Journal of Electron Spectroscopy and Related Phenomena 185 (2012) 625–629

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Journal of Electron Spectroscopy and

Related Phenomena
journal homepage: www.elsevier.com/locate/elspec

Short communication

Electron impact ionization cross sections of the CO2 clusters

Satyendra Pal a,∗ , Rajeev Kumar b , R. Singh a
a
Department of Physics, M.M.H. College, Ghaziabad 201009, India
b
Department of Physics, D.J. College, Baraut, Baghpat 250611, India

a r t i c l e i n f o a b s t r a c t

Article history: The modified Jain–Khare semi-empirical formalism for the evaluation of differential and integral electron
Received 18 June 2012 impact ionization cross sections for molecules has been extended to the evaluation of cross sections for
Received in revised form 8 October 2012 the electron ionization of CO2 clusters: (CO2 )240 and (CO2 )1700 . The energy dependent differential cross
Accepted 27 October 2012
sections are evaluated at the incident electron energies of 50, 100 and 200 eV. The integral total ionization
Available online 17 November 2012
cross sections have been calculated in the energy range varying from ionization thresholds to 1000 eV
which revealed a good agreement with the available experimental and the theoretical data. The ionization
PACS:
rate coefficients have also been evaluated using the presently calculated ionization cross sections and
36.90fg
Maxwell–Boltzmann energy distributions.
Keywords: © 2012 Elsevier B.V. All rights reserved.
Clusters
Cross sections
Electron impact
Rate coefficients

Recently, we have introduced a revisited Jain–Khare semi-
empirical formulation [1] for the calculation of partial and total
integral ionization cross sections for the C60 and C70 fullerenes
in the energy range from ionization threshold to 1000 eV which
yielded results in satisfactory agreement with available experimen-
tal and theoretical data [2,3]. Subsequently, we have extended and
generalized the same formulation for the evaluation of single dif-
ferential and integral ionization cross sections corresponding to
molecular clusters as a testimony of CO2 , viz. (CO2 )240 and (CO2 )1700
where the experimental and/or the theoretical data is available
for comparison of the present results. The necessity to rely on
this approach for the calculation of ionization cross sections for
clusters/fullerenes arises as it provides results in reasonably good
agreement with experimentally measured cross sections, within
experimental error bars, for several molecules of variety [4,5]. A
cluster is an ensemble of monomers encompassing a large num-
ber of constituents and geometrical structures ranging from a
hard sphere packing arrangement to a hollow cage structure. The
study of carbon fullerenes has attracted an enormous amount of
interest in recent years, both from the experimental and the theo-
retical viewpoints because of its characteristic electronic structure
reflecting its unique geometry. The exceptional stability, very high
symmetry and several other molecular properties may provide the
basis for important applications of CO2 clusters [6].
∗ Corresponding author.
E-mail addresses: s.pal@india.com, satyendrapal1@rediffmail.com (S. Pal).
In this letter, we have evaluated the differential cross sections
as a function of ejected primary or secondary electron energy for
the CO2 clusters, viz. (CO2 )240 and (CO2 )1700 at fixed incident elec-
tron energies of 50, 100 and 200 eV. The integral ionization cross
sections corresponding to these clusters are also evaluated in the
incident electron energy range varying from ionization threshold to
1000 eV. Notwithstanding the only experimental study of Vistrokov
et al. [7] on the ionization cross sections for these clusters is avail-
able in the literature. From a theoretical standpoint, calculations
for clusters are particularly challenging. Recently, Deutsch et al. [8]
extended their Deutsch and Märk (DM) formalism and the semi-
empirical concept, based on the modified additive rule (MAR) [9]
for the calculations for the total cross sections for clusters including
those of CO2 clusters and hence, presently, it is obvious to consider
(CO2 )240 and (CO2 )1700 . The present calculations for the ionization
cross sections leading to the single ionization of these clusters are
compared with the available experimental [7] and the theoretical
data [9] in the complete energy range covered in the present calcu-
lations. Moreover the DM formulation has provided total ionization
cross sections for a large number of atoms and molecules along-
with several atomic and molecular clusters [10,11]. A complete
description of DM formulation [8] and other established formula-
tions including those of Jain–Khare (JK) semiempirical formulation
[1] and Binary Encounter Bethe (BEB) formulation [12] for the eval-
uation of ionization cross sections for molecules are given in the
recent review article of Märk and co-workers [10]. Recently, Tribedi
and co-workers [13,14] have carried out the intensive study on the
fast heavy ion collision with the C60 fullerene. In their measure-
ments they highlighted the several structural properties including

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626 S. Pal et al. / Journal of Electron Spectroscopy and Related Phenomena 185 (2012) 625–629

Fig. 1. Single differential cross sections (SDCS) verses secondary electron energy in terms of energy loss W (sum of ionization threshold and the secondary electron energy)
for the CO2 molecule and its clusters following the electron impact ionization at 50, 100 and 200 eV.

those of giant resonance signatures and collective effects at micro- strengths dfi /dW, as a major input, that is directly proportional
scopic level in single and multiple ionization of fullerene. to the photoionization cross sections. In the present study, we
In addition to the differential and integral ionization cross have used the photoionization cross section data for CO2 in the
sections, we have also evaluated the ionization rate coefficients energy range 8–75 eV from the reliable experimental measurement
for clusters using the calculated ionization cross sections and of Hitchcock et al. [17]. These measurements were within ∼5%
Maxwell–Boltzmann distribution for the electrons as a function of uncertainty. Above 75 eV, we have extrapolated valance-shell pho-
energy [15]. The rate coefficient is an important parameter as input toionization cross-section data measured by Hitchcock et al. [17]
in various plasma processes and plasma modelling [16]. using Thomas–Reiche–Kuhn (TRK) sum rule. The collision param-
The secondary electron energy dependent cross sections, i.e. the eter Ci and energy parameter ε0 were employed as in the case of
single differential cross sections corresponding to the formation of CO2 [18]. The integral ionization cross sections Q(E) is evaluated by
the particular or ith type of ion in the ionization of a molecule by  E
the incident electron of energy E given by Qi (E,W) was already dis-
QiCO2 (E) = Qi (E, W )dW (2)
cussed in our papers [2–5] and will not be reiterated here in detail.
Ii
Evanescently, the energy dependent differential cross section at a
fixed incident electron energy E is given by The (CO2 )240 and (CO2 )1700 clusters have 240 and 1700
4a2 R
   monomers, i.e. CO2 . The effective differential and integral ioniza-
 R dfi(w,0)
QiCO2 (E, W ) = 0
E
1
(1+Ii /E)
1− E−Ii w dw ln(1 + C(E − Ii )) tion cross sections for these clusters are thus evaluated from the
  corresponding differential and integral cross sections of the CO2
+Si
(E−Ii )R
− 2
+ 3
(1) molecule, i.e. monomer from Eqs. (1) and (2), using a scaling rela-
E( 3 + 3 ) (E−) (E−) 2
tion, described elsewhere [9]. The differential cross section is given
0i
as
Symbols used in the Eq. (1) have their usual meanings [4,5].
The present formulation (Eq. (1)) requires the dipole oscillator Qicluster (E, W ) = m(2a−1) QiCO2 (E, W ) (3)
 S. Pal et al. / Journal of Electron Spectroscopy and Related Phenomena 185 (2012) 625–629 627

25 20

total ionization cross sections (10-17cm2 )

total ionization cross sections (10-17 cm2)
(CO2)240 (CO2)1700
20
15

15

10

10

5
5

0 0
0 200 400 600 800 1000 0 200 400 600 800 1000
E(eV) E(eV)

5
Total Ionizaon Cross Secons (10 -16 cm 2)

CO2
4

0
10 100 1000
E(eV)

Fig. 2. Total ionization cross section profiles corresponding the (CO2 )240 and (CO2 )1700 clusters along with the monomer CO2 by electron impact ionization (designated with
solid lines) in comparison with the experimental data designated by: – Vostrikov et al. [7] (with experimental error bars) for clusters, ♦ – Rapp and Englander-Golden [22],
 – Itikawa [23],  – Stebbings and Lindsay et al. [24], – Hudson et al. [25], and  – Orient and Srivastava [26] and the theoretical data designated by: – Deutsch et al.
[9] (for clusters), – BEB calculations [12] and – DM calculations (see Ref. [25]).

and the integral cross sections the monomer and other molecular targets [4,5]. The differential
cross sections are symmetrical about energy E/2 where the ener-
Qicluster (E) =m (2a−1)
QiCO2 (E) (4)
gies of primary and the secondary electrons in the exit channel are
where m is the number of monomers in the cluster. Exponent a equal. Above E/2, the energy transfer from incident/primary elec-
(=1/3) is a constant equal to hard-sphere packing fraction [19,20], tron to the secondary, increases up to the maximum, i.e. incident
however its best fit values lie between 0.4 and 0.5 [9]. In our calcula- electron energy (E − Ii ). The differential cross sections, especially,
tions, we have used a = 0.44 as the same employed by Deutsch et al. near threshold region are accompanied with the oscillations, struc-
[9]. The estimated error in our calculations is expected as the same tures and resonances, obviously due to the different path of
as for the measurement of the photoionization cross sections. As ionization.
CO2 is the fundamental unit for the formation of these clusters, in Fig. 2 shows the comparison of our integral ionization cross-
the ionization of these clusters, the ejection of electron is possibly section profiles for clusters with experimental [7] and theoretical
through the cavity resonances involving spherical standing waves data [9]. For the check of the accuracy of the cluster ionization cross
[21]. sections, the total ionization cross section for monomer is also com-
It is noted that the secondary electron energy dependent cross pared with the only recent established experimental [22–26] and
sections or the single differential cross sections for (CO2 )240 and the BEB calculations [12] and DM calculations carried out by Hud-
(CO2 )1700 along with monomer the CO2 molecule by the incident son et al. [25]. The numerical values are also presented in Table 1.
of electron at fixed incident electron energies of 50, 100 and 200 eV Our calculated results for monomer are in excellent agreement with
are shown in the Fig. 1. The cluster cross sections are several times the reliable experimental [22–26] and theoretical data [12,25]. It is
smaller than that of the corresponding monomer. No experimen- interesting to note that the cross sections corresponding to the clus-
tal data is available for comparison of our results for differential ters are also in good agreement with the only experimental data [7]
cross sections. However, the behaviour of the differential cross and the theoretical calculations [9]. At peak, our results for (CO2 )240
sections with secondary electron energy is almost similar as to and (CO2 )1700 are about 20% and 10%, respectively, higher than the
628 S. Pal et al. / Journal of Electron Spectroscopy and Related Phenomena 185 (2012) 625–629

Table 1
Table for integral ionization cross sections for monomer CO2 and its clusters, viz. (CO2 )240 and (CO2 )1700 versus incident electron energy E.

E (eV) Qi (E) (×10−17 cm2 ) E (eV) Qi (E)(×10−17 cm2 )

CO2 (CO2 )240 (CO2 )1700 CO2 (CO2 )240 (CO2 )1700

19 3.98 2.06 1.63 155 34.7 17.97 14.23

25 11.2 5.80 4.59 165 34.1 17.66 13.98
31 17.6 9.12 7.22 185 32.9 17.04 13.49
41 25.2 13.05 10.33 200 32.2 16.58 13.12
51 30.0 15.54 12.30 250 29.1 15.07 11.93
61 32.9 17.04 13.49 300 36.5 13.73 10.87
71 34.7 17.97 14.23 350 24.4 12.64 10.00
81 35.8 18.54 14.68 400 22.5 11.66 9.23
91 36.3 18.80 14.88 450 20.9 10.83 8.57
95 36.4 18.86 14.92 500 19.6 10.15 8.04
101 36.5 18.91 14.97 600 17.3 8.86 7.01
115 36.4 18.86 14.92 700 15.6 8.08 6.40
125 36.1 18.70 14.80 800 14.2 7.36 5.82
135 35.7 18.49 14.64 900 13.0 6.73 5.33
145 35.2 18.23 14.43 1000 12.1 6.27 4.96

experimental data (the data is accomplished with uncertainty of

25%) [7].
On the other hand, the theoretical data [9] based on the addi-
tive rule show the similar trend as the experimental data [7].
In their theoretical calculations, Deutsch et al. [9] employed the
experimental cross sections for monomer measured by Rapp and
Englander-Golden [22]. Most recently, we have also applied the
same formulation for the evaluation of partial and total ionization
cross sections for H2 clusters, viz. (H2 )n (n = 48,000, 85,000) and the
results revealed a satisfactory agreement with experimental data
[27]. The shapes of the present results for CO2 clusters are in consis-
tence with the H2 clusters [27] that predicts supportive information
on the capabilities of the present semi-empirical formulation for
the evaluation of ionization cross sections for molecular clusters.
Despite the relevance of clusters from a fundamental view point
as a new state of matter and despite the important role of clusters
in many technological applications, there have been few quanti-
tative investigations of the collisional interaction of electrons and
ions with clusters. Reliable data are particularly scarce for electron
impact ionization processes. This is due to experimental difficulties
e.g. due to the fact that the collisional interaction of an electron with Fig. 3. Ionization rate coefficients as a function of electron energy for CO2 and its
a comparatively weakly bound cluster often results in a break-up clusters, viz. (CO2 )240 and (CO2 )1700 by electron impact ionization designated with
of the cluster rather than in its ionization [28]. The present calcula- solid lines.

tions for ionization cross sections satisfy the necessary consistency

checks to access their consistency and reliability. The consistency
checks derived from the fact that the total integral ionization cross
sections corroborate the area covered by the single differential
cross sections at the respective incident electron energies. In low
energy limits, close to the onset of ionization, the shapes of the total
electron impact ionization cross section curves are governed by the
certain threshold law [29]. The precise shape of the cross section
in this region is especially important in determination of respec-
tive ionization thresholds, to compare with those derived by other
means. The most surprising result in the present study is that the
relative magnitude of the ionization cross sections is quite different
from those of ordinary polyatomic molecules [4,5,18]. In addition
to the ionization cross sections, the ionization rate coefficients as a
function of electron temperature shown in Fig. 3, have been eval-
uated using the calculated cross sections and Maxwell–Boltzmann
distribution of the electrons energy. Again there is no data for com-
parison of the present results however the trend of the curves is
the same as expected.
The accuracy of present results provides a justification of the
use of the present formalism for the calculation of cross sections for
these clusters, especially, in the low energy regime. The basis of the
accuracies of results provide the framework to develop predictive
capabilities that allow us to evaluate the ionization cross sections
for other clusters including those of van der Waals clusters where
the experimental and theoretical data are scarcely available.
Acknowledgements
R. Singh is thankful to the Department of Science and Technol-
ogy for awarding Junior Research Fellowship Award with Grant No.
PS/0008/2011 (SERC/DST). Authors wish to acknowledge the useful
comments of the revered referee(s).
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