PHYSICAL REVIEW A 84, 042711 (2011)

Electron-impact study of the S2 molecule using the R-matrix method

Jasmeet Singh Rajvanshi* and K L Baluja†

Department of Physics and Astrophysics, University of Delhi, Delhi 110 007, India
(Received 8 July 2011; published 17 October 2011)
The present study deals with the calculation of elastic [integrated and differential cross section (DCS)],
momentum-transfer, excitation, and ionization cross sections for electron impact on S2 molecules using the
R-matrix method. The target states are represented by including correlations via a configuration-interaction
technique. We used a double zeta plus polarization Gaussian basis set contracted as (12,8,1)/(6,4,1) for S
atoms. The results of the static exchange, correlated one-state, and 20-state close-coupling approximations
are presented. We have detected a stable anionic bound state 2 g of S2 − having the configuration
1σg2 · · ·5σg2 1σu2 · · · 4σu2 1πu4 1πg4 2πu4 2πg3 . The vertical electron affinity value is 1.42 eV, which is comparable
with the experimental value of 1.67 ± 0.015 eV. We detected two shape resonances, both of 2 u symmetry in
the excitation cross sections of the 1 g and 1 g+ excited states. The dissociative nature of these resonances is
explored by performing scattering calculations in which the S-S bond is stretched. These resonances support
dissociative attachment, yielding S and S− . We have also predicted six resonances of various symmetries (2 Au ,
2
B1g ,4 Au , 4 B1g ) in the X 3 g − → B 3 u − transition. We have calculated the DCS, in a correlated one-state model,
by using the POLYDCS program of Sanna and Gianturco. The data from the momentum-transfer cross section,
generated from DCS, are used to compute effective collision frequencies over a wide electron temperature range
(200–30 000 K). The ionization cross sections are calculated in the binary-encounter Bethe model in which
Hartree-Fock molecular orbitals at a self-consistent level are used to calculate kinetic and binding energies of
the occupied molecular orbitals. We have included up to g-partial wave (l = 4) in the scattering calculations.
For this molecule we have used a Born-closure top-up procedure to account for the higher partial waves for the
convergence of the cross section for the dipole-allowed excitation from the ground state. We have also evaluated
the scattering length of the S2 molecule, which is equal to 2.615a0 .

DOI: 10.1103/PhysRevA.84.042711 PACS number(s): [Link], [Link], [Link]

I. INTRODUCTION many-body perturbation theory with the full valence space

spanned by six valence orbitals 4σg , 4σu , 5σg , 2πu , 2πg ,
The study of the electronic structure of sulfur is very
5σu [9]. They reported potential curves and excitation energies
important for investigating its properties and applications. The
for several valence states and the results were compared
valance shell orbitals of sulfur are 3s and 3p atomic orbitals.
with CI calculations using the same primitive basis. The
The S2 molecule has its own astrophysical importance. It has
potential energy curves for 13 lowest electronic states of
been observed in the atmosphere of Jupiter [1], in comets
S2 were computed [10] at the multireference CI level using
[2], and in dense molecular clouds [3]. The molecule S2 is
complete active space self-consistent field (CASSCF) orbitals
responsible for the bulk of light emitted by the sulfur lamp [4].
with correlation-consistent cc-pVQZ basis set. Recently the
The B 3 u− –X 3 g− transition for the S2 molecule is very
electron-impact excitation of S2 molecules was studied using
intense and is widely observed in flames, shock tubes, and
the fixed-nuclei R-matrix method based on state-averaged
discharges [5].
CASSCF orbitals by Tashiro [11] with the cc-pVTZ basis
The valence configuration interaction (VCI) and self-
set. The author [11] included 13 target states, X 3 g− , a 1 g ,
consistent field (SCF) results of O2 and S2 were obtained by
Tait et al. [6] using an identical minimal basis set composed b 1 g+ , c 1 u− , A 3 u , A 3 u+ , B  3 g , B 3 u− , 1 1 g , 1 1 u ,
of Slater-type orbitals. The results of SCF and configuration- B  3 u , 1 1 u+ , and 1 1 u , in the R-matrix calculation. The
interaction (CI)-type calculations on 13 low-lying electronic author also reported the integral cross sections, for elastic
states of diatomic sulfur were reported by Swope et al. [7] collision as well as excitation of the seven lowest excited
using a basis set of double-zeta quality augmented with electronic states, and differential cross sections for elastic
polarization functions. The impact-parameter method for collision and excitation of a 1 g , b 1 g+ , and B 3 u− states.
diatomic molecules was used, for optically allowed transitions More recently the total ionization cross sections for S2 and
from the ground electronic state X 3 g − to two lower states of other molecules (formed by C, O, and S), for energies
3
u − symmetry and 3 u symmetry by Garrett et al. [8]. The ab from threshold to 5000 eV, were reported [12] using the
initio effective valence shell Hamiltonian of S2 was calculated complex spherical potential-ionization contribution method.
as a function of internuclear distance using quasidegenerate The ionization cross sections for S2 and other molecules of
sulfur were measured experimentally and reported by Freund
et al. [13] with an accuracy of ±10%. The total ionization
*
Also at Physics and Electronics Department, Keshav cross sections of 11 molecules, including the S2 molecule,
Mahavidyalaya, University of Delhi, India; rajvan- were presented for incident electron energies from threshold
shi jasmeet@[Link] to 1 keV by Kim et al. [14] using the binary-encounter-Bethe
† model with a Gaussian basis set (6-311-G set) provided by
kl baluja@[Link]

1050-2947/2011/84(4)/042711(11) 042711-1 ©2011 American Physical Society

JASMEET SINGH RAJVANSHI AND K. L. BALUJA PHYSICAL REVIEW A 84, 042711 (2011)

the GAMESS code. An experiment was performed on the In the present case, the target boundary amplitudes at 10a0
−3/2
dissociative electron attachment of S2 molecules by Le Coat are less than 10−5 a0 for the occupied and virtual orbitals.
et al. [15]. Inside the R-matrix sphere, the electron-electron correlation
The present study uses the ab initio R-matrix method and exchange interactions are strong. Short-range correlation
for low-energy scattering of the S2 molecule in the fixed- effects are important for accurate prediction of large-angle
nuclei approximation. The calculations use the UK molecular elastic scattering, and exchange effects are important for
R-matrix code [16,17]. The R-matrix method has the advan- spin-forbidden excitation cross sections.
tage over other scattering methods in providing cross sections A multicentered CI wave-function expansion is used in the
at a large number of scattering energies efficiently. It also has inner region. The calculation in the inner region is similar
the ability to include correlation effects and gives an adequate to a bound-state calculation, which involves the solution of
representation of several excited states of the molecule [18]. an eigenvalue problem for (N + 1) electrons in the truncated
We are interested in the low-energy region (10 eV), which space, where there are N target electrons and a single scattering
is a favorite ground for the R-matrix method. The incoming electron. Outside the sphere, only long-range multipolar
electron can occupy one of the many unoccupied molecular interactions between the scattering electron and the various
orbitals or can excite any of the occupied molecular orbital target states are included. Since only direct potentials are
as it falls into another one. These processes give rise to the involved in the outer region, a single-center approach is used to
phenomenon of resonances forming a negative molecular ion describe the scattering electron via a set of coupled differential
for a finite time before the resonance decays into energetically equations. The R matrix is a bridge between the two regions.
open channels. It describes how the scattering electron enters the inner region
Electron-scattering calculations are performed at static and how it leaves. In the outer region, the R matrix on the
exchange, one-state CI, and close-coupling approximations boundary is propagated outward [24,25] until the inner-region
in which we have retained 20 target states in the R-matrix solutions can be matched with asymptotic solutions, thus
formalism. The integrated elastic and the differential and yielding the physical observables such as cross sections.
momentum cross sections for electron impact on an S2 In the polyatomic implementation of the UK molecular
molecule from its ground state are reported. The excitation R-matrix code [16,17], the continuum molecular orbitals
cross sections from the ground state to a few low-lying excited are constructed from atomic Gaussian-type orbitals (GTOs)
states have also been calculated. We have also computed using basis functions centered on the center of gravity of
the binary-encounter-Bethe (BEB) ionization cross section the molecule. The main advantage of GTOs is that integrals
[19,20]. The BEB cross sections depend only on the binding involving them over all space can be evaluated analytically
energies, the kinetic energies, and the occupation number of the in closed form. However, a tail contribution is subtracted to
occupied molecular orbitals of the target, and on the energy of yield the required integrals in the truncated space defined by
the incident electron. The momentum-transfer cross sections the inner region [16].
calculated in the R-matrix approximation have been used to The target molecular orbital space is divided into core
calculate the effective collision frequency over a wide electron (inactive), valence (active), and virtual orbitals. The target
temperature range. We have also evaluated the scattering molecular orbitals are supplemented with a set of continuum
length of the S2 molecule. In this procedure we have included orbitals, centered on the center of gravity of the molecule.
only s waves which means only s orbitals are contributing. The continuum basis functions used in polyatomic R-matrix
We must point out that the R-matrix approach is not the calculations are Gaussian functions and do not require fixed
only scattering method that allows the ab initio inclusion boundary conditions. First, target and continuum molecular
of correlation effects and for studies of open-shell targets. orbitals are orthogonalized using Schmidt orthogonalization.
The complex Kohn variational method has been successfully Then symmetric or Löwdin orthogonalization is used to
employed for polyatomic targets [21]. orthogonalize the continuum molecular orbitals among them-
selves and remove linearly dependent functions [16,26]. In
II. METHOD general and in this work, all calculations are performed within
the fixed-nuclei approximation.
A. Theory
In the inner region, the wave function of the scattering
Since the R-matrix theory has been described in detail system, consisting of target plus scattering electron, is written
elsewhere [22,23], we only give an outline here. In an R-matrix using the CI expression:
approach, there are two distinct physically separated spatial
regions, an inner region and an outer region, that are defined  
kN+1 = A φiN (x1 , . . . ,xN ) ξj (xN+1 )aij k
with respect to electron-molecule distances. These are treated
i j
differently in accordance with the different forces operating 
in each region. When the scattering electron leaves the inner + χm (x1 , . . . ,xN ,xN+1 )bmk , (1)
region, the other target electrons are confined to the inner m
region. Here the R-matrix boundary radius was chosen to
be 10a0 centered at the center of mass of the S2 molecule; where A is an antisymmetrization operator, xN is the spatial
the resulting sphere encloses the entire charge density of the and spin coordinates of the N th electron, φiN represents the
molecule so that the amplitudes of the various occupied and ith state of the N -electron target, ξj is a continuum orbital
virtual target orbitals are negligible at the boundary. However, spin-coupled with the scattering electron, and k refers to a
the continuum orbitals have finite amplitudes at the boundary. particular R-matrix basis function. Coefficients aij k and bmk

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ELECTRON-IMPACT STUDY OF THE S2 MOLECULE . . . PHYSICAL REVIEW A 84, 042711 (2011)

are variational parameters determined as a result of the matrix The energy of the occupied 2πg orbital is −10.02 eV and by
diagonalization. Koopman’s theorem it is the first ionization energy. Since the
The first sum runs over the 20 target states of S2 included SCF procedure is inadequate to provide a good representation
in the present calculation, which are represented by a CI ex- of the target states, we improve the energy of the ground as well
pansion. To obtain reliable results, it is important to maintain a as the excited states by using CI wave functions. A CI approach
balance between the N -electron target representation, φiN , and is energetically much superior to a calculation based on a SCF
the (N + 1) electron-scattering wave function. The summation model. This lowers the energies and the correlation introduced
in the second term of Eq. (1) runs over configurations χm , provides a better description of the target wave function and
where all electrons are placed in target-occupied and virtual excitation energies. This also gives a better description of the
molecular orbitals. The choice of appropriate χm is crucial charge density, which is important in determining quadrupole
in this process [27]. These are known as L2 configurations and transition moments of the transition in the target states.
and are needed to account for orthogonality relaxation and In our limited CI model, we keep 20 electrons frozen in the
for correlation effects arising from virtual excitation to higher 1σg2 2σg2 3σg2 1σu2 2σu2 3σu2 1πu4 1πg4 configuration and allow the
electronic states that are excluded in the first expansion. The remaining 12 electrons to move freely in molecular orbitals
basis for the continuum electron is parametrically dependent 4σg , 5σg , 4σu , 5σu , 2πu , and 2πg . The CI ground-state energy
on the R-matrix radius and provides a good approxima- for the S2 molecule is −795.03737 hartree, at a bond length of
tion to an equivalent basis of orthonormal spherical Bessel Re = 3.676a0 . We computed the value of vertical electronic
functions [28]. affinity (VEA) by performing a bound-state calculation of S2 −
We have used 39ag , 20b2u , 20b3u , 16b1g , 23b1u , 18b3g , by including the continuum electron basis functions centered
18b2g , and 6au continuum orbitals for S2 . The target and at the origin. The vertical electron affinity is equal to the
the continuum orbitals of a particular symmetry form an difference in total energy of the neutral molecule and its anion
orthonormal set in the inner region; for example, the 5ag at the equilibrium geometry of the neutral molecule. We detect
orbitals of the target and 39ag orbitals of the continuum are a stable bound state of S2 − with 2 g symmetry having the
orthonormal to each other. The configuration state functions configuration 1σg2 · · · 5σg2 1σu2 · · · 4σu2 1πu4 1πg4 2πu4 2πg3 with
(CSFs) in the second term in Eq. (1) were constructed by a VEA value of 1.42 eV, which is in good agreement with
allowing the scattering electron to occupy any of the target the estimated experimental (adiabatic) value of about 1.67 ±
occupied or virtual orbitals. This term is responsible for the 0.015 eV [30] and also with theoretical data: adiabatic electron
polarization effects in the one-state CI calculation also. affinity 1.48 eV and vertical electron affinity 1.32 eV [31].
To provide additional information on the charge distribution
in the S2 molecule, we have also calculated the quadrupole
B. S2 target and scattering model moment. In our CI model the absolute value of quadrupole
The molecule S2 is a linear open-shell system that has component Q20 for the ground state is 0.668 a.u. The values
ground state X 3 g− in the D∞h point group, which is reduced of the ground-state energy and the ionization potential are
to the D2h point group when the symmetry is lowered. The compared with other works in Table I. The slight difference in
point group D2h is the highest Abelian group in our codes. the CI value of energy between this work and the other works is
The results are reported in the natural symmetry point group due to the change in the optimized bond length, which depends
as well as in the D2h point group for the sake of convenience. upon the basis set used.
We used a double zeta plus polarization (DZP) Gaussian basis In Table II, we list the quadrupole moment of each state
set [29] contracted as (12,8,1)/(6,4,1) for S. We avoided using (Q20 ), N , the number of CSFs, and the vertical excitation
diffuse functions as these would extend outside the R-matrix energies for the target states. We have good agreement with
box, which may cause linear dependency problems. We first the calculation of Tashiro [11], and reasonable agreement with
performed a SCF calculation for the ground state of the S2 [7,9,10] for vertical excitation energies.
molecule with the chosen DZP basis set and obtained a set of We have included 20 target states (2 of 1 Ag , 1 of 3 B2u , 1
occupied and a set of virtual orbitals. of B2u , 1 of 3 B3u , 1 of 1 B3u , 1 of 3 B1g , 1 of 1 B1g , 2 of 3 B1u ,
1

The Hartree-Fock electronic configuration for the ground 2 of 1 B1u , 1 of 3 B3g , 1 of 1 B3g , 1 of 3 B2g , 1 of 1 B2g , 2 of
3
state is 1σg2 · · · 5σg2 1σu2 · · · 4σu2 1πu4 1πg4 2πu4 2πg2 , which gives Au , and 2 of 1 Au ) in the trial wave function describing the
rise to the lowest-lying X 3 g − , a 1 g , and b 1 g + states. electron plus target system. However, excitation cross sections

TABLE I. Properties of the S2 target, ground-state energy (in a.u.), the rotational constant (Be , in cm−1 ), SCF at bond length Re = 3.538a0 ,
and CI at bond length Re = 3.676a0 .

Previous resultsb
Present work Previous resultsa (Re = 3.57a0 ) (Re = 3.9657a0 )
SCF CI SCF CI SCF VCI

E −794.99633 −795.03737 −795.00038 −795.14768 −793.2831 −793.2758

Be 0.301 0.280 0.299 0.292 0.2636 0.2396
a
Reference [6].
b
Reference [7].

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JASMEET SINGH RAJVANSHI AND K. L. BALUJA PHYSICAL REVIEW A 84, 042711 (2011)

TABLE II. The vertical excitation energies (eV), quadrupole moments (Q20 in a.u.), and the number of configuration state functions (CSFs),
N , for the target states of S2 at bond length Re = 3.676a0 . The experimental values, from [7], are given in square brackets.

State Present work Ref. [11] Ref. [7] Ref. [9] Ref. [10] Q20
C2v / C∞v (eV) (eV) (eV) (eV) (eV) (a.u.) N

X 3 B1g / X 3 g − 0.0 0.668 48

a(1 Ag , 1 B1g ) / a 1 g 0.603 0.60 0.674 [0.583] 0.675 0.55 0.599 60/36
b 1 Ag / b 1 g+ 0.912 0.92 1.214 [1.054] 1.214 0.99 0.572 60
c 1 Au / c 1 u− 2.808 2.77 2.145 [2.480] 2.145 2.45 0.894 36
A (3 Au ,3 B1u ) / A 3 u 2.950 2.93 2.269 [2.600] 2.269 2.59 0.882 48/48
A 3 B1u / A 3 u+ 3.047 3.03 2.343[2.724] 2.343 2.58 0.880 48
B  (3 B2g ,3 B3g ) / B  3 g 4.840 4.84 4.389[4.377] 4.390 4.36 4.127 48/48
B  (3 B2u ,3 B3u ) / B  3 u 4.945 5.03 4.364[3.930] 4.364 3.81 4.670 48/48
B 3 Au / B 3 u− 5.296 4.750[3.929] 4.750 3.89 0.9152 48
e(1 B2g ,1 B3g ) / e 1 g 5.786 5.332 5.493 5.62 3.9255 40/40
1
B2u , 1 B3u / 1 u 5.866 5.158 5.158 4.37 4.507 40/40
f (1 Au ,1 B1u ) / f 1 u 6.8 6.162[5.158] 6.162 5.56 0.850 44/36
1
B1u / 1 u+ 7.650 7.402[5.592] 5.55 0.700 44

are reported only for three excited states (a 1 g , b 1 g + , and In Figs. 3 and 4 we have shown the inelastic cross sections
B 3 u − ). Calculations were performed for doublet and quartet from the ground state to the three physical states, with vertical
scattering states with Ag ,B2u ,B3u ,B1g ,B1u ,B3g ,B2g , and Au excitation thresholds along with their quadrupole moments,
symmetries. Continuum orbitals up to l = 4 (g-partial wave) and the number of CSFs included in the CI expansion are
were included in the scattering calculation. given in Table II.
In Fig. 3 we notice sharp peaks at 2.6 eV in the cross section
of X 3 g − –a 1 g and X 3 g − –b 1 g + transitions. Each of
these resonances has a width of 0.11 eV. These resonances
III. RESULTS belong to degenerate (2 B2u and 2 B3u )2 u symmetries. We as-
sign a common configuration (4σg )2 (4σu )2 (5σg )2 (2πu )4 (2πg )3
A. Elastic and inelastic total cross sections
to these resonances, which is obtained from an attach-
The ground-state electronic configuration of S2 has two ment of the scattering electron to the excited c 1 u − ,
unpaired πg electrons. Due to vacancy in the 2πg orbital of A 3 u , and A 3 u + states of S2 with outer configuration
the ground state of S2 , the scattering electron can occupy it, (4σg )2 (4σu )2 (5σg )2 (2πu )4 (2πg )2 . The resonance properties of
forming a stable anionic ground state of S2 with symmetry these peaks are also given in Table III. In Fig. 3, we have
2
g . In our 20-state model, we found an R-matrix pole at compared our results with another R-matrix calculation [11],
−795.089545 a.u. at Re in the scattering symmetry 2 g , which which is in good agreement. We have also shown the electronic
is lower than the energy −795.037371 a.u. of the ground state excitation results, for e-O2 scattering [32] and e-SO scattering
X 3 g − of S2 , which indicates the detection of an anionic [33], using the R-matrix method. In contrast to O2 results for
bound state. We calculated the bound-state energies of this both excitation processes, there is marked resonance structure
anionic 2 g state at different bond lengths by performing an
L2 -type calculation. The potential energy curves of the 3 g −
state of the S2 molecule and the 2 g state of the S2 − anion are 6
3 -
shown in Fig. 1. The anion is stable at all the bond lengths. This Σg S 2
yields a vertical electron affinity of 1.42 eV at Re . From Fig. 1, 2
Πg S 2
-

we find that the equilibrium bond length for the ground state 4
of the S2 − anion is 4.0a0 . The S-S bond length is about 8.8%
Energy (eV)

elongated in the S2 − anionic state because the extra electron

is in a g ∗ orbital.
2
In Fig. 2, we have summed the contribution of doublet
and quartet symmetries for 20-state calculations. In this
figure we notice one peak in the cross sections at 2.6 eV.
The eigenphase sum shows a sudden jump of π rad cen- 0
tered at this position. This resonance belongs to degenerate
(2 B2u and 2 B3u )2 u symmetry. The retention of a large
number of closed electronic excitation channels in the 20- -2
3 4 5 6 7 8
state model provides the necessary polarization potential Bond length (units of a0)
in an ab initio way; this polarization potential is critical
in determining the resonance parameters of the detected FIG. 1. Ground-state potential energy curves of S2 and S2 −
resonances. molecules: dashed curve, S2 ; solid curve, S2 − .

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ELECTRON-IMPACT STUDY OF THE S2 MOLECULE . . . PHYSICAL REVIEW A 84, 042711 (2011)

150 1
Our results 2 2 2
Elastic cross sections (units of a0 )

20-state CI ( B2u / B3u) Πu

2

M. Tashiro [11]

125 0

Eigenphase sum
100 -1

75 -2

50 -3
0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5
Energy (eV) Energy (eV)

FIG. 2. Elastic cross sections of the electron impact on the S2 molecule. (left) Dotted curve, results of Tashiro [11] at bond length Re = 3.7a0 ;
solid curve, our results for 20-state CI calculations at bond length Re = 3.676a0 . (right) Eigenphase sum of (2 B2u /2 B3u )2 u symmetry for
20-state CI calculation.

in the case of S2 around 2.6 eV, and also in the SO molecule DEA experiments, the fragment negative ion yield is measured
at 4 eV. In general, the cross sections for S2 are slightly larger as a function of the kinetic energy of the incident electron. Due
because S2 is a bigger molecule than O2 or SO. to the mechanism of resonant electron capture by the neutral
Figure 4 depicts the excitation cross section for the optically molecule, a temporary negative ion is formed that may follow a
allowed transition X 3 B1g (X 3 g − )–B 3 Au (B 3 u − ) and also dissociative decay channel, in which the negative ion so formed
shows the comparison with [11] and [8]. We have also shown is sufficiently long-lived that it can be directed to a mass filter.
the contribution from each symmetry (doublets and quartets) The molecule initially in the ground state makes a vertical
in excitation cross sections for this X-B transition. We have transition to a repulsive electronic state of the scattering system
predicted a total of six resonances (two resonances in 2 Au , through which it dissociates. The study of DEA provides an
two in 2 B1g , one in 4 Au , and one in 4 B1g ). For this transition, important input in the modeling of plasmas. It is also known
the transition moment is compared with the results of [8] that the secondary electrons cause damage to DNA via DEA.
in Table IV. The resonance positions and widths are shown The present study identifies the presence of the bound state
in Table V. The Born correction is applied for this dipole of S− 2 2 2
2 in symmetry g ( B2g and B3g ) and shape resonance
2 2 2
transition in our results. This takes care of the partial-wave in u ( B2u and B3u ) symmetry. To explore the possible
contribution (l > 4) to the scattering cross section in the dissociative nature of this resonance state, we have investigated
R-matrix results. their dependence by stretching the S-S bond length from its
equilibrium value to 5a0 . This stretching mode asymptotically
B. Dissociative electron attachment correlates to the following two-body fragmentation channel:
The study of dissociative electron attachment (DEA) corre-
lates various resonances to the possible reaction channels. In S2 − (2 u ) → S(3 P ) + S− (2 P 0 ). (2)

1.25
e-O2 Noble and Burke [32]
cm )

cm )

e-O2 Noble and Burke [32]

2

0.8 3 - 1 +
3 - 1 e-SO (X Σ --> b Σ ) Rajvanshi and Baluja [33]
1 e-SO (X Σ --> a Δ) Rajvanshi and Baluja [33] e-S2 Present results
-16

-16

e-S2 Present results e-S2 M. Tashiro [11]

Excitation cross section (10

Excitation cross section (10

e-S2 M. Tashiro [11]

0.6
0.75 3 - 1
R-matrix method (X Σ g --> a Δg) 3 - 1 +
R-matrix method (X Σg --> b Σg )
0.4
0.5

0.25 0.2

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. 3. (Color online) Electron-impact excitation cross sections from the ground state: X 3 g − (3 B1g ) of the S2 molecule to the a 1 g
a ( Ag /1 B1g ) and b 1 g + b(1 Ag ), present study, solid line; Tashiro [11], dash-dotted curve; X 3 g − of the O2 molecule to the a 1 g and b 1 g + ,
1

Noble and Burke [32], dotted curve; X 3  − of the SO molecule to the a 1  and b 1  + , Rajvanshi and Baluja [33], dashed curve.

042711-5
JASMEET SINGH RAJVANSHI AND K. L. BALUJA PHYSICAL REVIEW A 84, 042711 (2011)

0.35 1.5 4
Excitation cross section (units of a0 )

Excitation cross section (units of a0 )

Ag (b) Quartets
2

2
(a) Doublets 2
Ag 4
3 - 3 - B2u 3 - 3 -
0.3 X Σg --> B Σu 2 X Σg --> B Σu
B2u 1.25 4
B3u
2 4
0.25 B3u B1g
2
B1g 1 4
B1u
0.2 2 4
B1u B3g
2
0.75 4
B3g B2g
0.15
4
2 Au
B2g 0.5
0.1 2
Au
0.05 0.25

0 0
5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10
Energy (eV) Energy (eV)

3
cm )

(c)
2

3 - 3 -
-16

X Σ g --> B Σ u
Excitation cross section (10

2
Born correction
Born corrected
Sum (Doublets + Quartets)
M. Tashiro [11]
Garrett et al
1

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

FIG. 4. (Color online) Electron-impact excitation cross sections from the ground X 3 g − (3 B1g ) state of the S2 molecule to the B 3 u−
3
( Au ) state for 20-state calculation: contribution in the excitation cross sections from each symmetry (a) in doublets and (b) in quartets.
(c) dash-dotted curve, Tashiro [11]; dashed curve, Garrett et al. [8]; thin solid line, total sum (doublets + quartets); dotted curve, Born
correction; thick solid line, Born corrected (sum of doublets, quartets, and Born correction).

C. Ionization cross section

In Fig. 5, we have shown the resonance position and the Figure 6 shows electron-impact ionization cross section of
resonance width as a function of stretching bond S-S in D2h S2 from threshold 10.02 eV to 5000 eV by using the standard
symmetry for 2 u (2 B2u and 2 B3u ). From Fig. 5 we observed formalism of the BEB model [19,20]. This formalism requires
that the resonance width and position decrease with increase the binding energy and kinetic energy of each occupied orbital
in bond length of the S-S bond and they approach zero at in a molecular structure calculation. The ionization cross
4.8a0 ; beyond this the resonance width and position vanish, section rises from threshold to a peak value of 7.7 Å2 at
which implies that these resonances become bound and support 63.96 eV and then shows ln(E/E) behavior as E approaches
dissociative electron attachment. The variation of position higher values. We have also shown the results of previous
and width of the 2 u resonance with respect to the energy theoretical works [12,14] and experimental data by Freund
of the ground state as a function of internuclear distance is et al. [13]. The molecular orbital data used in the calculation of
shown in Table VI. These data are useful to find DEA cross BEB cross sections is given in Table VII, which is generated at
sections. the SCF level, and compared with theoretical results reported

TABLE III. Resonance properties of S2 at bond length R = 3.676a0 .

Electronic configuration Er r Type of Parent

of resonant state (eV) (eV) resonance state

1(σg )2 · · ·5(σg )2 1(σu )2 · · ·4(σu )2 1(πu )4 1(πg )4 2(πu )4 2(πg )3 :2 u 2.63 0.11 Shape resonance a 1 g
1(σg )2 · · ·5(σg )2 1(σu )2 · · ·4(σu )2 1(πu )4 1(πg )4 2(πu )4 2(πg )3 :2 u 2.63 0.11 Shape resonance b 1 g+

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TABLE IV. Comparison of transition moments of allowed transitions for S2 , at bond length Re = 3.676a0 , with [8].

Transition moment1 Transition moment (this work)

Transition (a.u.) (a.u.)
3
g − → 3 u 0.033 0.046
3
g − → 3 u − 1.1 0.886
1
Garrett et al. [8].

by Kim et al. [14] using the binary-encounter-Bethe model R-matrix model. The DCS for a general polyatomic molecule
with a Gaussian basis set (6-311-G set) provided by the is given by the familiar expression
GAMESS code. For an open-shell S2 molecule, they [14]
dσ 
found that the unrestricted Hartree-Fock method produced = AL PL (cos θ ), (4)
more realistic orbital energies for valence orbitals than the d L
restricted open-shell Hartree-Fock method, which they took where PL is a Legendre polynomial of order L. The AL
as the electron binding energies as prescribed by the Koopman coefficients have already been discussed in detail [35]. For
theorem. The BEB ionization cross section σ is obtained by a polar molecule this expansion over L converges slowly. To
summing over each orbital cross section σi , where circumvent this problem, we use the closure formula
dσ dσ B 
      = + (AL − AL B )PL (cos θ ). (5)
s 1 1 1 ln t d d
σi (t) = 1 − 2 ln t + 1 − − , L
t +u+1 2 t t t +1
The superscript B denotes that the relevant quantity is
(3)
calculated in the Born approximation with an electron-point
dipole interaction. The convergence of the series is now rapid
where t = T /B, u = U/B, and s = 4π a0 2 N(R/B)2 . Here R since the contribution from the higher partial waves to the DCS
is the Rydberg energy, T is the kinetic energy of the incident is dominated by the electron-dipole interaction. The quantity
electron, U is the orbital kinetic energy, N is the electron d
dσ
for any initial rotor state |J m is given by the sum over all
occupation number, and B is the binding energy of the orbital. final rotor states |J  m ,
dσ  dσ
= (J m → J  m ), (6)
d J  m
d
D. Differential cross section where J is the rotational angular momentum and m is its
The evaluation of the differential cross section (DCS) projection on the internuclear axis. To obtain converged results,
provides a more stringent test for any theoretical model. The the maximum value is J  = 5. We have calculated the DCS
rotational excitation cross sections for electron impact on a by using the POLYDCS program of Sanna and Gianturco [36]
neutral molecule can be calculated from the scattering param- that requires basic molecular input parameters along with K
eters of elastic scattering in the fixed-nuclei approximation, matrices evaluated in a particular scattering calculation. We
provided the nuclei are assumed to be of infinite mass [34]. In have used this code to compute the DCS in a one-state CI
particular, starting from an initial rotor state J = 0, the sum of
all transitions from the J = 0 level to a high enough J value
for convergence is equivalent to the elastic cross section in the 2.5
Resonance Width/ Position (eV)

fixed-nuclei approach. We have employed this methodology 2

to extract rotationally elastic and rotationally inelastic cross Width of resonance in Πu
2 2
sections from the K-matrix elements calculated in the one-state Position of resonance in Πu

1.5
−
TABLE V. Resonance properties of S2 molecule for X g → 3

B 3 u − transition at bond length R = 3.676a0 . 1

Position Er Width r
Symmetry (eV) (eV) 0.5

2
Au 5.39 0.048
2 0
Au 5.62 0.036 3.6 3.8 4 4.2 4.4 4.6 4.8 5
2
B1g 6.20 0.06 Bond length (units of a 0)
2
B1g 6.33 0.03
4 FIG. 5. (Color online) Variation of resonance width and position
Au 6.47 0.52
4
B1g 7.00 0.45 with bond length: dashed curve, position of resonance (2 u ); solid
curve, width of resonance (2 u ).

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JASMEET SINGH RAJVANSHI AND K. L. BALUJA PHYSICAL REVIEW A 84, 042711 (2011)

TABLE VI. Position and width of the 2 u resonance with respect TABLE VII. S2 molecular orbital binding and average kinetic
to the energy of the ground state as a function of internuclear distance, energies for DZP basis set at equilibrium geometry: |B| is binding
R (a0 ). energy, U is kinetic energy, and N is occupation number.

R Position (Er ) Width r Our results Previous results

(a0 ) (eV) (eV) Molecular orbital |B| (eV) U (eV) |B|a (eV) U a (eV) N
3.676 2.63 0.11 1σg (1ag ) 2503.90 3296.83 2
3.7 2.51 0.108 1σu (1b1u ) 2503.89 3296.83 2
3.8 2.10 0.106 2σg (2ag ) 245.38 509.0 245.93 509.43 2
3.9 1.70 0.102 2σu (2b1u ) 245.37 509.25 245.92 509.43 2
4.0 1.35 0.091 3σg (3ag ) 182.24 477.69 182.81 478.98 2
4.1 1.13 0.082 3σu (3b1u ) 182.21 478.32 182.80 478.55 2
4.2 0.96 0.066 1πu (1b2u ) 182.15 478.48 182.72 478.98 2
4.4 0.65 0.052 1πu (1b3u ) 182.15 478.48 182.72 478.98 2
1πg (1b3g ) 182.15 478.51 182.72 478.28 2
1πg (1b2g ) 182.15 478.51 182.72 478.28 2
model. Since S2 is an open-shell molecule having X 3 g − as 4σg (4ag ) 29.89 62.92 29.25 60.84 2
its ground state, the spin coupling between this target state 4σu (4b1u ) 21.67 70.87 22.35 72.54 2
and the spin of the incoming electron allows two spin-specific 5σg (5ag ) 14.08 57.54 13.42 54.39 2
channels, namely the doublet (D) and quartet (Q) couplings. 2πu (2b2u ) 12.93 43.91 12.59 43.13 2
The spin-averaged DCSs for elastic electron scattering from 2πu (2b3u ) 12.93 43.91 12.59 43.13 2
the S2 molecule are calculated by using the statistical weights 2πg (2b3g ) 5.01 54.52 4.68 56.46 1
2/6 for doublet and 4/6 for quartet scattering channels. We 2πg (2b2g ) 5.01 54.52 4.68 56.46 1
then use Eq. (3) as follows to calculate the DCS: a
  Kim et al. [14]
   
dσ 1 dσ Q dσ D
= 2 + , (7)
d 3 d d
of the final rotational angular momentum J  . Because of the
where ( ddσ )Q,D
represents DCSs for quartet and doublet cases, nonpolar nature of the S2 molecule, the contribution of 0 →
respectively. 1,3,5 is much smaller (less than 0.1 × 10−16 cm2 /sr) than the
In Fig. 7 we have shown the spin-averaged DCS calculated contribution from the even J  values. The component 0 → 0 is
in the one-state R-matrix model at different energies. We have most dominant among all the components because it represents
compared our results with the results of Tashiro [11], who rotational elastic scattering. The contribution of the 0 → 2
used the angular momentum representation of the T-matrix component comes mainly from the quadrupole moment of the
elements for the first Born approximation. Our results are in molecule.
reasonable agreement with the results of Tashiro [11] at 7, 10, In addition, the data on DCS are further used to calculate
and 13 eV. In this figure we have also shown the state-to-state the momentum-transfer cross section (MTCS) that shows the
rotational components of DCSs to investigate the effect of importance of backward angle scattering. Since the DCSs
convergence of a DCS with respect to the increasing value are not very sensitive to correlation effects for backward
scattering, we expect our MTCS to be quite reliable in the
0.01–10 eV range. These are calculated in the one-state CI
M. Vinodkumar et al [12] model with spin averaging. MTCS provides a useful input in
cm )
2

8 Freund et al [13] solving the Boltzmann equation for the electron distribution
Kim et al (U/3) [14]
function. In contrast to the diverging nature of DCSs in the
-16

Present result BEB (U/3)

Ionization cross sections (10

Kim et al [14] forward direction, MTCSs show no singularity due to the

6 Present result BEB weighting factor (1 − cos θ ), where θ is the scattering angle.
This factor vanishes as θ → 0. The MTCS is useful in the
study of electrons drifting through a molecular gas. When a
4 swarm of electrons travels through a molecular gas under the
influence of an electric field, several transport observables,
such as the diffusion coefficient D and the mobility μ, can be
2 obtained if we have a knowledge of the momentum-transfer
cross sections. In Fig. 8, we have shown the calculated MTCSs
at different energies for electron collision with a S2 molecule.
0
10 100 1000
Electron energy (eV)
E. Effective collision frequency of electrons
FIG. 6. (Color online) Electron-impact BEB ionization cross
sections of the S2 molecule: dashed curve, Vinodkumar et al. [12]; The effective electron-neutral collision frequency v,
dotted curve, Kim et al. (theoretical) [14]; dash-dotted curve, Freund which is averaged over a Maxwellian distribution, can be
et al. (experiment) [13]; thick solid line, our BEB model. obtained from the momentum-transfer cross section Q(m) (v)

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ELECTRON-IMPACT STUDY OF THE S2 MOLECULE . . . PHYSICAL REVIEW A 84, 042711 (2011)

15

cm /sr)
cm /sr)

10
2 eV (b) 7 eV Our results

2
2

(a) 4 eV M. Tashiro [11]

6 eV 12

-16
-16

Differential cross section (10

Differential cross section (10

3
1

0
20 40 60 80 100 120 140 160 180 20 40 60 80 100 120 140 160 180
Angle (deg) Angle (deg)

30

cm /sr)
cm /sr)

25 (c) 10 eV Our results (d) 13 eV Our results

2
2

M. Tashiro [11] 25 M. Tashiro [11]

-16
-16

20

Differential cross section (10

Differential cross section (10

20

15
15

10
10

5 5

0 0
20 40 60 80 100 120 140 160 180 20 40 60 80 100 120 140 160 180
Angle (deg) Angle (deg)

10

Summed over all J’

(e) 4 eV J=0 --> J’=0
J=0 --> J’=2
J=0 --> J’=4
cm /sr)
2

1
-16
DCS (10

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

FIG. 7. (Color online) (a) Differential cross sections (DCSs) at 2, 4, and 6 eV. Comparison of DCS, at (b) 7, (c) 10, and (d) 13 eV, with
results of Tashiro [11]; dotted curve, Tashiro [11]; solid curve, present result (with spin average) for one-state CI model at Re ; (e) DCS at 4 eV
for state-to-state rotational components of DCS for initial state J = 0 to final state J  = 0,2,4.

as follows [37]: over a Maxwellian speed distribution function for an electron

  ∞  2 temperature Te , which is given by
8 me 5/2 −me v
v = N v 5 Q(m) (v) exp dv,
3π 1/2 2kTe 2kTe  3/2  
0 me −me v 2
(8) f (v) = 4π v 2
exp . (9)
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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JASMEET SINGH RAJVANSHI AND K. L. BALUJA PHYSICAL REVIEW A 84, 042711 (2011)

30
cm )
2

[Effective collision frequency/N] (10 s )

10

-8 -1
-16
Momentum transfer cross sections (10

<υ>
25 ⎯υ

20

15
0 1 2 3 4 5 6 7 8 9 10
Energy (eV) 1000 10000
Electron temperature (K)
FIG. 8. Momentum transfer cross sections, at different energies,
with spin average of S2 molecule ground state at one-state CI level. FIG. 9. (Color online) Effective collision frequency as a function
of electron temperature: dashed curve, v̄; solid curve, v.
collision frequency for electrons can be defined from the dc
conductivity as follows [37,38]: We obtained a value of 2.615a0 for the scattering length.
    Then we evaluated the cross section σ = 4π a 2 corresponding
8 me 5/2 ∞ v 3 −me v 2
v̄ −1 = exp dv. to this scattering length, which is equal to 85.866a0 2 ; this
3π 1/2 N 2kTe 0 Q(m) (v) 2kTe
result is comparable with the cross section 85.7a0 2 at the same
(10) energy (E = 0.025 eV) coming from the direct calculation
This explicit form of effective collision frequency v̄ is related (R-matrix method).
to the drift velocity of electrons in a gas, insofar as a Maxwell
distribution can be assumed. When Q(m) (v) is proportional to IV. CONCLUSIONS
v −1 , the two effective collision frequencies, v and v̄, agree.
In Fig. 9, we have shown both types of effective collision This is a comprehensive ab initio study of electron impact
frequencies as a function of electron temperature. It is to on the S2 molecule using the UK molecular R-matrix codes.
be noted that v lies higher than v̄ in the entire electron Elastic (integrated and differential), momentum-transfer, ex-
temperature range. citation, and ionization cross sections have been presented.
The results of the static-exchange, one-state CI, and 20-state
close-coupling approximations are presented. We detect a
F. Scattering length
stable bound state of S2 − with a vertical electronic affinity
We have also evaluated scattering length in our study of value of 1.42 eV, which is in good agreement with the estimated
electron impact on the S2 molecule. In this procedure we experimental value of about 1.67 ± 0.015 eV. The target states
have included only an s-wave approximation for the scattering are represented by including correlations via a configuration-
electron. The scattering length is given by interaction technique. Our target calculations give reasonable
− tan δ0 agreement with the calculated vertical excitation spectrum of
,k → 0, a= (11) Tashiro [11], Swope et al. [7], Wang et al. [9], and Kiljunen
k
et al. [10]. We have also reported the quadrupole moment for
where δ0 is the eigenphase sum corresponding to the energy each state. We detected two resonances, both of 2 u symmetry,
(E = 0). In practice, we have chosen E = 0.025 eV to in the excitation cross sections of the states 1 g and 1 g + .
compute a. Here k is the wave number of the scattering The dissociative nature of these resonances is explored by
electron. performing scattering calculations in which the S-S bond is
We have calculated scattering length separately for doublets stretched. These resonances support dissociative attachment,
(aD ) and quartets (aQ ); the spin-averaged scattering length is yielding S and S− . The derived MTCS from the DCS and
given by two types of effective collision frequencies have also been
1/2 presented. We have also evaluated the scattering length of the
a= 1
(a 2
3 D
+ 2aQ 2 ) . (12) S2 molecule, which is equal to 2.615a0 .

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