  description of F,, the use of a correlated F2 
ground state in the static-exchange approximation would significantly modify these 
results. Work along these lines is presently under study. 
2146 T N Rescigno, C F Bender, C W McCurdy and V McKoy  
References 
Caledonia G E 1975 Chem. Ret.. 75 333-51 
Calgero F 1967 The Variable Phase Approach to Potential Scattering (New York: Academic Press) 
Das G and Wahl A C 1966 J .  Chem. Phys. 44 87-96 
-1972 J .  Chem. Phys. 56 353240 
Dunning T H 1970 J .  Chem. Phys. 53 2823-33 
-1971 J .  Chem. Phys. 55 3958-66 
Fano U 1970 Comments on Atomic and Molecular Physics 1 140-4 
Gilbert T L and Wahl A C 1971 J .  Chem. Phys. 55 5247-61 
Hazi A U 1973 Chem. Phys. Lett. 20 251-6 
Hazi A U and Fels M F 1971 Chem. Phys. Lett. 18 582-6 
Hazi A U and Taylor H S 1970 Phys. Ret.. A 1 1109-20 
McCurdy C W, Rescigno T N and McKoy V 1976 J .  Phys. B :  Atom. Molec. Phys. 9 691-8 
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Cross sections for the elastic scattering of low-energy electrons by molecular fluorine: an approximate theoretical treatment using discrete basis functions

The Variable Phase Approach to Potential Scattering (New York: Academic Press) Das G and Wahl A C

http://authors.library.caltech.edu/11307/1/RESjpb76.pdf

Cross sections for the elastic scattering of low-energy electrons by molecular fluorine: an approximate theoretical treatment using discrete basis functions

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