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Low temperature rate coefficients for reactions of the butadiynyl radical,

C4H, with various hydrocarbons. Part II:w reactions with alkenes
(ethylene, propene, 1-butene), dienes (allene, 1,3-butadiene)
and alkynes (acetylene, propyne and 1-butyne)
Coralie Berteloite, Sébastien D. Le Picard,* Nadia Balucani,z
André Canosa and Ian R. Sims*
Published on 19 March 2010. Downloaded by Northeastern University on 22/10/2014 22:49:57.

Received 12th November 2009, Accepted 8th February 2010

First published as an Advance Article on the web 19th March 2010
DOI: 10.1039/b923867k

The kinetics of the reactions of the linear butadiynyl radical, C4H (CCCCH), with a variety
of unsaturated hydrocarbons have been studied over the temperature range of 39–300 K using a
CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme, or reaction kinetics in
uniform supersonic flow) apparatus combined with the pulsed laser photolysis–laser induced
fluorescence technique. The rate coefficients for all the reactions studied are found to all be in
excess of 1010 cm3 molecule1 s1 over the entire temperature range. They can be fitted with the
following expressions (valid from 39 K to 300 K, with RMS deviations of the experimental points
from the predicted values shown, to which should be added 10% possible systematic error) for
reaction of C4H with alkenes:
kC2H4 = (1.95  0.17)  1010 (T/298 K)0.40 exp(9.4 K/T) cm3 molecule1 s1;

kC3H6 = (3.25  0.12)  1010 (T/298 K)0.84 exp(48.9 K/T) cm3 molecule1 s1;

k1-C4H8 = (6.30  0.35)  1010 (T/298 K)0.61 exp(65.0 K/T) cm3 molecule1 s1,
for reaction of C4H with dienes:
kC3H4 = (3.70  0.34)  1010 (T/298 K)1.18 exp(91.1 K/T) cm3 molecule1 s1;

k1,3-C4H6 = (5.37  0.30)  1010 (T/298 K)1.25 exp(116.8 K/T) cm3 molecule1 s1,
and for reaction of C4H with alkynes:
kC2H2 = (1.82  0.19)  1010 (T/298 K)1.06 exp(65.9 K/T) cm3 molecule1 s1;

kC3H4 = (3.20  0.08)  1010 (T/298 K)0.82 exp(47.5 K/T) cm3 molecule1 s1;

k1-C4H6 = (3.48  0.14)  1010 (T/298 K)0.65 exp(58.4 K/T) cm3 molecule1 s1.
Possible reaction mechanisms and product channels are discussed in detail for each of these reactions.
Potential implications of these results for models of low temperature chemical environments,
in particular cold interstellar clouds and star-forming regions, are considered.

Introduction involving atomic carbon or small carbon-containing molecules

An understanding of the formation of complex carbon bearing
molecules is an important issue in many scientific fields such as
combustion, the environment, terrestrial and extraterrestrial
atmospheres and astrophysics. Elementary gas phase reactions
Institut de Physique de Rennes, Equipe Astrochimie Expe´rimentale
UMR 6251 du CNRS - Universite´ de Rennes 1, Bât. 11c,
Campus de Beaulieu, 35042 Rennes Cedex, France.
E-mail: sebastien.le-picard@univ-rennes1.fr, ian.sims@univ-rennes1.fr
w For Part I see ref. 8.
z Visiting scientist. Permanent address: Dipartimento di Chimica,
Università degli Studi di Perugia, 06123 Perugia, Italy.
or radicals, such as C2, CH, C2H and C4H, are believed to
participate in the growth of hydrocarbon chains in these
environments and are also likely to play a role in the formation
of aromatic hydrocarbons.
The C4H (CCCCH) radical has been observed in many
astrophysical environments spanning a wide variety of
physical conditions. Since its first identification in 1978 in
the interstellar medium by Guélin et al.,1 who observed C4H
in a circumstellar envelope (IRC +10216), it has been detected
in many objects (see Gupta et al.2 and references therein): cold
quiescent molecular clouds, protostellar cores, hot cores and
hot corinos as well as photon-dominated regions (PDRs),

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encompassing a temperature range from 10 K to more than
100 K. In all these regions unsaturated hydrocarbons are also
present and can react with C4H to form larger hydrocarbons.
C4H is also believed to be present in some planetary
atmospheres such as Titan or Saturn where diacetylene,
C4H2, which is known to photodissociate into C4H + H after
UV irradiation,3 has been observed in relatively large
abundance. Such atmospheres also contain methane and
photochemistry leads to the production of numerous
Published on 19 March 2010. Downloaded by Northeastern University on 22/10/2014 22:49:57.
a number of alkanes (CH4, C2H6 C3H8 and C4H10). In
this paper we present a similar kinetics study on the
reactions involving the C4H radical and several unsaturated
hydrocarbons, namely the alkynes C2H2, C3H4, 1-C4H6,
the alkenes C2H4, C3H6, 1-C4H8 and the dienes C3H4 and
1,3-C4H6.
To our knowledge this work presents the first direct
measurements of rate coefficients for reactions of C4H with
unsaturated hydrocarbons. A previous theoretical study on

hydrocarbons, including several unsaturated hydrocarbons.
In order to model the chemistry of all these astrophysical
objects and planetary atmospheres, and to reproduce or
predict the abundances of species such as C4H and other
hydrocarbons, a knowledge of rate coefficients of the relevant
elementary reactions measured at the actual temperature of
these environments is of major importance.
The C4H radical has never been directly identified in flames,
probably because of its high reactivity. Reactions of C4H with
hydrocarbon molecules and radicals however, are included in
chemical models of combustion. For example, their role in the
growth of polyynes has been suggested by several authors,4–7
and according to some of them5,7 the reactions of the C2nH
the reaction C4H + C2H2 has recently been published by
Mebel and co-workers.9
The possible reaction channels for these reactive systems are
listed below. The enthalpy of reaction has been given for the
channels for which the enthalpies of formation of the possible
products are known. We have used the enthalpy of reaction for
the channels (1a) and (1b) calculated at the CCSD(T)/CBS +
ZPE level by Landera et al.,9 while for the other reactions we
have used enthalpies of formation from the NIST-CCCBD
Computational Chemistry Comparison and Benchmark
Database,10 as well as values for specific product species
calculated by Hansen et al.4 The enthalpy of formation

DfH0 K of the C4H radical is deduced to be 802 kJ mol1
J

radicals, including C4H, leading to the formation of long from the dissociation energy of diacetylene recently calculated

by Landera et al.9 combined with DfH0 K for diacetylene from
J
polyynes can play an important role in the formation of soot.

Hansen et al.4 and DfH0 K for H from the NIST-CCCBD
J
In the preceding companion paper (referred to hereafter
as Part I),8 we have reported on a low temperature Computational Chemistry Comparison and Benchmark
(T = 39 to 300 K) kinetics study of the reactions of C4H with Database.10


- C6H2 + H = 131 kJ mol1
J
C4H + HCRCH DrH0 K (1a)

- C4H2 + C2H 1
J
DrH0 K = 7 kJ mol (1b)

- C6H2 + CH3 = 159 kJ mol1
J
C4H + CH3–CRC–H DrH0 K (2a)

- HCRC–CRC–CRC–CH3 + H 1
J
DrH0 K = 135 kJ mol (2b)

- HCRC–CRC–CHQCQCH2 + H = 114 kJ mol1
J
DrH0 K (2c)

- HCRC–CRC–CH2–CRCH + H 1
J
DrH0 K = 94 kJ mol (2d)

- C6H2 + C2H5 = 177 kJ mol1
J
C4H + C2H5–CRC–H DrH0 K (3a)

- HCRC–CRC–CRC–C2H5 + H (3b)

- HCRC–CRC–CHQCQCH–CH3 + H (3c)

- HCRC–CRC–CHQCH–CHQCH2 + H (3d)

- C6H2 + CH3 = 165 kJ mol1
J
C4H + CH2QCQCH2 DrH0 K (4a)

- HCRC–CRC–CRC–CH3 + H 1
J
DrH0 K = 142 kJ mol (4b)

- HCRC–CRC–CHQCQCH2 + H = 121 kJ mol1
J
DrH0 K (4c)

- HCRC–CRC–CH2–CRCH + H 1
J
DrH0 K = 101 kJ mol (4d)

- HCRC–CRC–CHQCH2 + H = 124 kJ mol1
J
C4H + CH2QCH2 DrH0 K (5)

- HCRC–CRC–CHQCH2 + CH3 1
J
C4H + CH3–CHQCH2 DrH0 K = 164 kJ mol (6a)

- HCRC–CRC–CHQCH–CH3 + H (6b)

- HCRC–CRC–C(CH3)QCH2 + H (6c)

- HCRC–CRC–CH2–CHQCH2 + H (6d)

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C4H + C2H5–CHQCH2 - C4H2 + CH3–CHCHQCH2 (7a)


- HCRC–CRC–CHQCH2 + C2H5 1
J
DrH0 K = 181 kJ mol (7b)
- HCRC–CRC–CHQCH–C2H5 + H (7c)
- HCRC–CRC–C(C2H5)QCH2 + H (7d)
C4H + CH2QCH–CHQCH2 - HCRC–CRC–CHQCH–CHQCH2 + H (8a)
- H2CQC(C4H)–CHQCH2 + H (8b)
Published on 19 March 2010. Downloaded by Northeastern University on 22/10/2014 22:49:57.

Experimental techniques
The kinetic data presented here were obtained using the
CRESU apparatus in Rennes. The CRESU apparatus has
been described elsewhere11,12 and the experimental apparatus
and methods relevant to the study of the kinetics of C4H
reactions have been described in Part I,8 so only details specific
to this study will be given here. As a reminder, C4H radicals
were generated within the cold supersonic flow by pulsed
248 nm excimer laser photolysis of diacetylene (C4H2) and
detected by laser-induced fluorescence in the B̃2Pi–X̃2S+
electronic system at l B 408 nm.13 Excellent signal-to-noise
was achieved in these experiments, as may be seen from the
sample LIF decay shown in Fig. 1. As before, this enabled the
use of very low initial concentrations of C4H, estimated
at below ca. 1010 cm3, ensuring that pseudo-first-order
conditions were maintained throughout.
The stated purities of the reagents used in this study are
listed below, all of them being provided by Air Liquide with
the exception of acetylene which was furnished by AGA: C2H4
(99.95%), C3H6 (99.5%), 1-C4H8 (99%), C3H4 allene (95%),
1,3-C4H6 (99.6), C2H2 (99.6%), C3H4 propyne (96%) and Fig. 1 The upper panel shows the decay of C4H LIF signal at 39 K in
1-C4H6 (95%). All of these gases were taken directly from the presence of C3H6 ([C3H6] = 6.70  1012 molecule cm3) and N2
their cylinders apart from acetylene, which was flowed through buffer ([N2] = 3.3  1016 molecule cm3), fit to a single-exponential
a trap cooled to 40 1C prior to use in order to eliminate decay function. The lower panel shows a second order plot for the
traces of acetone vapour which result from the method of reaction of C4H with C3H6 at 39 K in N2 buffer, leading to a value for
storage. In view of the rapidity of the reactions under study, the second-order rate coefficient of k = (5.16  0.57)  1010 cm3
any impurities could not influence the measured rate molecule1 s1, where only the statistical uncertainty is quoted
coefficients outside of the stated error limits. (see text).
As in Part I, rate coefficient measurements were performed
in the uniform supersonic flow provided by the CRESU
apparatus at 39, 52, 83, 145, 200 K. In addition, rate
coefficients were also determined at room temperature (300 K),
by increasing the pressure in the main chamber up to the same
pressure as the reservoir (B10 mbar); in this case, a subsonic
flow at the temperature of the reservoir is generated. For each
temperature, the pseudo-first-order decays of C4H radicals
were then monitored for different reagent concentrations of
hydrocarbons. The data were used to extract the second order
rate coefficients of the reactions under study as explained in
detail in Part I. An example LIF decay plot and a second order
plot, both for the reaction of C4H with propene at 39 K in an
N2 buffer, are shown in Fig. 1.

Results
The measured rate coefficients for the reactions of C4H with
alkenes, dienes and alkynes are given in Tables 1–3 along with
the corresponding experimental conditions (temperature,
Fig. 2 Rate coefficients for the reaction of C4H with alkenes
(C2H4, ; C3H6, and 1-C4H8, K) as a function of temperature,
displayed on a log–log scale. The dotted, dashed and solid lines
respectively show the fits to these data for each reaction (see Table 4
for details of the fits).

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Fig. 3 Rate coefficients for the reaction of C4H with dienes (C3H4,
and 1,3-C4H6, K) as a function of temperature, displayed on a log–log
scale. The dashed and solid lines respectively show the fits to these data
for each reaction (see Table 4 for details of the fits).
Fig. 4 Rate coefficients for the reaction of C4H with alkynes (C2H2, ;
C3H4, and 1- C4H6, K) as a function of temperature, displayed on a
log–log scale. The dotted, dashed and solid lines respectively show the
fits to these data for each reaction (see Table 4 for details of the fits).
buffer gas, total density, range of reactant gas density). The
quoted uncertainties include statistical and systematic
elements and are calculated as the square root of the sum of
these two independent errors squared. The latter, estimated
to be less than 10%, are essentially due to flow control
inaccuracies or inaccuracies in the determination of the buffer
gas total density. Fig. 2–4 show the rate coefficients for
reactions of C4H radical with unsaturated hydrocarbons
of the three different families plotted as a function of
temperature using log–log scales. In order to facilitate the
insertion of these results in databases or in chemical schemes,
the experimental data were fitted to the following equation:
k(T) = A(T/298 K)n exp(y/T). A, y and n parameters,
derived for each reaction, are summarised in Table 4. We
emphasise that the fits have been obtained between 39 K and
300 K and are only valid for this temperature range. The root
mean square (RMS) average deviations of the experimental
data from the fits are also given in Table 4, and in all cases are
less than 10% of the average values of the corresponding rate
coefficients.
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As in Part I, measurements were carried out at ca. 50 K
for two different argon buffer gas concentrations (0.52 
1017 cm3 and 1.03  1017 cm3, respectively) using two
different Laval nozzles in order to test the possible pressure
dependence of the studied reactions. As can be seen in Tables 1
to 3, the two series of measurements were found to be identical
taking into account the uncertainties, except for the case of
C4H + 1-butene and C4H + 1,3-butadiene, where the
variation was only just outside of the range of the combined
uncertainties. It would appear that either the reactions
are bimolecular in nature, or that they are termolecular
association reactions occurring in the high pressure limit.
Discussion
The measured rate coefficients for all of the reactions of C4H
with unsaturated hydrocarbons reported here are very large
and display slightly negative temperature dependences down
to 100 K. The room temperature rate coefficients appear to
show a trend in the increase of the rate coefficient with the size
of the hydrocarbon under consideration, but this trend
becomes less evident at lower temperatures. At lower
temperatures, with the exception of the reaction of C4H with
C2H4 where the rate coefficient continues to increase, the rate
coefficients for all the other reactions either remain constant or
start to decrease. A similar negative temperature dependence
has been observed in the case of the reactions of C4H with
saturated hydrocarbons such as propane and butane, which
have been also found to be very fast with a rate coefficient
close to the gas kinetic collisional limit at room temperature.8
The reactions of C4H with unsaturated hydrocarbons reported
here appear to be even more rapid than those with saturated
hydrocarbons, especially for those with two or three carbons.
As noted in Part I, similar temperature dependences have
been observed for the rate coefficients of a wide variety of
reactions of hydrocarbon radicals (such as C, C2, CH, C2H,
and CN),14–25 indicating that there is no ‘absolute barrier’
above the energy of the reactants along the minimum energy
path on the lowest electronic potential energy surface
connecting those reactants to products. Presumably, the first
step corresponds to the electrophilic addition of the C4H
radical to the multiple (p) bond of the unsaturated
hydrocarbon to form an addition complex, followed by
rearrangement(s) over subsequent ‘submerged’ barrier(s) to
yield products. At low temperatures, long-range attractive
interactions between the reactive partners are likely to
be important. Both Clary et al.26 and Georgievskii and
Klippenstein27 have discussed the low temperature limiting
behaviour of barrierless chemical reactions in terms of the
long-range electrostatic and dispersion interactions existing
between the reactants. For reactions of the C4H radical,
which possesses a small dipole moment of only 0.87 D,28 the
dispersion interaction is likely to be dominant owing to the
large polarisability of the reactive partners, yielding a T1/6
temperature dependence to the rate coefficient in the low
temperature limit (where it can be calculated using capture
theory). There will also be a contribution from the dipole–
quadrupole interaction (which, if taken in isolation, yields a
rate coefficient in the low temperature limit showing no
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Table 1 Rate coefficients measured at different temperatures for the reaction of C4H with the alkenes C2H4, C3H6 and 1-C4H8

Total density/ Range of reactant gas density/ Number of Rate coefficient/

T/K Buffer gas 1016 molecules cm3 1012 molecules cm3 points 1010 cm3 molecule1 s1
C4H + ethylene C2H4
39 N2 3.3 3–33 10 5.57  0.64a
52 Ar 5.1 6–61 6 5.01  0.72
52 Ar 10.3 14–137 9 4.84  0.49
b
Statistically weighted mean at 52 K: 4.85  0.50
83 N2 4.9 4–26 10 3.19  0.39
145 N2 9.2 10–110 10 3.27  0.35
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300 Ar 25 25–386 10 1.80  0.19

C4H + propene C3H6
39 N2 3.3 2–22 10 5.16  0.57
52 Ar 5.1 4–42 7 6.35  0.80
52 Ar 10.3 0–100 9 5.48  0.59
Statistically weighted mean at 52 K: 5.64  0.60
83 N2 4.9 3–26 11 4.99  0.61
145 N2 9.2 7.5–75 11 4.62  0.63
300 Ar 25 20–360 9 2.57  0.27
C4H + 1-butene C4H8
39 N2 3.3 3.5–11.5 10 4.81  1.08
52 Ar 5.1 3–30 9 4.01  0.50
52 Ar 10.3 3–34 10 5.28  0.67
Statistically weighted mean at 52 K: 4.43  0.51
83 N2 4.9 2–24 9 5.90  0.77
145 N2 9.2 4–42 10 7.19  0.85
300 Ar 25 10–95 9 4.58  0.51
a
Uncertainties (here and throughout the Table) are calculated using the standard error evaluated from the second order plot, multiplied by the
appropriate Student’s t factor for 95% confidence. An estimated systematic error of 10% was combined with this to yield the overall estimated
uncertainty (see Part I 8 for details). b The statistically weighted mean (here and throughout the table) was calculated using only the statistical
uncertainties resulting from the scatter in the second-order plots. An estimated systematic error of 10% was combined with the resulting combined
statistical uncertainty to yield the overall estimated uncertainty.

Table 2 Rate coefficients measured at various temperatures for the reactions of C4H with the dienes C3H4 and 1,3-C4H6

Total density/ Range of reactant gas density/ Number of Rate coefficient/

T/K Buffer gas 1016 molecules cm3 1012 molecules cm3 points 1010 cm3 molecules1 s1
C4H + allene C3H4
39 N2 3.3 3.5–19 11 3.28  0.74a
52 Ar 5.1 4–44 6 6.29  0.73
52 Ar 10.3 9.4–86 9 6.26  0.63
Statistically weighted meanb at 52 K: 6.22  0.64
83 N2 4.9 0–34 11 4.91  0.58
145 N2 9.2 8–79 10 4.66  0.57
300 Ar 25 18–82 9 2.88  0.38
C4H + 1,3-butadiene C4H6
39 N2 3.3 3.8–17.8 9 2.77  0.48
52 Ar 5.1 3–20 5 7.08  0.75
52 Ar 10.3 7.5–33 8 5.51  0.58
Statistically weighted mean at 52 K: 6.10  0.63
83 N2 4.9 2.5–26.7 11 5.99  0.71
145 N2 9.2 13–64 9 5.97  0.73
300 Ar 25 6.5–83 10 3.71  0.43
a
Uncertainties (here and throughout the Table) are calculated using the standard error evaluated from the second order plot, multiplied by the
appropriate Student’s t factor for 95% confidence. An estimated systematic error of 10% was combined with this to yield the overall estimated
uncertainty (see Part I 8 for details). b The statistically weighted mean (here and throughout the Table) was calculated using only the statistical
uncertainties resulting from the scatter in the second-order plots. An estimated systematic error of 10% was combined with the resulting combined
statistical uncertainty to yield the overall estimated uncertainty.

temperature dependence), the dipole-induced dipole inter-
action (yielding again a T1/6 dependence), and finally where
the hydrocarbon possesses a dipole moment (propylene,
1-butene, propyne, 1-butyne) a relatively small contribution
from the dipole–dipole interaction, which if taken in isolation
would yield a negative T1/6 temperature dependence to
the rate coefficient at low temperatures. Georgievskii and
Klippenstein27 have calculated magnitudes of the long
range transition state theory predictions for the capture rates
at low temperatures due to these different interactions
for a number of reactions, including that between the
C2H radical and propyne which may serve as a comparison
with the reactions under study here. For this reaction,
at a temperature of 63 K the calculated rate coefficients are

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Table 3 Rate coefficients measured at different temperatures for the reactions of C4H with the alkynes, C2H2, C3H4 and 1-C4H6

Total density/ Range of reactant gas density/ Number of Rate coefficient/

T/K Buffer gas 1016 molecules cm3 1012 molecules cm3 points 1010 cm3 molecules1 s1
C4H + acetylene C2H2
39 N2 3.3 3–32 12 2.57  0.35a
52 Ar 5.1 6–60 6 3.90  0.42
52 Ar 10.3 13–77 10 3.88  0.41
Statistically weighted meanb at 52 K: 3.89  0.40
83 N2 4.9 2.5–47.5 12 2.74  0.28
145 N2 9.2 10–110 10 2.54  0.32
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300 Ar 25 13–264 11 1.54  0.16

C4H + propyne C3H4
39 N2 3.3 2–14 10 4.93  0.58
52 Ar 5.1 4–20 5 6.08  0.97
52 Ar 10.3 5–33 7 5.66  0.60
Statistically weighted mean at 52 K: 5.69  0.61
83 N2 4.9 3–34 10 5.04  0.62
145 N2 9.2 8–79 10 4.13  0.53
300 Ar 25 14–164 11 2.80  0.38
C4H + 1-butyne C4H6
39 N2 3.3 1.8–11.5 12 2.84  0.75
52 Ar 5.1 3–20 11 2.01  0.62
52 Ar 10.3 2–24 9 3.95  0.43
Statistically weighted mean at 52 K: 3.82  0.41
83 N2 4.9 2–35 10 3.57  0.51
145 N2 9.2 8.5–72 9 4.03  0.51
300 Ar 25 10–120 11 2.75  0.32
a
Uncertainties (here and throughout the Table) are calculated using the standard error evaluated from the second order plot, multiplied by the
appropriate Student’s t factor for 95% confidence. An estimated systematic error of 10% was combined with this to yield the overall estimated
uncertainty (Part I 8 for details). b The statistically weighted mean (here and throughout the Table) was calculated using only the statistical
uncertainties resulting from the scatter in the second-order plots. An estimated systematic error of 10% was combined with the resulting combined
statistical uncertainty to yield the overall estimated uncertainty.

(in units of 1010 cm3 molecule1 s1): 1.77 (dipole–dipole), submerged barriers29,30 which, at shorter reagent separations,
2.60 (dipole–quadrupole), 1.17 (dipole–induced dipole, and will result in an inner, low-entropy (‘tight’) transition state.
5.01 (dispersion). This confirms that the dispersion interaction With increasing temperature, this inner transition state starts
is dominant in determining the rate coefficient—and thus its to influence the reactive rate coefficient, due to its much lower
negative temperature dependence—at low temperatures, and entropy.29 This increasing role of the inner transition state
the argument is likely to be even stronger for the case of initially yields a reduction in the rate coefficient (a negative
the equivalent C4H reaction with that radical’s greater temperature dependence of the rate coefficient on temperature)
polarisability. However it should be noted that a variational as the temperature rises,29 except for the very lowest tempera-
transition state calculation taking into account all these tures, and at least up to 300 K. This appears to be the case for
interactions together yields a rate coefficient of 5.66  the reactions studied here (indeed, for C4H + ethylene this is
1010 cm3 molecule1 s1 at 63 K,27 roughly twice the experi- true over the entire temperature range).
mental value determined by Carty et al.,19 showing that at this Smith et al.31 and Sabbah et al.30 have correlated the height
temperature the rate coefficient is already being determined of the barrier corresponding to the inner transition state in
in part by other factors, such as the presence of so-called radical-molecule reactions to the difference (IP–EA) between
 n  
T y
Table 4 Fit parameters (A, n, y) for the kinetic data according the following equation k2nd ¼ A   exp for the reactions of C4H
298 K T
with unsaturated hydrocarbons over the range T = 39—300 K

RMS deviationa/
Reactant A/1010 cm3 molecules1 s1 n y/K 1010 cm3 molecules1 s1
Ethylene C2H4 1.95 0.40 9.39 0.17
Alkenes Propene C3H6 3.25 –0.84 48.92 0.12
1-Butene C4H8 6.30 –0.61 65.03 0.35
Dienes Allene C3H4 3.70 –1.18 91.10 0.34
1,3-Butadiene C4H6 5.37 –1.25 116.77 0.30
Acetylene C2H2 1.82 –1.06 65.87 0.19
Alkynes Propyne C3H4 3.20 0.82 47.45 0.08
1-Butyne C4H6 3.48 0.65 58.39 0.14
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2
a Sðk 2nd exp k2nd fitÞ
The RMS deviation is calculated as , and should be combined with a likely 10% systematic error to give an
number of experimental points
estimate of the uncertainty at any given temperature.

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the ionisation potential of the hydrocarbon molecular
co-reactant (IP) and the electron affinity (EA) of the radical
reagent, proposing a threshold value of 8.75 eV for this
difference, below which the reaction is likely not to possess
any absolute barrier and remain rapid down to very low
temperatures. Employing a value for the EA of C4H of
3.558 eV,32 and IP values taken from the NIST Chemistry
Webbook,33 all of the values of (IP–EA) for the reactions
studied in this work lie below 8.75 eV (the largest being 7.84 eV
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for C4H + C2H2). This corresponds well with the experi-
mental results reported here, where all the reactions under
study display behaviour characteristic of barrierless reactions
as described above. The only C4H reaction studied so far
which possesses a value for (IP–EA) above 8.75 eV, that with
methane, has been shown to display a positive temperature
dependence at room temperature and below.8
A quantitative comparison of the differing magnitudes of
the rate coefficients for the reaction of the C4H radical with the
range of hydrocarbons employed in this study is rendered
difficult by the lack of reliable potential energy surface
calculations for all of these reactions. In all likelihood any
submerged barriers are, in fact well submerged below the
reagent energy. This has been shown for the reaction of C4H
with C2H2, the only reaction under consideration where high
level ab initio potential energy surface calculations have been
performed. A schematic representation of the potential energy
profile based on the calculations of Landera et al.9 is shown in
Fig. 5. A reaction pathway exists from C4H + C2H2 reactants
to C6H2 + H products via an initial deep well at an energy
relative to the reactants of 255 kJ mol1, and a deeply
submerged barrier at a relative energy of 101 kJ mol1. This
implies that, for this reaction at least (and probably for all
those under study here, in the light of the semi-empirical
arguments presented above), the rate coefficients will be
determined at room temperature and below mainly by capture
on a potential surface dominated by long range forces. In
order to facilitate comparison, Table 5 presents the van der
Waals well depths for the reactions under study, calculated on
a Lennard-Jones potential in the same way as presented in
Part 1,8 according to the prescriptions of Cambi et al.34 As
before, the average polarisabilities of the relevant hydro-
carbons have been calculated by standard group additivity
rules (with values of 0.65 Å3 per CH bond, 0.64 Å3
Fig. 5 A schematic representation of the energy profile for the
reaction C4H + C2H2. Based on the calculations by Landera et al.9
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per aliphatic CC bond, 1.66 Å3 per olefinic CC bond and
2.03 Å3 per acetylenic CC bond). For the reactant C4H the
polarisability is estimated to be 5.79 Å3 by adding the
contributions of the C4H bonds and 0.44 Å3 for the carbon
atom which is at the centre of the radical.
The resulting well depths, e/kB (where kB is the Boltzmann
constant), are displayed in Table 5 along with the measured
room temperature rate coefficients. The reactants are
displayed in order of increasing well depth. It can be seen
that, within the quoted error limits, the measured rate
coefficients follow essentially the same ordering as the
calculated well depths, providing support for the hypothesis
that these rate coefficients are determined largely by capture
and that the dominant interaction is due to dispersion. This
analysis relates of course only to the overall rate coefficient,
and does not give any further insight into the subsequent
reaction mechanism leading to products, beyond the necessity
of a pathway possessing only well-submerged barriers. Nor
does it take into account other contributions to the long
range potential such as dipole–dipole and higher order
electrostatic forces. Furthermore, it does not explain the
reduction in the rate coefficients observed at higher tempera-
tures which may rather be due to submerged barriers
associated with relatively tight transition states. In order to
explore this aspect further, we will now discuss the possible
reaction mechanisms.
In Part 1,8 reactions of C4H with alkanes were assumed to
take place via H-abstraction. In the case of the reactions with
unsaturated hydrocarbons, however, the reaction mechanism
is expected to be different, as suggested by an analysis of the
trend of the rate coefficients with the molecular structure of the
unsaturated hydrocarbon involved. For instance by comparing
the essentially similar values for the rate coefficients for
reaction of C4H with acetylene and ethylene at room tempera-
ture (k300K = (1.54  0.16)  1010 cm3 molecule1 s1 and
k300K = (1.80  0.19)  1010 cm3 molecule1 s1, respectively)
it can be inferred that these reactions occur primarily by
addition to the unsaturated carbon–carbon bonds. The
hydrogen abstraction mechanism to form C4H2 and C2H/C2H3
radicals, in fact, can be excluded as a major pathway because
the C–H bond strengths of acetylene and ethylene are very
different (DC2H–H B 556 kJ mol1 and DC2H3–H B 465 kJ mol1)35
and, if H-abstraction were the dominant reaction pathway,
one would expect a greater difference in their overall room
temperature rate coefficients. In addition, the increase in
the rate coefficient values moving from acetylene to the
alkyl-substituted methyl-acetylene (propyne) and ethyl-
acetylene (butyne) might be explained by a competition
between radical addition and H-abstraction from the alkyl
group. However, one would expect the H-abstraction from the
ethyl group to be easier because of the presence of more
H atoms, two of which are also secondary. Since reaction
(2) is slightly faster than reaction (3), the possible alkyl
H-abstraction channel does not seem to contribute signifi-
cantly. Finally, this interpretation is also supported by the
comparison between the rate coefficients for reactions (2) and
(4), where the molecular reactants are the isomeric species
propyne and allene. The substantial similarity of the rate
coefficient values for reactions (2) and (4) points to a similar
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Table 5 Calculated van der Waals well depths for the reactions under study, compared with measured room temperature rate coefficients.
The reactants are displayed in order of increasing well depth
Reactant Average polarisability/Å3
Acetylene C2H2 3.33
Ethylene C2H4 4.26
Propyne C3H4 5.27
Allene C3H4 5.92
Propene C3H6 6.2
1-Butyne C4H6 7.21
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1,3-Butadiene C4H6 7.86
1-Butene C4H8 8.14
reaction mechanism of the addition type, because the different
nature of the H atoms of propyne and allene would be
reflected in the value of the rate coefficients if H-abstraction
were the dominant reaction channel.
In the sequence C2H4, C3H6 and 1-C4H8 (reactions (5), (6)
and (7), respectively), there is an increase of the reactivity at
room temperature (Table 1). However, the rate coefficient of
reaction (7) is significantly larger than that of reaction (3),
even though, in the case of a purely addition mechanism, the
addition site is a p bond in both cases and the ethyl groups
of 1-butyne and 1-butene have the same characteristics.
Comparing reactions (7) and (8), both 1-butene and 1,3-
butadiene have C4 carbon chains, but 1,3-butadiene has two
unsaturated bonds, that is, two possible addition sites.
The rate coefficient of reaction (7) was found to be higher
than that for reaction (8). While this is consistent with
the larger polarisability of 1-butene (see Table 5), this fact and
the large rate coefficients associated with the reactions of C4H
with relatively large saturated hydrocarbons, such as C3H8
and C4H10, could also imply that at least for reaction (7) H
abstraction might be an important reaction pathway.
This simple analysis of the rate coefficients for the reactions
between C4H and unsaturated hydrocarbons appears to be in
line with previous observations on the reactions of other
electrophilic radicals (such as C2H or CN). As a matter of
fact, for several C2H and CN reactions with unsaturated
hydrocarbons it has been verified that they proceed via the
formation of one or more addition intermediates without any
entrance barrier.14,16,36–49 The addition intermediates are
formed with a large amount of internal energy, so that, in
the absence of collisional relaxation, they fragment into one or
more sets of products. The current work has shown that
reactions (1)–(8) are characterised by very large room
temperature rate coefficients which increase or remain roughly
constant with decrease in temperature, implying that they
take place on a potential energy surface which is essentially
barrierless. As already noted, our experimental results are
the first on C4H reactions with unsaturated hydrocarbons
and little is known on the chemical behaviour of this
radical species. On the other hand, the analogous reactions
involving the strongly related C2H radical have been widely
investigated.9,16,19,37–44,50–59 We expect many similarities
between the chemical behaviour of C2H and C4H and, there-
fore, it is worth to summarize briefly the most important
results on the C2H reactions analogous to reactions (1)–(8).
Experimental studies coupled with theoretical calculations38
have shown that the favoured approach for the reaction of
3684 | Phys. Chem. Chem. Phys., 2010, 12, 3677–3689
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Reactant + k300K/
C4H van der Waals well depth e/kB/K 1010 cm3 molecule1 s1
306 1.54  0.16
352 1.80  0.19
408 2.80  0.38
424 2.88  0.38
443 2.57  0.27
487 2.75  0.32
498 3.71  0.43
514 4.58  0.51
C2H with acetylene is the attack on the p electrons of the triple
CC bond to form an addition intermediate that decomposes to
give the final products
C2H + HCRCH - HCCHC2Hz - C4H2 + H (9)
Other reaction channels are possible. For instance, the H-atom
abstraction channel that gives back acetylene and C2H
is thermoneutral. Nevertheless, the fast rate coefficient
(k298K = 1.3  1010 cm3 molecule1 s1)60 and the slightly-
negative temperature dependence16 are more in line with the
addition–elimination mechanism rather than hydrogen
abstraction. Recent crossed beam experiments at a relatively
high collision energy have confirmed that the diacetylene
formation channel is the dominant reaction pathway and also
shown that a little contribution from an endothermic channel
leading to C4H + H2 is open.38 An interesting conclusion of
the theoretical investigation of the relevant potential energy
surface is that the CRCH moiety of the radical reactant, once
added to the triple bond, remains essentially unchanged
(‘spectator’).38 Some theoretical information on the C6H3
potential energy surface9 is available and confirms the
analogous nature of reactions (1) and (9). As can be seen from
Fig. 5, as expected, the C4H radical adds without a barrier to
the triple C–C bond of acetylene thus forming a relatively
stable addition intermediate, HCCHCCCCH, which lies at
B255 kJ mol1 below the reactant asymptote (at the
CCSD(T)/CBS level of calculations employed in that study).
Once the addition intermediate is formed, it can lose an H
atom from the carbon in position 2 and generate triacetylene.
This pathway is characterized by a barrier with respect to the
product asymptote (B30 kJ mol1), which is, in any case, well
below the reactant asymptote. Alternatively, the addition
intermediate can isomerise via 2,1 H migration to give the
1-hexene-3,4-diynil-2 radical, H2CCCCCCH(2B2), through a
barrier of B168 kJ mol1. The 1-hexene-3,4-diynil-2 radical
can lose a hydrogen atom from the CH2 or CH groups, so
producing triacetylene or H2CCCCCC. The formation of the
triacetylene isomer H2CCCCCC was predicted to be endo-
thermic by 76 kJ mol1 at the CCSD(T)/CBS level of
calculations, and therefore its formation is not possible at
the temperatures of our experiments. The H-exchange channel
between C4H and C2H2 is slightly exothermic in this case
(B7 kJ mol1).9 The H-abstraction barrier9 is around
38 kJ mol1 and, therefore, this reaction channel is
not accessible at the low temperatures of our experiments.
Nevertheless, C4H2 and C2H can also be formed by the
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C–C bond fission of the HCCCHCCCH and HCCC(CH)CCH
intermediates that can be formed by the rearrangements of the
initial addition intermediate.9 These theoretical findings are
perfectly in line with the present observation of a barrierless
reaction and imply a strong similarity between C2H and C4H
reactive behaviour. The increased reactivity of C4H
with respect to C2H is most likely due to the larger size
(and therefore larger polarisability and greater long range
interactions) of C4H, but the increased stability of the
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addition intermediate (248 kJ mol1 for reaction with
C4H vs. 208.8 kJ mol1 for reaction with C2H) could also
play a role by ensuring that any subsequent barriers are so
deeply submerged that they have little or no influence on the
thermal rate coefficient.
The reactions of C2H with propyne and allene have
also been investigated, both theoretically41,42 and experi-
mentally.19,40–43 The identified reaction channels are
C2H + CH3CRCH
- C5H5z - C4H2+CH3 (10a)
- CH2QCQCH–CRCH (ethynylallene) + H (10b)
- CH3–CRC–CRCH (methyldiacetylene) + H (10c)
C2H + CH2QCQCH2
- C5H5z - C4H2 + CH3 (11a)
- CH2QCQCH–CRCH (ethynylallene) + H (11b)
- CH3–CRC–CRCH (methyldiacetylene) + H (11c)
- HCRC–CH2–CRCH (1,4-pentadiyne) + H (11d)
Kaiser et al. investigated reaction (10) in crossed beam
experiments.41 They could not identify C4H2 as an important
primary product, but they were able to discriminate between
ethynylallene and methyldiacetylene by isotopic substitution
and provided a branching ratio of 10–30% for channel (10b)
and 90–70% for channel (10c). More recently, Goulay et al.,43
using a slow flow reactor coupled to a multiplexed photo-
ionization mass spectrometer that exploits the vacuum UV
radiation of the Advanced Light Source at Lawrence Berkeley
National Laboratory, have determined a different branching
ratio, with the channel (10a) leading to diacetylene and the
methyl radical accounting for at least 50% (up to a maximum
of 70%). When considering the H-displacement channels
leading to C5H4, a C5H4-isomer distribution of 15–20% for
ethynylallene (channel (10b)) and 85–80% for methyldi-
acetylene (channel (10c)) was obtained. Goulay et al. also
investigated the reaction of C2H with allene, reaction (11).43
The production of diacetylene through reaction (11a) was
not definitely confirmed (an upper limit for the branching
ratio of 30% was found) while ethynylallene, methyldi-
acetylene and 1,4-pentadiyne were all identified as primary
reaction products with yields of 35–45%, 20–25% and
30–45%, respectively.
The significant differences between the product branching
ratios as determined in the crossed beam experiments of
Kaiser et al.41 and the flow tube photoionisation experiments
of Goulay et al.43 are not really surprising, given the much
higher average collision energy (B40 kJ mol1) and single
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collision conditions used by Kaiser et al. as compared to the
much lower room temperature equivalent mean collision
energy (B4 kJ mol1), and relatively high pressure conditions
(B5 mbar) of Goulay et al. Gannon et al.,61 using a calibrated
vacuum-UV LIF technique, observed strongly pressure
dependent H-atom product yields for the reactions of CN
with propylene and iso-butene at room temperature and over a
pressure range of B2.7–270 mbar. Clearly, there is a pressing
need for studies of product branching ratios under tempera-
ture and pressure conditions relevant to the environments in
which these reactions are taking place.
The experimental results are in agreement with the theoretical
calculations of the C5H5 PES,41,42 according to which the
favoured approach is the addition of the ethynyl radical to the
carbon–carbon triple bond of propyne or to the terminal
carbon of allene. The addition intermediates can fragment
into the observed products or rearrange to other isomeric
species before fragmenting into products. Quite interestingly,
in these two cases the addition intermediates can extensively
rearrange to different isomeric forms,42 including some cyclic
structures where the initial C2H moiety is engaged in the
formation of new bonds, so losing its ‘spectator’ nature.
Nevertheless, these are not suggested to be the major reaction
pathways, as confirmed by the available experimental
results.41–43 To the best of our knowledge, there is no informa-
tion on the potential energy surfaces describing the reactions
(2) and (4), but it is reasonable to expect a behaviour very
similar to that of reactions (10) and (11), in the light of the
similarities observed for the reactions (1) and (9). By analogy
with reactions (10) and (11), we can therefore expect that C4H
adds to the p triple bond of propyne, thus forming, in an
exothermic process and without a barrier, the addition inter-
mediates CH3–CQCH–C4H or HC4–C(CH3)QCH (with the
latter less favoured) or to the terminal/central carbon atoms of
allene forming HC4–CH2–CCH2 or HC4–C(CH2)QCH2.
Analogously to reactions (10) and (11), the possible reaction
products are
C6H2 + CH3 (2a)
HCRC–CRC–CRC–CH3 (hepta-1,3,5-triyne) + H
(2b)
H2CQCQCH–C4H (butadiynylallene) + H (2c)
HCRC–CRC–CH2–CRCH (hepta-1,3,6-triyne) + H
(2d)
In a similar fashion to the case of reaction (10) and (11), the
initial addition intermediates of reactions (2) and (4) can
probably rearrange and form complex cyclic species. To
address this issue, theoretical calculations of the C7H5
PES are desirable. Quite interestingly, butadiynylallene and,
possibly, its isomer hepta-1,3,5-triyne have been recently
identified in a photoionization mass spectrometric study of
fuel-rich flames and the reactions (2) and (4) were suggested as
the possible formation pathways.4
There is one last reaction with alkynes to comment on here,
that is, the reaction with 1-butyne. There is no information on
the related C2H reaction, but the most likely pathway would
appear to be via an addition–elimination mechanism with a
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preferential site for C4H addition being the alpha acetylenic
carbon atom yielding CH3CH2CQCHC4H. An atomic
hydrogen elimination can occur from three different sites, thus
forming (3b) ethyl-triacetylene (octa-1,3,5-triyne) if the H
released is the one bound to the carbon atom where C4H
has added; (3c) octa-5,6-diene-1,3-diyne if one of the
secondary H atoms of the ethyl group is eliminated; (3d)
octa-5,7-diene-1,3-diyne if one of the primary H atoms of
the ethyl group is eliminated. Finally, within the hypothesis
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that extensive rearrangements of the initial addition inter-
mediate(s) can take place, several stable isomers with
molecular formula C8H6 could also be formed, such as
oct-2,4,6-triyne and phenyl-acetylene. Similarly to the case of
reaction (2), the formation of C6H2 + C2H5 is probably a
viable reaction channel.
When comparing the reactions of C2H + alkenes with the
analogous reactions of C4H investigated here, several
comments can be made. The reactions
C2H + CH2QCH2 - products (12)
C2H + CH3CHQCH2 - products (13)
C2H + C2H5CHQCH2 - products (14)
have been investigated down to low temperatures and have
been found to be very fast with a slight negative temperature
dependence.16,55 The rate coefficients at 296 K for the three
reactions are k(12) = (1.13  0.14)  1010 cm3 molecule1 s1,
k(13) = (1.85  0.36)  1010 cm3 molecule1 s1, and
k(14) = (2.12  0.30)  1010 cm3 molecule1 s1.55 The
reaction with 1,3-butadiene
C2H + CH2QCH–CHQCH2 - products (15)
was also investigated and the rate coefficient at 296 K is
k(15) = (3.3  0.6)  1010 cm3 molecule1 s1.44 While the
rate coefficients for reactions (5), (6) and (8) follow a trend
similar to that of reactions (12), (13) and (15), with the
reactions involving C4H systematically faster, the rate
coefficient for reaction (7) deviates from the trend and is larger
than that of reaction (8), as already noted. This could be taken
as evidence that H-abstraction gives an important contri-
bution at least for reaction (7), possibly benefiting from the
presence of secondary H-atoms in the ethyl group. Such a
deviation in the trend for the equivalent reaction (14) has not
been observed. This also could point to a contribution from
H-abstraction for this specific reaction, as the C4H reactions
with alkanes are significantly faster than the equivalent
reactions of C2H.
To the best of our knowledge there are no theoretical
investigations of either C2H or C4H reactions with alkenes
that could help to clarify the reaction mechanisms. However,
some theoretical and experimental investigations are available
on the reaction mechanism for CN + ethylene46,61,62 and
CN + propene.61,62 In particular, there is a consensus that
an addition/elimination mechanism is operative for these two
systems as well. For the CN + C2H4 reaction, it has been
established that the only reaction products are cyanoethene
(C2H3CN) and atomic hydrogen46,61,62 which are formed after
the fragmentation of the addition intermediate C2H4CN. For
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the reaction CN + CH3CHQCH2, instead, the products
observed are C2H3CN + CH3 (with a yield of 75  15%)
and C4H5N isomers + H (with a yield of 25  15%).62
57  15% of the C4H5N isomers was identified as 1-cyano-
propene, 43  15% as 2-cyanopropene and o15% can be
attributed to 3-cyanopropene.62 Interestingly, there was
no experimental evidence of direct H abstraction or HCN
formation,62 thus suggesting that H-abstraction is not an
important channel for the reaction CN + CH3CHQCH2,
even though the formation of the relatively stable allyl radical
was believed to facilitate the H abstraction from the methyl
group of propene.61 If we assume that the C4H reactions with
ethylene and propene behave in a similar way, the expected
products are: for reaction (5), hex-1-ene-3,5-diyne + H;
for reaction (6) hex-1-ene-3,5-diyne + CH3, channel (6a),
hept-5-ene-1,3-diyne + H, channel (6b), 2-methylhex-1-ene-
3,5-diyne + H, channel (6c), and hept-6-ene-1,3-diyne + H,
channel (6d). For the reaction (7), the expected products are
(channel (7a)) C4H2 + methyl-allyl radical for the abstraction
channel, (channel (7b)) hex-1-ene-3,5-diyne + C2H5 for the
possible ethyl-loss channel, and/or some C8H8 isomers
(HCRC–CRC–CHQCH–C2H5 + H, channel (7c) and
HCRC–CRC–C(C2H5)QCH2 + H, channel (7d)) from
the H-displacement channels. Finally, in the case of reaction (8),
the addition/elimination channel products that can be
envisaged are (channel (8a)) octa-1,3-diene-5,7-diyne + H
and (channel (8b)) 5-methylidenehept-6-ene-1,3-diyne + H.
Astrophysical implications
Among the more than 150 molecules identified to date in
interstellar and circumstellar clouds, about 75% are carbon
bearing molecules and 25% are hydrocarbons.63 In general
therefore, model chemical reaction networks for the various
constituent environments of the interstellar medium (ISM)
involve a wide range of hydrocarbons either present or
suspected to be present there. Observing carbon chains and
rings, and understanding their formation and destruction in
various astrophysical objects from dark clouds to photon-
dominated regions (PDRs) or circumstellar envelopes, have
been important aims of astrochemistry for more than three
decades.64–72 Unsaturated chain radicals (CnH), carbenes
(CnH2) and cyanopolyynes (HC2nCN) are usually associated
with circumstellar envelopes, where C4H 1 and C5H 73 for
instance were first detected, or with the cold (B10 K) quiescent
dark cloud stage of star formation, where they are efficiently
shielded from interstellar radiation.63 Recent observations by
Sakai et al.67 however, revealed the presence of these molecules
in the ‘lukewarm’ (T B 20–30 K) gas associated with the
low-mass star forming region L1527. They detected high
excitation lines of various carbon-chain molecules such as
C4H2, C4H, l-C3H2, and CH3CCH, C5H, C6H and C6H2
towards this protostar (IRAS 04368 + 2557). This work was
the first detection of C4H2 toward star forming regions, and
the high excitation lines were found to originate from the inner
dense part of the protostar. Carbon chain molecules
are generally deficient in low-mass star forming regions64,74
however, and according to Sakai et al.,67 the explanation
of their presence in L1527 requires some regeneration
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mechanisms in the vicinity of the protostar. Near the proto-
star, where the temperature is higher than 30 K, the evapora-
tion of CH4 from dust grains could be an important supply of
hydrocarbons giving rise to a subsequent carbon-chain
production in the gas phase, called ‘‘warm carbon-chain
chemistry’’ (WCCC) by the authors.67 This chemistry of
regeneration of carbon-chain molecules in protostellar cores
has been recently modelled by Aikawa et al.75 In this model
gas phase reactions and grain surface reactions regenerate
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carbon chain molecules after sublimation of CH4 and C2H3
present in ice mantles of grains. When methane sublimes for
instance, it can react with C+ to form C2H3+, and subsequent
ion–molecule reactions produce larger unsaturated hydro-
carbons. Gas phase photochemistry, including neutral–neutral
reactions, can lead to the formation and growth of long
carbon chains, while adsorbed species on the other
hand, experience hydrogenation and dissociation by cosmic
radiation.
For polyynes for instance, the following polymerisation
process can occur, starting with C2H2:
H(CRC)nH + hn - (CRC)nH + H (16)
(CRC)nH + (CRC)mH2 - H(CRC)(n+m)H + H (17)
This scheme explains both the formation and the destruction
of C4H via the photolysis of C4H2 and subsequent reactions
with other species.
Unsaturated chain radicals have also been reported in the
diffuse gas of the interstellar medium where the chemical
processes are dominated by radiation, and ion–molecule
reactions play a key role in the chemistry. Quite recently,
carbon budget and carbon chemistry in PDRs, which are
denser than diffuse clouds, has been reviewed and the presence
of small carbon chain and rings investigated.63 Mapping of the
Horsehead Nebula, the cloud r Oph L1688 and the cometary-
shaped cloud IC 63 revealed the presence of C2H, c-C3H2 and
C4H, and showed numerous small hydrocarbons out to the
edge of all these PDRs. These observations were not expected,
as small hydrocarbons can be easily photodissociated by UV
radiation in these areas. At the edge of the Horsehead Nebula
for instance, the abundances of C2H, c-C3H2 and C4H were
found to be nearly as high as in dense and well shielded
molecular cores, and C6H was detected for the first time in a
PDR.63 The kinetic temperature of the observation location
was derived to be 40  2 K63 from the CO maps of Abergel
et al.,76 and the hydrogen number densities derived to be of the
order of a few times 104 cm3. Modelling the chemistry of the
PDR using two different networks, the New Standard Model
of Terzieva et al.77 and the UMIST95 chemical rate file of
Millar et al.,78 predicted abundances for C2H, C3H2 and C4H
relative to H2, were found to be lower by an order of
magnitude than abundances derived from observations.63
More recently, Pety et al.79 used the New Standard Models
chemical rate file of Lee et al.80 and the UMIST chemical rate
file of Le Teuff et al.81 and also failed to reproduce the relative
abundances of small hydrocarbons in the Horsehead Nebula.
In both papers,63,79 the authors suggest that among the
possible explanations to these discrepancies, the chemical
networks used may not include the relevant chemical reactions
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for forming carbon chains and radicals, especially those
involving neutral-neutral reactions for carbon containing
species. More recent experimental results on reactions
involving C(3P),20 C2,23 C2H,19 which were not included in
the chemical networks used, as well as this work on C4H,
demonstrate that these species react very rapidly with unsaturated
hydrocarbons even at very low temperatures (o50 K).
They may contribute therefore, to the production of
hydrocarbon chains in PDR regions. Another possible
explanation of the discrepancies between models and observa-
tions may be connected with the strong spatial correlation
found between the observations of mid-infrared emission
due to polycyclic aromatic hydrocarbons (PAHs) and the
distribution of carbon chains. This correlation suggests
that the fragmentation of PAHs due to UV-radiation could
seed the interstellar medium with carbon clusters, chains and
rings that might react with gas phase species present in the
environment. This assumption has also been proposed by
Fuente et al.82 to explain the abundance of c-C3H2 in
other PDRs.
The C4H radical, which was first detected in a circumstellar
shell (toward IRC +10216) by Guélin et al.,1 is actually
present in most of the various environments of the ISM, from
cold dense cores (T B 10 K), to the warm gas (T B 20 to 30 K)
of protostellar cores, and the hot gas (T B 40 to 100 K) of hot
corinos or PDRs. In most of these astrophysical objects
however, models fail to reproduce its high abundance as well
as those of many other hydrocarbon chains.70,79 This work
demonstrates the very high reactivity of the C4H radical with
various unsaturated hydrocarbons that would contribute to its
destruction as well as to the growth of other carbon chains.
While the presumably dominant pathway for the generation of
C4H—photolysis of C4H2—is already included in the models,
along with the photo-erosion of larger molecules,79 other
major formation routes must be found if the presence of
C4H in significant amounts in many environments is to be
explained.
Summary and conclusions
A comprehensive study has been presented of the low
temperature kinetics of the reactions of the linear butadiynyl
radical, C4H (CCCCH), with ethylene, propene, 1-butene,
allene, 1,3-butadiene, acetylene, propyne and 1-butyne over
the temperature range of 39–300 K, using a CRESU apparatus
combined with the pulsed laser photolysis—laser induced
fluorescence technique. This is the first time that the reaction
kinetics of the C4H radical with unsaturated hydrocarbons
has been investigated. The rate coefficients for all the reactions
studied remain very rapid down to the lowest temperature
of this study, indicating that these reactions take place on
potential energy surfaces without substantial barriers above
the energy of the reagents. In each case, possible reaction
products have been considered, and the need for more
high quality ab initio calculations and experimental determi-
nations of the product branching ratios has been highlighted.
Finally, the implications for the chemistry of low temperature
environments (in particular, interstellar clouds) have been
discussed.
Phys. Chem. Chem. Phys., 2010, 12, 3677–3689 | 3687

Acknowledgements
We thank the ‘‘Programme National de Planétologie’’, the
‘‘Programme National Physique et Chimie du Milieu Inter-
stellaire’’, the ‘‘Région de Bretagne’’, ‘‘Rennes Métropole’’
and the European Union (RTN Network ‘‘Molecular
Universe’’, contract MRTN-CT-2004-512302; Marie Curie
Chair ‘‘Chemistry at Extremely Low Temperatures’’, contract
MEXC-CT-2004-006734) for support. This work was
also supported by the US National Science Foundation
Published on 19 March 2010. Downloaded by Northeastern University on 22/10/2014 22:49:57.
‘Collaborative Research in Chemistry Program’ (NSF-CRC;
CHE-0627854). We are grateful to the Galileo Programme
2008/2009 for support for collaborative work between Rennes
and Perugia.
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