PHYSICAL REVIEW A 82, 032706 (2010)

Electron-impact study of the SO radical using the R-matrix method

Jasmeet Singh Rajvanshi* and K. L. Baluja†

Department of Physics and Astrophysics, University of Delhi, Delhi 110007, India
(Received 28 April 2010; published 15 September 2010)
The SO radical with an even number of electrons belongs to an open-shell system due to its π 2 ground-state
electronic configuration. This configuration gives rise to three low-lying states X 3  − , a 1 , and b 1  + . The
inclusion of these target states in a trial wave function of the entire scattering have important implications in
the resonances that may be detected in this open-shell molecule. The R-matrix method is a well-established
ab initio formalism which is employed to calculate elastic differential and integral cross sections, momentum-
transfer cross sections, and inelastic cross sections. The Hartree-Fock ground-state configuration of SO is
1σ 2 2σ 2 3σ 2 4σ 2 1π 4 5σ 2 6σ 2 7σ 2 2π 4 3π 2 . We have included 28 target states in the trial wave function of the
scattering system. In our configuration-interaction (CI) model, we freeze 12 electrons in orbitals 1σ , 2σ , 3σ ,
4σ , and 1π , the remaining 12 electrons are free to move among the eight orbitals 4σ , 5σ , 6σ , 7σ , 8σ , 9σ ,
2π , and 3π . We have carried our scattering calculations in static-exchange, one-state with CI wave function,
and 28-state models. We have detected a stable anionic bound state 2 B1 of SO at various bond lengths of SO
molecule. The vertical electron affinity value is 0.970 eV, which is comparable to the experimental value of
1.125 eV. We also detected two core-excited shape resonances, both of 2  symmetry and with 1  and 1  + as
the parent states.

DOI: 10.1103/PhysRevA.82.032706 PACS number(s): [Link], [Link], [Link]

I. INTRODUCTION The present study applies the ab initio R-matrix method to

low-energy scattering of the SO molecule in the fixed nuclei
Sulfur-containing compounds are important in many pro-
approximation. The calculations use code developed by the
cesses. It is well known that SO2 is one of the major
UK Molecular R-Matrix Group [11,12]. The R-matrix method
atmospheric pollutants to cause acid rain. During the eruption
has the advantage over other scattering methods in efficiently
of volcanoes or the use of fossil fuels, a large amount of this
providing cross sections at a large number of scattering
gas is thrown into the Earth’s atmosphere. The SO2 -containing
plasmas also play an important role in planetary atmospheres energies. It also has the ability to include correlation effects
[1,2]. The low-temperature processing plasmas containing and give an adequate representation of several excited states of
SO2 have been employed in the plasma-assisted surface the molecule [13]. We are interested in the low-energy region
treatment of biocompatible material and biomedical devices (
10 eV) which is a favorite ground for the R-matrix method.
[3], the SO radical is an abundant byproduct of the plasma The incoming electron can occupy one of the many unoccupied
remediation of SO2 from any combustion source using fossil molecular orbitals or can excite any of the occupied molecular
fuels [4,5]. Sulfur oxide is a species of both astrochemical [6] orbital as it falls into another one. These processes give
and technological importance [7]. Technologically, it is used as rise to the phenomenon of resonances forming a negative
a laser in the near-ultraviolet region. At the molecular level, the molecular ion for a finite time before the resonance decays
a 3 –X 3  − transition is the one involved in the lasing process into energetically open channels.
in SO. In the literature, the determination of partial and total Electron scattering calculations are performed at static
ionization cross sections have been reported [8]. Recently, a exchange, one-state CI and close-coupling approximation in
study on electron collision with SO and some other sulfur- which we have retained 28 target states in the R-matrix
containing molecules using a spherical complex potential was formalism. The integrated elastic, differential, and momentum
reported [9], and in that study, elastic integral and grand-total cross sections for electron impact on the SO molecule from
cross sections and total ionization cross sections for incident its ground state are reported. The excitation cross sections
energies ranging from ionization threshold to 2000 eV were from the ground state to few low-lying excited states have also
computed. In the theoretical area, a very recent calculation been calculated. We have also computed the binary-encounter-
was performed at the static-exchange-polarization-absorption Bethe (BEB) ionization cross section [14,15]. The BEB cross
level of approximation using a combination of the iterative sections depend only on the binding energies, kinetic energies,
Schwinger variation method [10] and the distorted-wave and the occupation number of the occupied molecular orbitals
approximation. More specifically, in that study, differential of the target and on the energy of the incident electron. The
cross sections (DCSs), integral cross sections (ICSs), and momentum-transfer cross sections calculated in the R-matrix
momentum-transfer cross sections (MTCSs) were computed approximation have been used to calculate effective collision
in the 1–500 eV energy range. frequency over a wide electron temperature range. We must
point out that the R-matrix approach is not the only scattering
method that allows the ab initio inclusion of correlation effects
*
Also at Keshav Mahavidyalaya, Physics and Electronics Depart- and is applicable to studies of open-shell targets. The complex
ment, University of Delhi; rajvanshi jasmeet@[Link] Kohn variational method has been successfully employed for
†
kl baluja@[Link] polyatomic targets [16].

1050-2947/2010/82(3)/032706(10) 032706-1 ©2010 The American Physical Society

JASMEET SINGH RAJVANSHI AND K. L. BALUJA PHYSICAL REVIEW A 82, 032706 (2010)

II. METHOD to orthogonalize the continuum molecular orbitals among

themselves and remove linearly dependent functions [11,21].
A. Theory
In general and in this work, all calculations are performed
In an R-matrix approach [17,18], the configuration space within the fixed-nuclei approximation. This is based on the
of the scattering system is divided into two spatial regions: assumption that electronic, vibrational, and rotational motions
an inner region and an outer region. These regions are treated are uncoupled.
differently in accordance with the different interactions in In the inner region, the wave function of the scattering
each region. The center of the R-matrix sphere coincides system, consisting of target plus scattering electron, is written
with the center of mass of the molecule. When the scattering using the CI expression
electron leaves the inner region, the other target electrons


are confined to the inner region. In the present work, the kN+1 = A φiN (x1 , . . . ,xN ) ξj (xN+1 )aij k
R-matrix boundary radius dividing the two regions was i j


chosen to be 10a0 , centered at the SO center of mass. This + χm (x1 , . . . ,xN ,xN+1 )bmk , (1)
sphere encloses the entire charge cloud of the occupied m
and virtual molecular orbitals included in the calculation.
At 10a0 , the amplitudes of the molecular orbitals are less where A is an antisymmetrization operator, xN is the spatial
−3/2 and spin coordinates of the N th electron, φiN represents the
than 10−5 a0 . However, the continuum orbitals have finite
ith state of the N -electron target, ξj is a continuum orbital
amplitudes at the boundary. Inside the R-matrix sphere,
spin-coupled with the scattering electron, and k refers to
the electron-electron correlation and exchange interactions
a particular R-matrix basis function. Coefficients aij k and
are strong. Short-range correlation effects are important for
bmk are variational parameters determined as a result of
accurate prediction of large-angle elastic scattering, and
the matrix diagonalization. To obtain reliable results, it is
exchange effects are important for spin-forbidden excitation
important to maintain a balance between the N -electron target
cross sections. A multicentered CI wave-function expansion
representation, φiN , and the (N + 1) electron-scattering wave
is used in the inner region. The calculation in the inner region
function. The summation in the second term of Eq. (1) runs
is similar to a bound-state calculation, which involves the
over configurations χm , where all electrons are placed in
solution of an eigenvalue problem for (N + 1) electrons in
target-occupied and virtual molecular orbitals. The choice of
the truncated space, where there are N target electrons and a
appropriate χm is crucial in this [22]. These are known as
single scattering electron. Most of the physics of the scattering
L2 configurations and are needed to account for orthogonality
problem is contained in this (N + 1) electron bound-state
relaxation and for correlation effects arising from virtual
molecular-structure calculation. Outside the sphere, only
excitation to higher electronic states that are excluded in
long-range multipolar interactions between the scattering
the first expansion. The basis for the continuum electron is
electron and the various target states are included. Because
parametrically dependent on the R-matrix radius and provides
only direct potentials are involved in the outer region, a
a good approximation to an equivalent basis of orthonormal
single center approach is used to describe the scattering
spherical Bessel functions [23]. In the one-state CI model,
electron via a set of coupled differential equations. The
we have included ground state only but have used a CI wave
R matrix is a mathematical entity that connects the two regions.
function to describe it. In the 28-state model calculation, each
It describes how the scattering electron enters and leaves the
target state is represented by a CI wave function.
inner region. In the outer region, the R matrix on the boundary
is propagated outward [19,20] until the inner-region solutions
can be matched with asymptotic solutions, thus yielding the B. SO target model
physical observables such as cross sections. We include only The molecule SO is a linear open-shell system that has
the dipole and quadrupole moments in the outer region. ground state X 3  − in the C∞v point group which is reduced
In the polyatomic implementation of the UK molecular to the C2v point group when the symmetry is lowered. In
R-matrix code [11,12], the continuum molecular orbitals the R-matrix suite of programs, the highest Abelian group is
are constructed from atomic Gaussian-type orbitals (GTOs) D2h , and therefore we work in the C2v point group, which is
using basis functions centered on the center of gravity of a subset of the D2h point group. The results are reported in
the molecule. The main advantage of GTOs is that integrals the natural symmetry point group as well as in the C2v point
involving them over all space can be evaluated analytically group for the sake of convenience. We used a double zeta plus
in closed form. However, a tail contribution is subtracted to polarization (DZ + P) Gaussian basis set [24] contracted as
yield the required integrals in the truncated space defined by (12,8,1)/(6,4,1) for S and (9,5,1)/(4,2,1) for O. We avoided
the inner region [11]. using diffuse functions, as these would extend outside the
The target molecular orbital space is divided into core R-matrix box. We first performed a self-consistent-field (SCF)
(inactive), valence (active), and virtual orbitals. The target calculation for the ground state of the SO molecule with the
molecular orbitals are supplemented with a set of continuum chosen DZP basis set and obtained a set of occupied orbitals
orbitals, centered on the center of gravity of the molecule. and a virtual set of orbitals.
The continuum basis functions used in polyatomic R-matrix The Hartree-Fock electronic configuration for the ground
calculations are Gaussian functions and do not require fixed state is 1σ 2 2σ 2 3σ 2 4σ 2 1π 4 5σ 2 6σ 2 7σ 2 2π 4 3π 2 that gives rise
boundary conditions. First, target and continuum molecular to lowest-lying X 3  − , a 1 , and b 1  + states correlating
orbitals are orthogonalized using Schmidt orthogonaliza- with the first dissociation channel [S(3 P ) + O(3 P )]. The
tion. Then symmetric or Löwdin orthogonalization is used energy of the occupied 3π orbital is −11.12 eV, and by

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ELECTRON-IMPACT STUDY OF THE SO RADICAL USING . . . PHYSICAL REVIEW A 82, 032706 (2010)

TABLE I. Properties of the SO target, ground-state energy, and dipole moment (in a.u.) and the ionization potential (IP, in eV), SCF at bond
length Re = 2.777a0 , and CI at bond length Re = 2.9a0 .

Present work Previous theory ISVM

a
SCF CI SCF CIa CSP-icb DWAc

E −472.333 53 −472.380 80 −472.333 54 −472.511 70 −472.137 52

µ 0.96 0.79 0.95 0.77 0.61 0.73
IP 11.12 11.12 10.29
a
W. C. Swope et al. [26].
b
Joshipura and Gangopadhyay [9].
c
Lee et al. [10].

Koopman’s theorem it is the first ionization energy. Since the the ionization potential are compared with other work in
SCF procedure is inadequate to provide a good representation Table I.
of the target states, we improve the energy of the ground as well In Table II, we list the dominant configuration, the transition
as the excited states by using CI wave functions. This lowers moments, number N of configuration state functions (CSFs),
the energies, and the correlation introduced provides a better dipole moments, and vertical excitation energies (VEEs) for
description of the target wave function and excitation energies. the target states. We have good agreement with the calculation
In our limited CI model, we keep 12 electrons frozen in the of Borin et al. [27] for VEEs and dipole and transition
1σ 2 2σ 2 3σ 2 4σ 2 1π 4 configuration and allow the remaining moments, who employed a state-averaged complete active
12 electrons to move freely in molecular orbitals 4σ , 5σ , space self-consistent field, internally contracted multirefer-
6σ , 7σ , 8σ , 9σ , 2π , and 3π . The CI ground-state energy ence configuration interaction approach using quintuple-zeta
for the SO molecule is −472.3808 hartrees, at a bond length basis sets.
of Re = 2.9a0 . We computed the value of vertical electronic
affinity (VEA) by performing a bound-state calculation of SO−
by including the continuum electron basis functions centered C. Scattering model
at the origin. The VEA is equal to the difference between We have included 28 target states (three of 1A2 , four of
3
the total energy of the neutral molecule and its anion at the A2 , four of 1A1 , two of 3A1 , three of 1B1 , five of 3B1 , three of
1
equilibrium geometry of the neutral molecule. We detect a B2 , and five of 3B2 ) in the trial wave function describing the
stable bound state of SO− with 2  symmetry having the con- electron plus target system. However, excitation cross sections
figuration 1σ 2 2σ 2 3σ 2 4σ 2 1π 4 5σ 2 6σ 2 7σ 2 2π 4 3π 3 with a VEA are reported only for the four excited states (a 1, b 1 + ,
of 0.970 eV, which is in good agreement with the estimated B 3  − , and C 3 ) that lie below the first ionization threshold.
experimental (adiabatic) value of about 1.125 eV [25]. Calculations were performed for doublet and quartet scattering
To provide additional information on the charge distribution states with A1 ,A2 ,B1 , and B2 symmetries. Continuum orbitals
in the SO molecule, we have also calculated the dipole and up to l = 4 (g-partial wave) were included in the scattering
quadrupole moments. In our CI model the dipole moment calculation. Due to the presence of the long-range dipole in-
and the absolute values of the quadrupole component Q20 teraction, the elastic cross sections are formally divergent in the
for the ground state are 0.7945 and 0.86 a.u., respectively. fixed-nuclei approximation, because the differential cross sec-
The values of the ground-state energy, dipole moment, and tion is singular in the forward direction. To obtain converged

TABLE II. Dominant configuration, transition moments (in a.u.), number N of configuration state functions (CSFs), the vertical excitation
energies (VEEs in eV), and dipole moments (µ in a.u.) for the target states of SO at bond length Re = 2.9a0 .

VEE (eV) µ (a.u.)

State Transition
a
C2v /C∞v Present Previous moments (a.u.) N Present Previousa

X 3 A2 /X 3  − 0.0 – – 864 0.79 0.62

a(1 A2 ,1 A1 )/a 1  0.75 0.71 – 584 696 0.73 0.59
b(1 A1 )/b 1  + 1.14 1.28 – 696 0.71 0.55
c(1A2 )/c 1  − 3.95 4.20 – 584 0.04 0.03
A (3A2 ,3 A1 )/A 3  4.10 4.40 0.002 864 822 0.04 0.07
A (3A1 )/A 3  + 4.21 4.50 – 822 0.04 0.06
A 3B1 ,3B2 /A 3  5.53 4.92 0.013 858 0.38 0.25
C 3B1 ,3B2 /C 3  5.84 5.70 0.173 858 0.37 0.26
d 1B2 ,1B1 /d 1  6.62 5.62 – 620 0.36 0.18
e 1B2 ,1B1 /e 1  6.71 6.65 – 620 0.33 0.21
B 3A2 /B 3  − 7.06 5.90 0.645 864 0.22 0.28
a
Borin et al. [27].

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JASMEET SINGH RAJVANSHI AND K. L. BALUJA PHYSICAL REVIEW A 82, 032706 (2010)

2 300

3 - Doublets
Σ SO Quartets
1.5 2 - 250
Π SO Total (Doublets + Quartets)
Born correction

Elastic cross section (units of a0 )

2
Born corrected
1
200
Energy (eV)

0.5
150

0
100
-0.5

50
-1

0
-1.5 0 1 2 3 4 5 6 7 8 9 10
2.5 2.6 2.7 2.8 2.9 3 3.1 Energy (eV)
Bond length (units of a0)

FIG. 3. Elastic cross sections of the electron impact on the SO

FIG. 1. Ground-state potential energy curves of SO and SO−
molecule at Re for 28-state calculations. Dash-dot curve, doublets
molecules. Dashed curve, SO; solid curve, SO− .
sum ; dashed curve, quartets sum; thin solid curve, total (doublets +
quartets); dotted curve, Born correction; thick solid line, Born
cross sections, the effect of rotation must be included along corrected (sum of doublets, quartets, and Born correction).
with a very large number of partial waves. The effects of partial
waves with l > 4 were included using a Born correction via a
closure approach [28]. Our g-partial wave cross section using of SO, which indicates the detection of an anionic bound
the R-matrix method nearly coincided with the g-wave Born state. We calculated the bound-state energies of this anionic
results. This establishes the correctness of our procedure to 2
 state at different bond length by performing an L2 -type
use Born correction beyond the g-partial wave. The use of the calculation. The potential-energy curves of the 3  − state of
rotationally resolved Born closure procedure has also been put the SO molecule and 2  state of the SO− anion are shown in
forth in [29]. Fig. 1. The anion is stable at all the bond lengths. This yields
a vertical electron affinity of 0.97 eV at Re . From Fig. 1, we
III. RESULTS find that the equilibrium bond length for the ground state of
the anion SO− is 3.1a0 . The S–O bond length is about 6.9%
A. Elastic and inelastic total cross sections elongated in the anionic state SO− because the extra electron
The ground-state electronic configuration of SO has two is in a ∗ orbital. Our value of electron affinity is 0.970 eV,
unpaired π electrons. Due to vacancy in the 3π orbital of which is in good agreement with the estimated experimental
the ground state of SO, the scattering electron can occupy it, (adiabatic) value of about 1.125 eV [25].
forming a stable anionic ground state of SO with symmetry In Fig. 2, we have summed the contribution of doublet and
2
. In our 28-state model, we found an R-matrix pole at quartet symmetries for SCF, one-state CI, and 28-state calcu-
−472.4164 a.u. at Re in the scattering symmetry 2  which is lations. In this figure, we have shown the elastic cross section
lower than the energy −472.3808 a.u. of ground state X 3  − calculated by including only the ground state which is corre-
lated, where the active space spans orbitals up to 9σ and 3π .
1000

Static exchange
1-state CI 2
28-state CI 0 28-states CI B1
800
2
Elastic cross section (units of a0 )
2

B2

600 -1
Eigen phase sum

400
-2

200
-3

0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Energy (eV)
-4
3 3.5 4 4.5 5
Energy (eV)
FIG. 2. Elastic cross sections of the electron impact on the SO
molecule. Dotted curve, SCF at a bond length Re = 2.777a0 ; dashed
FIG. 4. Eigenphase sum of 2 B1 and 2 B2 symmetries for 28-state
curve, one-state CI, and solid curve, 28-state CI calculations at a bond
CI calculation. Solid curve, 2 B1 ; dotted curve, 2 B2 .
length Re = 2.9a0 .

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ELECTRON-IMPACT STUDY OF THE SO RADICAL USING . . . PHYSICAL REVIEW A 82, 032706 (2010)

350 of doublets and quartets to get an elastic cross section that

28-state CI (R-matrix) includes the contribution of higher partial waves neglected in
300 Lee et al the R-matrix calculation. In Fig. 4, we show the eigenphase
Total elastic cross section (units of a0 )

sum of 2 B1 and 2 B2 symmetries in the 28-state model. Figure 5

2

250
shows the comparison of total elastic cross sections (TCSs)
for the 28-state CI calculation with the calculation of Lee
200
et al. [10], who applied the Born-closure approximation at
150
the amplitude level to account for the contribution of the high
angular momentum state. We observe that at all values of
100 electron-impact energies, our values lie higher than those of
Lee et al. [10].
50 In Figs. 6–8, we show the inelastic cross sections from
the ground state to the four physical states whose vertical
0
1 2 3 4 5 6 7 8 9 10
excitation thresholds along with their dipole moments and the
Energy (eV) number of CSFs included in the CI expansion are given in
Table II.
FIG. 5. Comparison of total elastic cross sections (TCSs). Dashed
In Fig. 6 we notice sharp peaks at 4.06 eV, having widths of
curve, Lee et al. [10]; solid curve, R-matrix results for 28-state CI
0.170 and 0.164 eV in the cross sections of the X 3  − –a 1 
calculation.
and X 3  − –b 1  + transitions, respectively. These resonances
belong to degenerate (2B1 /2B2 )2  symmetries. We assign a
We notice one peak in the cross sections at 0.77 eV in the SCF common configuration 2π 4 3π 2 3π to these core excited shape
calculation and which is shifted to 0.25 eV in the one-state cal- resonances which decay to different parent states a 1 and
culation due to inclusion of extra correlation effects. The eigen- b 1 + , respectively, by dissociating a 3π molecular orbital. The
phase sum shows a sudden jump of π radian centered at this resonance properties of these peaks are also given in Table III.
position. This resonance belongs to degenerate (2B1 /2B2 )2  We have also shown the electronic excitation results for e-O2
symmetry. To investigate whether this resonance is real, we scattering using the R-matrix method [30]. In contrast to the
performed the calculation in a 28-state model. The resonance O2 results for both the excitation processes, there is a marked
seen in the SCF and one-state CI model is washed out in this resonance structure in the case of SO around 4 eV. In general,
28-state model due to the inclusion of higher excited states. the cross sections for SO are slightly larger because SO is a
The retention of a large number of closed electronic exci- bigger molecule than O2 .
tation channels in the 28-state model provides the necessary Figure 7 depicts the excitation cross section for the
polarization potential in an ab initio way; this polarization optically allowed transition X 3A2 (X 3  − )–b 3A2 (b 3  − ). The
potential is critical in determining the resonance parameters of contribution of quartet and doublet symmetries is shown
the detected resonances. In Fig. 3, we have present the elastic separately. The contribution of quartets is more than that of
cross sections of the electron impact on the SO molecule at Re doublet symmetries due to their higher spin multiplicity by a
for the 28-state calculation. We have shown the contribution factor of nearly 2 than that of doublet symmetries. The Born
of doublet and quartet symmetries separately. We notice one correction is also included for this dipole transition.
peak in the cross sections of doublets around 4 eV which is due Figure 8 depicts the excitation cross section for the
to degenerate (2 B1 /2 B2 )2  symmetry. The eigenphase sum optically allowed transition X 3A2 (X 3  − )–C 3B1 /3 B2 (C 3 ).
shows a sudden jump of π radian centered at this position. The contribution of quartet and doublet symmetries is shown
The Born correction shown in Fig. 3 is added to the sum separately. The contribution of quartets is once again higher

R-matrix method R-matrix method

2 2
3 - 1 3 - 1 +
e-SO (X Σ --> a ∆) Our results e-SO (X Σ --> b Σ ) Our results
Excitation cross section (units of a0 )

Excitation cross section (units of a0 )

2

3 - 1 3 - 1 +
e-O2 (X Σ g --> a ∆g) Noble et al e-O2 (X Σ g --> b Σ g) Noble et al

1.5 1.5

1 1

0.5 0.5

0 0
0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10
Energy (eV) Energy (eV)

FIG. 6. Electron-impact excitation cross sections from the ground state: X 3  − (3A2 ) of the SO molecule to the a 1  a(1A2 /1A1 ) and b 1  +
b(1A1 ), solid line; X 3 g− of the O2 molecule to the a 1 g and b 1 g+ , dotted curve, from Noble and Burke [30].

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JASMEET SINGH RAJVANSHI AND K. L. BALUJA PHYSICAL REVIEW A 82, 032706 (2010)

TABLE III. Resonance properties of SO at bond length R = 2.9 a0 .

Electronic configuration Er r Type of Parent

of resonant state (eV) (eV) resonance state

1σ 2 -7σ 2 1π 4 2π 4 3π 2 (a 1 )(3π ) : 2  4.06 0.170 Core-excited shape a 1 A1 /1A2 (a 1 )

1σ 2 -7σ 2 1π 4 2π 4 3π 2 (b 1  + )(3π ) : 2  4.06 0.164 Core-excited shape b 1A1 (b 1  + )

than that of doublet symmetries. The Born correction is also C. Differential cross section
included for this dipole transition. The evaluation of the differential cross sections (DCSs)
provides a more stringent test for any theoretical model. The
B. Ionization cross section
rotational excitation cross sections for electron impact on a
neutral molecule can be calculated from the scattering param-
Figure 9 shows electron-impact ionization cross sections eters of elastic scattering in the fixed nuclei approximation
of SO from threshold 11.12 eV to 5000 eV by using the provided the nuclei are assumed to be of infinite masses [31].
standard formalism of the binary-encounter-Bethe (BEB) In particular, starting from an initial rotor state J = 0, the sum
model [14,15]. This formalism requires the binding energy and of all transitions from the J = 0 level to a high enough J value
kinetic energy of each occupied orbital in a molecular structure for convergence is equivalent to the elastic cross section in the
calculation. The ionization cross section rises from threshold fixed nuclei approach. We have employed this methodology
to a peak value of 4.8 Å2 at 77.8 eV and then shows ln(E/E) to extract rotationally elastic and rotationally inelastic cross
behavior as E approaches higher values. We have also shown sections from the K-matrix elements calculated in the one-state
the results of previous theoretical work [8–10]. The molecular R-matrix model. The DCS for a general polyatomic molecule
orbital data used in the calculation of the BEB cross section is is given by the familiar expression
given in Table IV, which is generated at SCF level. The BEB
dσ

ionization cross section σ is obtained by summing over each = AL PL (cos θ ). (3)
orbital cross section σi , where d L
      where PL is a Legendre polynomial of order L. The AL
s 1 1 1 ln t
σi (t) = 1 − 2 ln t + 1 − − , coefficients have already been discussed in detail [32]. For
t +u+1 2 t t t +1
a polar molecule, this expansion over L converges slowly. To
(2) circumvent this problem, we use the closure formula
where t = T /B, u = U/B, and s = 4π a0 2 N (R/B)2 . Here, R dσ dσ B
 
= + AL − AL B PL (cos θ ). (4)
is the Rydberg energy, T is the kinetic energy of the incident d d L
electron, U is the orbital kinetic energy, N is the electron
occupation number, and B is the binding energy of the orbital. The superscript B denotes that the relevant quantity is
calculated in the Born approximation with an electron-point
dipole interaction. The convergence of the series is now rapid,
3 since the contribution from the higher partial waves to the DCS
Total (Doublets + Quartets) is dominated by the electron-dipole interaction. The quantity
2.5
Born correction
Born corrected d
dσ
for any initial rotor state |Jm is given by the sum over all
Doublets
Excitation cross section (units of a0 )
2

Quartets

0.6
1.5
Excitation cross section (units of a0 )
2

0.5
3 - 3 -
X Σ --> B Σ
1
0.4

0.5 Doublets 3 - 3
0.3 Quartets X Σ --> C Π
Sum (Doublets + Quartets)
Born correction
0 0.2 Born corrected
7 8 9 10 11 12 13 14
Energy (eV)
0.1
FIG. 7. Electron-impact excitation cross sections from the ground
X 3  − (3A2 ) state of the SO molecule to the b 3  − (3A2 ) state for 0
6 7 8 9 10 11 12 13 14
the 28-state calculation. Dash dot curve, doublets sum; dashed curve, Energy (eV)
quartets sum; thin solid line, total (doublets + quartets); dotted curve,
Born correction; thick solid line, Born corrected (sum of doublets, FIG. 8. Same as Fig. 7, but for the ground X 3  − (3A2 ) state of the
quartets, and Born correction). SO molecule to the C 3  (3B1 /3 B2 ) state for the 28-state calculation.

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6 TABLE V. Number of coupled channels for a doublet or a quartet

BEB model scattering symmetry of SO molecule for 28-state calculation.
Lee et al
Tarnovsky et al (expt.)
Ionization cross sections (units of 10 cm )

5
2

Tarnovsky et al (theoretical) Scattering symmetry Number of coupled channels

-16

Joshipura et al
2
4 A1 174
2
B1 176
2
B2 176
3 2
A2 174
4
A1 90
4
2 B1 95
4
B2 95
4
1
A2 95

0 use Eq. (3) as follows to calculate the DCS:

10 100 1000
Energy (eV)     
dσ 1 dσ Q dσ D
FIG. 9. Electron-impact BEB ionization cross sections of the SO = 2 + , (6)
d 3 d d
molecule. Dashed curve, Joshipura et al. [9]; dotted curve, Tarnovsky
et al. (theor.) [8]; dash-dot curve, Tarnovsky et al. (expt.) [8]; thin
where ( ddσ )Q,D represent DCS for quartet and doublet cases,
solid curve, Lee et al. [10]; thick solid line, our BEB model.
respectively. [The number of coupled channels for a doublet or
a quartet scattering symmetry are shown later in Table V.] The
final rotor states |J  m  number of closed channels depend upon the scattering energy
dσ
dσ of the incident electron.
= (Jm → J  m ). (5) In Fig. 10, we show the spin-averaged DCSs calculated
d J  m
d
in the one-state R-matrix model at different energies. We
where J is the rotational angular momentum, and m is its have compared our results with results of Lee et al. [10],
projection on the internuclear axis. To obtain converged results, who used the iterative Schwinger variational method at the
the maximum value of J  = 5 and L = 30. We have calculated static-exchange-polarization absorption level. At 2 eV, as
DCS by using the POLYDCS program of Sanna and Gianturco we approach forward angles, the DCSs rise abruptly due to
[33], which requires basic molecular input parameters along the dipolar nature of the SO molecule. Our results are in
with K matrices evaluated in a particular scattering calculation. reasonable agreement with the results of Lee et al. [10] for
We have used this code to compute the DCS in the one-state angles up to 40◦ , beyond which our results are slightly lower,
CI model. Since SO is an open-shell molecule having X 3  − this is due to large correlation effects included in the CI model
as its ground state, the spin coupling between this target state in the present calculations. We notice similar trends at 4, 6, 8,
and the spin of the incoming electron allows two spin-specific and 10 eV, which are shown in Fig. 10.
channels, namely, the doublets (D) and quartets (Q) couplings. Besides this, the data on DCS are further used to calculate
The spin-averaged DCS for elastic electron scattering from the the momentum-transfer cross section (MTCSs), which show
SO radical are calculated by using the statistical weight 2/6 the importance of backward angle scattering. Since the DCSs
for doublet and 4/6 for quartet scattering channels. We then are not very sensitive to correlation effects for backward
scattering, we expect our MTCSs to be quite reliable in the
0.01–10 eV range. These are calculated in the one-state CI
TABLE IV. SO molecular orbital binding and average kinetic
energies for the DZ+P basis set at equilibrium geometry. |B| is binding
model with spin averaging. MTCS provides a useful input in
energy (eV), U is kinetic energy (eV), and N is occupation number. solving the Boltzmann equation for the electron distribution
function. In contrast to the diverging nature of DCS in the
Molecular orbital |B| (eV) U (eV) N forward direction, MTCS shows no singularity due to the
weighting factor (1 − cos θ ), where θ is the scattering angle.
1σ (1a1 ) 2505.28 3296.87 2 This factor vanishes as θ → 0. The MTCS is useful in the
2σ (2a1 ) 560.84 794.53 2 study of electrons drifting through a molecular gas. When a
3σ (3a1 ) 246.64 509.37 2 swarm of electrons travel through a molecular gas under the
4σ (4a1 ) 183.48 478.62 2 influence of an electric field, several transport observables such
1π (1b1 ) 183.42 478.62 2 as diffusion coefficient D and mobility µ can be obtained if we
1π (1b2 ) 183.42 478.08 2 have a knowledge of the momentum-transfer cross sections. In
5σ (5a1 ) 38.34 77.00 2 Fig. 11, we show the comparison of calculated MTCSs with
6σ (6a1 ) 23.73 75.64 2 those of [10]. We observe that at high energy, they both seem
7σ (7a1 ) 16.45 66.39 2
to be converging.
2π (2b1 ) 15.81 61.22 2
2π (2b2 ) 15.81 61.22 2
D. Effective collision frequency of electrons
3π (3b1 ) 5.56 54.42 1
3π (3b1 ) 5.56 54.42 1 The effective electron-neutral collision frequency v which
is averaged over a Maxwellian distribution can be obtained

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JASMEET SINGH RAJVANSHI AND K. L. BALUJA PHYSICAL REVIEW A 82, 032706 (2010)

100 100

2 eV Present result 4 eV Present result

cm /str)

cm /str)
Lee et al Lee et al
2

2
-16

-16
Differential cross section (units of 10

Differential cross section (units of 10

10 10

1 1

0.1 0.1
20 40 60 80 100 120 140 160 180 20 40 60 80 100 120 140 160 180
θ (deg) θ (deg)

100 100

6 eV Present result 8 eV Present result

cm /str)
cm /str)

Lee et al Lee et al

2
2

-16
-16

Differential cross section (units of 10

Differential cross sections (units 10

10 10

1 1

0.1 0.1
20 40 60 80 100 120 140 160 180 20 40 60 80 100 120 140 160 180
θ (deg) θ (deg)

100

10 eV Present result
cm /str)

Lee et al
2
-16
Differential cross section (units of 10

10

0.1
20 40 60 80 100 120 140 160 180
θ (deg)

FIG. 10. Comparison of differential cross sections (DCSs) at 2, 4, 6, 8, and 10 eV. Dotted curve, Lee et al. [10]; solid curve, present result
(with spin-average) for one-state CI model at Re .

from the momentum-transfer cross section Q(m) (v) as follows over a Maxwellian speed distribution function for an electron
[34]: temperature Te which is given by
   
8 me 5/2 ∞ 5 (m) −me v 2
v = N v Q (v) exp dv,  3/2  
3π 1/2 2kTe 2kTe me −me v 2
0
f (v) = 4π v 2
exp . (8)
(7) 2π kTe 2kTe
where me and Te are the electron mass and temperature,
respectively, k is Boltzmann’s constant, v is the velocity, and This type of collision frequency is often used to evaluate the
N is the number density of the gas particles. The averaging is energy transfer between particles. Alternatively, the effective

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ELECTRON-IMPACT STUDY OF THE SO RADICAL USING . . . PHYSICAL REVIEW A 82, 032706 (2010)

100

[Effective collision frequency/N](units of 10 cm s )

-3 -1
cm )

Lee et al
2

Present result
-16

80

-8
Momentum transfer cross section (units of 10

60

<υ>
1
40 ⎯υ

20

0
0 1 2 3 4 5 6 7 8 9 10
Energy (eV) 100 1000 10000
Electron temperature (K)

FIG. 11. Momentum-transfer cross sections (MTCSs) at different FIG. 12. Effective collision frequency as a function of electron
energies. Dotted curve, Lee et al. [10]; solid curve, with spin average temperature. Dashed curve, v̄; solid curve, v.
of the SO molecule ground state at the one-state CI level.
IV. CONCLUSIONS
collision frequency for electrons can be defined from the dc This is a comprehensive ab initio study of electron
conductivity as follows [34,35]: impact on the SO molecule using the UK molecular R-
matrix codes. Elastic (integrated and differential), momentum-
 5/2 ∞   transfer, excitation, and ionization cross-section have been
8 me v3 −me v 2
v̄ −1 = exp dv. presented. The results of the SCF, one-state CI, and 28-
3π 1/2 N 2kTe 0 Q(m) (v) 2kTe state close-coupling approximation are presented. We de-
(9) tect a stable bound state of SO− having the configuration
1σ 2 2σ 2 3σ 2 4σ 2 1π 4 5σ 2 6σ 2 7σ 2 2π 4 3π 3 with a vertical elec-
This explicit form of effective collision frequency v̄ is related tronic affinity value of 0.970 eV, which is in good agreement
to the drift velocity of electrons in a gas, insofar as a Maxwell with the estimated experimental value of about 1.125 eV. The
distribution can be assumed. When Q(m) (v) is proportional target states are represented by including correlations via a
to v −1 , the two effective collision frequencies v and v̄ configuration-interaction technique. Our target calculations
agree. Figure 12 shows both types of effective collision give reasonable agreement with the calculated vertical exci-
frequencies as a function of electron temperature. Note that tation spectrum of Borin et al. [27]. The derived MTCS from
v lies higher than v̄ in the entire electron temperature DCS and two types of effective collision frequencies have also
range. been presented that may be useful to the scientific community.

[1] A. L. Broadfoot et al., Science 204, 979 (1979); 206, 962 (1979). [13] J. Tennyson, J. Phys. B 29, 1817 (1996).
[2] K. Becker, W. van Wijngaarden, and J. W. McConkey, Planet. [14] Y. K. Kim and M. E. Rudd, Phys. Rev. A 50, 3954 (1994).
Space Sci. 31, 197 (1983). [15] W. Hwang, Y. K. Kim, and M. E. Rudd, J. Chem. Phys. 104,
[3] A. S. Hoffman, J. Appl. Polym. Sci.: Appl. Polym. Symp. 42, 2956 (1996).
251 (1988). [16] C. W. McCurdy and T. N. Rescigno, Phys. Rev. A 39, 4487
[4] I. Gallinberti, Pure Appl. Chem. 60, 663 (1988). (1989).
[5] M. B. Chang, M. J. Kushner, and M. J. Rood, Plasma Chem. [17] P. G. Burke and K. A. Berrington Atomic and Molecular
Plasma Process. 12, 565 (1992). Processes: An R-matrix Approach (IOP Publishing, Bristol, UK,
[6] B. E. Turner, Astrophys. J. 455, 556 (1995). 1993).
[7] Z. Cao and D. W. Setser, J. Phys. Chem. 92, 1169 (1988). [18] C. J. Gillan, J. Tennyson, and P. G. Burke, in Computational
[8] V. Tarnovsky, A. Levin, H. Deutsch, and K. Becker, J. Chem. Methods for Electron-Molecule Collisions, edited by W. M. Huo
Phys. 102, 770 (1995). and F. A. Gianturco (Plenum, New York, 1995).
[9] K. N. Joshipura and S. Gangopadhyay, J. Phys. B 41, 215205 [19] K. L. Baluja, P. G. Burke, and L. A. Morgan, Comput. Phys.
(2008). Commun. 27, 299 (1982).
[10] M.-T. Lee, I. Iga, L. E. Machado, and L. M. Brescansin, Phys. [20] L. A. Morgan, Comput. Phys. Commun. 31, 419 (1984).
Rev. A 80, 022706 (2009). [21] B. M. Nestmann, K. Pfingst, and S. D. Peyerimhoff, J. Phys. B
[11] L. A. Morgan, C. J. Gillan, J. Tennyson, and X. Chen, J. Phys. 27, 2297 (1994).
B 30, 4087 (1997). [22] J. Tennyson, J. Phys. B 29, 6185 (1996).
[12] L. A. Morgan, J. Tennyson, and C. J. Gillan, Comput. Phys. [23] A. Faure, J. D. Gorfinkiel, L. A. Morgan, and J. Tennyson,
Commun. 114, 120 (1998). Comput. Phys. Commun. 144, 224 (2002).

032706-9
JASMEET SINGH RAJVANSHI AND K. L. BALUJA PHYSICAL REVIEW A 82, 032706 (2010)

[24] T. H. Dunning and P. J. Hay, in Methods of Electronic Structure [29] M. T. N. Varella, M. H. F. Bettega, M. A. P. Lima, and L. G.
Theory, Vol. 2, edited by H. F. Schaefer (Plenum, New York, Ferreira, J. Chem. Phys. 111, 6396 (1999).
1977). [30] C. J. Noble and P. G. Burke, J. Phys. B 19, L35 (1986).
[25] [[Link] [31] E. S. Chang and A. Temkin, Phys. Rev. Lett. 23, 399 (1969).
[26] W. C. Swope, Y.-P. Lee, and H. F. Schaefer III, J. Chem. Phys. [32] F. A. Gainturco and A. Jain, Phys. Rep. 143, 347 (1986).
71, 3761 (1979). [33] N. Sanna and F. A. Gianturco, Comput. Phys. Commun. 114,
[27] A. C. Borin and F. R. Ornellas, Chem. Phys. 247, 351 (1999). 142 (1998).
[28] S. Kaur, K. L. Baluja, and J. Tennyson, Phys. Rev. A 77, 032718 [34] Y. Itikawa, Phys. Fluids 16, 831 (1973).
(2008). [35] I. P. Shkarofsky, Can. J. Phys. 39, 1619 (1961).

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