New Journal of Physics The open–access journal for physics

Absolute elastic cross-sections for low-energy

electron scattering from tetrahydrofuran
C J Colyer1,2,3 , V Vizcaino1,2 , J P Sullivan1,2 , M J Brunger1,3
and S J Buckman1,2,4
1
Centre for Antimatter–Matter Studies
2
Research School of Physical Sciences and Engineering,
Australian National University, Canberra 0200, Australia
3
SOCPES, Flinders University, GPO Box 2100, Adelaide 5001,
South Australia, Australia
E-mail: [email protected]
New Journal of Physics 9 (2007) 41
Received 14 December 2006
Published 26 February 2007
Online at http://www.njp.org/
doi:10.1088/1367-2630/9/2/041

Abstract. We present results for elastic electron collision cross-sections with

tetrahydrofuran (C4 H8 O) in the energy range of 6.5–50 eV. The absolute cross-
sections are determined from crossed beam measurements using the relative
flow technique and cover the angular range between 10◦ and 130◦ . Integral and
momentum transfer cross-sections have also been derived from these results. The
data, where possible, are compared to recent experimental results and theoretical
calculations.

Contents

1. Introduction 2
2. Experimental apparatus 3
3. Results and discussion 4
4. Conclusion 9
Acknowledgments 10
References 10

4
Author to whom any correspondence should be addressed.

New Journal of Physics 9 (2007) 41 PII: S1367-2630(07)39286-0

1367-2630/07/010041+11$30.00 © IOP Publishing Ltd and Deutsche Physikalische Gesellschaft
2 DEUTSCHE PHYSIKALISCHE GESELLSCHAFT

1. Introduction

Ionizing radiation is used widely in medicine as a probe in radio-diagnostic examinations and as

a genotoxic agent in radiotherapy. It has been the commonly held belief that ballistic, high energy
impacts were responsible for the bulk of cell and tissue damage when ionizing radiation enters
the body. In recent years, experimental studies have indicated that secondary species generated
by the primary ionizing particle can also play a significant role in radiation damage to DNA [1, 2].
Upon entering the body, high energy ionizing radiation quickly thermalizes through various
scattering processes that liberate large numbers of low energy (0–20 eV) secondary electrons.
These electrons then interact with bio-molecules such as water [3, 4], sugars [5] and DNA
bases [6]–[11], and have been shown to cause significant damage to DNA through the process
of dissociative attachment [12, 13]. This either directly leads to single or double DNA strand
breaks, or results in the formation of free radicals, which can then chemically react with DNA
to lead to strand breaking.
In this present experiment, we have investigated electron collisions with the tetrahydrofuran
(THF) molecule using the crossed beam method. THF is a common organic solvent used in large
amounts for a variety of industrial purposes [14]. There is also significant interest in THF as it
presents a simple model for the deoxyribose building block of DNA. In particular, the backbone
of DNA may be considered as a series of THF molecules held together by phosphate bonds to
which the important bases are attached. The objective of the present study is to understand how
electrons interact with this simple model of part of the DNA backbone. Such studies may help to
understand the mechanism of dissociative electron attachment, and the measurement of absolute
scattering information can be used to both test, and aid, the development of quantum scattering
theory for such bio-molecules.
THF has previously been the subject of several theoretical and experimental studies. Early
study by Le Page et al [15] was focused on differences in electron spectroscopy between
the gas and solid phases. A resonance feature is reported for gaseous THF at 8.5 eV in the
vibrational excitation of the C–H stretch modes, but is shifted about 1 eV lower for the solid-
state measurements. Low-energy electron damage in the solid phase was reported by Breton
et al [16], who discuss the production of aldehydes in terms of electron resonances, and also list
previous investigations with gas, liquid and solid state THF.
Several absolute experimental scattering measurements in the gas phase have appeared
more recently. Zecca et al [17] reported grand total cross-section (GTCS) measurements for
both electrons and positrons at energies below 21 eV, while Mozejko et al [18] reported
similar measurements, using electrons only, from 1–370 eV. Both groups observe a broad shape
resonance centred around 6–8 eV in the GTCS. The first differential cross-sections (DCS)
for elastic electron scattering were published by Milosavljevic et al [19] in the energy range
20–300 eV for scattering angles ranging from 10 to 110◦ . A recent publication also reports
elastic DCS and vibrational excitation of the C–H stretch modes at 10 eV and for scattering
angles from 20 to 180◦ [20].
Theoretical investigations concerning THF have also become more common in recent times.
DCS for elastic electron scattering have been computed by Mozejko and Sanche [21] using the
independent atom method (IAM) for collision energies in the range 50–2000 eV. They also
calculated the cross-section for electron impact ionization of THF, from the ionization threshold
up to energies of 4000 eV. Integral cross-sections, both elastic and electronically inelastic, have
been calculated for THF by Bouchiha et al [22] using the R-matrix method, at collision energies

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3 DEUTSCHE PHYSIKALISCHE GESELLSCHAFT

from 1–10 eV. Although they did not observe a shape resonance, a few core-excited resonances
are reported. Trevisan et al [23] completed calculations of DCS and momentum transfer cross-
sections (MTCS) of elastic electron scattering by THF using the complex Kohn variational
method, and report a broad shape resonance in the 8–10 eV energy range in the MTCS. Elastic
integral cross-sections for both THF and phosphoric acid, which constitutes the remainder of
the DNA backbone, have been computed by Tonzani and Greene [24], who also use a variation
of the R-matrix method. Resonances for THF have been observed around 8.6 and 14.1 eV, but
the authors indicate that their model usually predict resonances 1–2 eV higher than experiment
due to the use of the static exchange approximation. Most recently Winstead and McKoy [25]
published elastic integral, DCS and MTCS from deoxyribose and related molecules, including
THF. Using the Schwinger multichannel method, shape resonances in the integral cross-section
and MTCS of THF are reported at energies of 8.3 and 13.5 eV, after compensating for the static
exchange approximation.

2. Experimental apparatus

Elastic electron scattering from THF has been studied using a crossed electron-target beam
apparatus. The THF vapour has been obtained from a liquid sample of THF, which has a purity
greater than 99% (Sigma–Aldrich Australia), and has been further purified by a number of freeze,
pump and thaw cycles. It is admitted to the scattering system at a relatively low driving pressure
via a temperature-controlled needle valve and gas-handling system. To prevent condensation,
the needle valve and gas lines are heated to about 323 K and the beam-forming needle, by which
the gas enters the collision region, is maintained near 348 K.
The monoenergetic (FWHM ∼70 meV) electron beam is obtained from a conventional
electron monochromator, and scattered electrons are energy analysed before being detected by
a channel electron multiplier. The absolute value of the incident energy was determined through
calibration against the position of the negative ion resonance feature for electron scattering from
helium at 19.365 eV [26]. The experimental apparatus has been described in detail in a number
of previous publications (e.g. [27]).
To determine absolute cross-sections the relative flow technique is implemented. The
technique involves measuring the relative electron scattering intensities for the gas under study
and for a standard gas for which there is an accurate set of DCS, in our case THF and helium
respectively. The variational calculations of Nesbet [28] for the He cross-section is used as
the absolute calibration for energies below 20 eV, and the rational function fits of Boesten and
Tanaka [29] to a range of helium cross-sections are used for the higher energy measurements.
The driving pressures for both gases are determined such that the collisional mean free path
in the beam-forming needle are the same, and thus the collision-dependent profile of the gas
beams should be identical in the collision volume, which is situated just above the needle exit.
Initially the hard sphere diameter for THF, from which the mean free path is calculated, was
estimated using molecular bond lengths. However, this value was found to be similar to hard
sphere diameters determined via both the Lennard–Jones model [30] and the equation of state.
In order to test the effect that these different values might have on the DCS, we conducted
measurements using different values for the hard sphere diameter, and thus different driving
pressures for THF. These different operating conditions appeared to have no significant effect on
the DCS in the region around the calculated values. Typical driving pressures used were 0.2 Torr
for THF and 1.0 Torr for He.

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4 DEUTSCHE PHYSIKALISCHE GESELLSCHAFT

Table 1. Experimentally determined DCS for elastic electron scattering by gas

phase THF, in units of 10−16 cm2 sr −1 , as a function of scattering angle and incident
energy. Integral and MTCS in units of 10−16 cm2 are shown at the foot of each
column. Absolute errors are given in parentheses. The uncertainty in the integral
cross-sections is estimated to be 20–25%.
E0 (eV)

θ (◦ ) 6.5 8 10 15 20 30 40 50

10 – – – – – – – 69.0(5.48)
20 – – 17.4(2.87) 16.1(3.52) 21.4(2.07) 23.7(2.76) 15.3(1.26) 11.1(0.84)
25 9.62(0.86) 10.4(1.78) – – – – – –
30 6.16(0.65) 6.34(0.72) 7.66(0.60) 7.00(0.73) 5.09(0.38) 3.80(0.31) 2.36(0.18) 1.79(0.14)
40 3.34(0.28) 3.29(0.38) 3.17(0.25) 2.38(0.20) 2.07(0.16) 1.69(0.12) 1.32(0.10) 1.08(0.08)
50 2.47(0.28) 2.33(0.19) 2.27(0.18) 1.86(0.16) 1.65(0.12) 1.21(0.10) 0.90(0.07) 0.75(0.05)
60 2.13(0.17) 1.83(0.15) 1.82(0.14) 1.50(0.11) 1.31(0.12) 0.91(0.07) 0.67(0.05) 0.49(0.04)
70 1.57(0.15) 1.45(0.13) 1.51(0.11) 1.32(0.10) 1.14(0.11) 0.71(0.06) 0.45(0.04) 0.31(0.03)
80 1.27(0.11) 1.49(0.11) 1.48(0.11) 1.27(0.10) 1.02(0.10) 0.55(0.05) 0.34(0.03) 0.27(0.02)
90 1.43(0.12) 1.74(0.13) 1.63(0.12) 1.26(0.11) 0.92(0.10) 0.47(0.05) 0.33(0.04) 0.25(0.02)
100 1.89(0.15) 2.03(0.15) 1.79(0.14) 1.35(0.11) 0.89(0.10) 0.51(0.06) 0.38(0.05) 0.24(0.02)
110 2.45(0.19) 2.30(0.17) 1.97(0.16) 1.45(0.13) 0.99(0.12) 0.66(0.09) 0.53(0.08) 0.32(0.02)
120 2.79(0.23) 2.57(0.19) 2.24(0.18) 1.54(0.16) 1.11(0.14) 0.94(0.11) 0.82(0.14) 0.49(0.05)
130 2.93(0.27) 2.63(0.20) 2.42(0.18) 1.57(0.15) 1.30(0.16) 1.26(0.16) 1.22(0.23) 0.74(0.08)
Qi 41.01 38.18 40.97 36.93 37.71 33.38 27.81 22.95
Qm 29.31 28.26 29.72 20.46 19.20 14.82 14.02 7.71

3. Results and discussion

Absolute DCS for electron scattering from the THF molecule at eight incident energies between
6.5 and 50 eV are presented in table 1. They are also shown in figures 1 and 2, together with
other available experimental and theoretical cross-sections. The energy dependences of the elastic
scattering cross-section for scattering angles of 60, 90 and 120◦ are also shown in figure 3. The
elastic integral and MTCS are presented at the foot of each column of DCS data in table 1 and
are shown in figure 4. The experimental uncertainties on the present DCS vary typically from
7 to 10%, and in a few cases are as high as 20%. The estimated errors on the derived elastic
integral and MTCS are 15–20%.
In figures 1 and 2, a comparison is made at selected energies between the present data, the
theoretical calculations of Trevisan et al [23] and Winstead and McKoy [25] and the experimental
DCS of Milosavljevic et al [17, 18] and Dampe et al [31]. At both 6.5 and 8 eV (figures 1(a) and
(b)) the present values are in excellent agreement with both of the theoretical calculations across
the entire angular range. Note that in figure1(a) the calculation of Trevisan et al is at the slightly
different energy of 6 eV. We also note that at this energy the cross-section is quite large, being
everywhere greater than 1 × 10−16 cm2 sr −1 . At 10 eV, once again the agreement between the
two theoretical calculations and the present experiment is excellent across the entire, common
angular range. At 15 eV (figure 1(d)) in addition to comparison with the theoretical calculations,
we can also compare with the recent results of Dampe et al. The level of agreement between

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5 DEUTSCHE PHYSIKALISCHE GESELLSCHAFT

(a) (b)

THF 6.5 eV THF 8.0 eV

elastic elastic
Present Data Present Data
Trevisan et al. (6 eV) Trevisan et al.
10 Winstead & McKoy Winstead & McKoy

10
DCS (10 cm /sr )

DCS (10 cm /sr)

2

2
-16

-16
1

1
0 30 60 90 120 150 180 0 30 60 90 120 150 180
Scattering Angle (deg.) Scattering Angle (deg.)

(c) (d)
100
THF 10 eV THF 15 eV
elastic elastic
Present Data Present Data
Trevisan et al. Dampe et al.
Winstead & McKoy Trevisan et al.
Winstead & McKoy
10
DCS (10 cm /sr)

DCS (10 cm /sr)

2

10
-16

-16

1 1

0 30 60 90 120 150 180 0 30 60 90 120 150 180

Scattering Angle (deg.) Scattering Angle (deg.)

Figure 1. Absolute DCS (in units of 10−16 cm sr −1 ) for electron scattering from
THF at energies of (a) 6.5 eV, (b) 8.0 eV, (c) 10 eV and (d) 15 eV. The key to the
data is shown on each plot.

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6 DEUTSCHE PHYSIKALISCHE GESELLSCHAFT

(a) (b)
100
THF 20 eV THF 30 eV
Elastic Elastic
Present Data Present Data
Milosavljevic et al. Milosavljevic et al.
Trevisan et al. Winstead & McKoy
Winstead & McKoy 10
DCS (10 cm /sr)

DCS (10 cm /sr)

2

2
10
-16

-16
1

0 30 60 90 120 150 180 0 30 60 90 120 150 180

Scattering Angle (deg.) Scattering Angle (deg.)
(c) (d)
100

THF 40 eV THF 50 eV
100
Elastic Elastic
Present data Present Data
Milosavljevic et al. Milosavljevic et al.
Winstead & McKoy Mozejko & Sanche
10 Winstead & McKoy
10
DCS (10 cm /sr)

DCS (10 cm /sr)

2

2
-16

-16

1
1

0.1 0.1
0 30 60 90 120 150 180 0 30 60 90 120 150 180
Scattering Angle (deg.) Scattering Angle (deg.)

Figure 2. Absolute DCS (in units of 10−16 cm2 sr −1 ) for electron scattering from
THF at energies of (a) 20 eV, (b) 30 eV, (c) 40 eV and (d) 50 eV. The key to the
data is shown on each plot.

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7 DEUTSCHE PHYSIKALISCHE GESELLSCHAFT

(a) (b)
4 2.5
o
THF 60 THF 90
o Present Data
3.5 from DCS
Elastic 2 Elastic Trevisan et al.
3 Present Data Winstead & McKoy

DCS (10 cm /sr)

DCS (10 cm /sr)
from DCS
2.5

2
2

Trevisan et al. 1.5

Winstead & McKoy

-16
-16

1.5 1

1
0.5
0.5

0 0
0 5 10 15 20 25 0 5 10 15 20 25
Energy (eV) Energy (eV)

(c)
4
o
3.5 THF 120 Present Data
from DCS
Elastic Trevisan et al.
3
Winstead & McKoy
DCS (10 cm /sr)

2.5
2
-16

1.5

0.5

0
0 5 10 15 20 25
Energy (eV)

Figure 3. Absolute excitation functions (in units of 10−16 cm2 sr −1 ) for elastic
scattering from THF at (a) 60◦ , (b) 90◦ and (c) 120◦ . The key to the data is shown
on each plot.

the two experimental cross-sections is very good at all angles, and once again there is
generally good accord with the two theoretical calculations, in particular that of Winstead and
McKoy.
At an energy of 20 eV (figure 2(a)) the present experimental DCS can be compared with that
of Milosavljevic et al [17, 18] and we see relatively good agreement in both shape and magnitude
of the DCS. The present cross-section is also in excellent agreement with the calculated values of
Winstead et al but is about a factor of two lower than the Kohn variational calculation above about
60◦ . At 30 eV (figure 2(b)) the present cross-section is slightly lower than that of Milosavljevic
et al at most angles less than 90◦ and, while it is in good agreement with the Schwinger variational
calculation at forward and backward angles, it lies about 30–40% below the theory between
50–110◦ . Very similar trends between the two experimental data sets, and between experiment
and theory, are seen at energies of 40 and 50 eV (figures 2(c) and (d) respectively). At 50 eV it is
also possible to compare with the independent atom model calculation of Mozejko and Sanche
which predicts the shape of the cross-section rather well but is larger than experiment at all
angles by between 10 and 50%. We note also that at this and other energies at forward angles, the
Schwinger variational calculation is significantly lower in magnitude than the experimental cross-
sections, principally because there is no explicit inclusion of the long-range dipole interaction
through a Born-type approach.
In addition to the angular DCS determinations, measurements of the energy dependence of
the elastic cross-section at a number of fixed scattering angles (elastic ‘excitation functions’or EF)

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8 DEUTSCHE PHYSIKALISCHE GESELLSCHAFT

(a)
100
THF
Integral Elastic
80 Present Data (Elastic ICS)
Mozejko et al. (Total CS)
Zecca et al. (Total CS)
ICS (10 cm )
2

Bouchiha et al. (Total CS)

60
Winstead & McKoy (Elastic ICS)
-16

40

20

0
0 5 10 15 20 25
Energy (eV)

(b)
60
THF
50 Elastic Momentum Transfer
Present Data
MTCS (10 cm )

Trevisan et al.
2

40
Winstead & McKoy
-16

30

20

10

0
0 5 10 15 20 25
Energy (eV)

Figure 4. (a) Integral elastic and (b) elastic MTCS for electron scattering from
THF in units of 10−16 cm.

have been performed. A comparison of these EF, at scattering angles of 60, 90 and 120◦ , with
the Kohn variational and Schwinger variational calculations is made in figures 3(a)–(c). The data
from the angular DCS measurements are also shown where applicable and, in general, these are
in very good agreement with the EF results. At a scattering angle of 60◦ (figure 3(a)) the energy
dependence and magnitude of all the cross-sections are in good agreement, and each indicate the
(weak) presence of a shape resonance around 6–8 eV. At 90◦ (figure 3(b)) the EF measurement
and DCS data are in excellent agreement with the calculation of Winstead and McKoy, while
the Kohn variational calculation shows a similar energy dependence but the features are shifted
about 2 eV higher in energy relative to the experiment. At 120◦ (figure 3(c)) the broad shape
resonance is observed to be quite strongly present in both of the theoretical calculations at
around 8 eV, whilst in the present measurement it is observed at around 6.5 eV. Consistent with
the theoretical calculations however, its presence in the experimental cross-section is much
more dominant at higher angles. Our preliminary investigations into the vibrational excitation
of C–H stretching modes for THF have also indicated the presence of a negative ion resonance
at ∼6.5 eV. The small structure observed in each of the EF at approximately 19.4 eV is due
to the He− resonance, which appears as a consequence of the normalization process against
helium.

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9 DEUTSCHE PHYSIKALISCHE GESELLSCHAFT

The angular distributions have been used to derive elastic ICS and MTCS, at each incident
energy, using the phase shift analysis technique of Campbell et al [32]. This technique removes
some of the subjective nature of the alternative approach—an extrapolation by eye. For a molecule
such as THF with a large dipole moment, the extrapolation to forward angles can be a highly
uncertain process and the fitting of partial waves to the angular distribution helps yield more
physically reasonable values for the forward and backward scattering angles.
In figure 4(a), a comparison of the present elastic ICS data is made with the total cross-
section measurements of Zecca et al [17] and Mozejko et al [18], as well as with the R-matrix
total cross-section calculation of Bouchiha et al [22] and the Schwinger variational calculation
of Winstead and McKoy [25]. We see from the present measurements that the elastic ICS is
quite constant in magnitude between 6.5 and 20 eV, and this is in excellent agreement with the
Schwinger variational calculation. We also note that the shape resonance is only weakly present
in the calculated elastic ICS and its appearance in the present measurements is not conclusive.
A broad resonance-like feature is also observed in the total cross-section measurements of both
Mozejko et al and Zecca et al. The present elastic scattering data is uniformly larger than the total
cross-section of Zecca et al, which indicates that their measurement may well underestimate the
total scattering cross-section. Zecca et al did not correct their results for forward angle scattering
and the present measurements suggest that could be a serious limitation in their results. On
the other hand the present measurement is consistent with the total cross-section of Mozejko
et al, lying about 15–20% lower in magnitude and suggesting an appreciable contribution to
the total cross-section comes from inelastic scattering. The present data is also compared to the
R-matrix calculation of Bouchiha et al below 10 eV. They do not detect a shape resonance in
their calculation but instead observe a rapidly rising cross-section at low energies and a few
core-excited resonances around 8–9 eV.
The present results for the MTCS are shown in figure 4(b) and are compared to the theoretical
efforts of Trevisan et al and Winstead and McKoy. These two calculations are in good agreement
with one another and both show a strong resonant enhancement in the cross-section at around
8 eV. The present measurements are in good accord with the calculations and do not exclude the
presence of a resonance in this region.
It is interesting to note that the shape resonance observed in both the present experiment,
and the theoretical calculations, is relatively narrow in width (∼2 eV). In previous work (see for
example Allan and Andric [33]) it has been observed that broad features in saturated, linear
hydrocarbons become quite narrow when studied in the related cyclic compounds. A good
example of this effect is seen in studies of n-propane and cyclopropane, and also in cyclopentane
[33]. It may well be that the resonance observed in THF is of a similar character, although
measurements of vibrational excitation should provide more detailed information.

4. Conclusion

This paper reports absolute DCS for elastic electron scattering from THF at energies from
5–50 eV, as well as integral and MTCS. The experimental cross-sections are in good agreement
with the recent theoretical calculations of Trevisan et al and Winstead and McKoy. Measurements
at energies between 10 and 50 eV are also shown to be in good agreement with results of
Milosavljevic et al and Dampe et al. A broad shape resonance, predicted at around 8 eV by the
calculations of Trevisan et al and Winstead and McKoy, and previously observed in the total

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10 DEUTSCHE PHYSIKALISCHE GESELLSCHAFT

cross-sections of Zecca et al and Mozejko et al is observed in the present study in the elastic
channel at 6.5 eV and at a scattering angle of 120◦ . Preliminary investigations of the C–H stretch
vibrational excitation channel have shown that a negative ion resonance also appears strongly
at around 6.5 eV. Further investigations into vibrational excitation, and the role of resonant
scattering, are currently being carried out.

Acknowledgments

This study is supported by the Australian Research Council, the Australian National University
and Flinders University. It is a pleasure to acknowledge discussions with Cynthia Trevisan,
Tom Rescigno and Anne Orel and we are grateful for their provision of tabulated data prior to
publication. We also thank Carl Winstead and Mariusz Zubek for providing tabulated results
of their cross-sections, and Greg Karwasz for information regarding the hard sphere diameter
of THF. Christopher Colyer acknowledges the financial support of both the Australian National
University and Flinders University. It is also a pleasure to acknowledge helpful comments and
suggestions regarding the resonance from a referee.

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