Dissociation and multiple ionization energies for five polycyclic aromatic

hydrocarbon molecules
A. I. S. Holm, H. A. B. Johansson, H. Cederquist, and H. Zettergren

Citation: J. Chem. Phys. 134, 044301 (2011); doi: 10.1063/1.3541252

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 THE JOURNAL OF CHEMICAL PHYSICS 134, 044301 (2011)

Dissociation and multiple ionization energies for five polycyclic

aromatic hydrocarbon molecules
A. I. S. Holm, H. A. B. Johansson, H. Cederquist, and H. Zettergrena)
Department of Physics, Stockholm University, SE-106 91 Stockholm, Sweden
(Received 21 October 2010; accepted 21 December 2010; published online 24 January 2011)

We have performed density functional theory calculations for a range of neutral, singly, and mul-
tiply charged polycyclic aromatic hydrocarbons (PAHs), and their fragmentation products for H-,
H+ -, C2 H2 -, and C2 H+
2 -emissions. The adiabatic and vertical ionization energies follow linear de-
pendencies as functions of charge state for all five intact PAHs (naphthalene, biphenylene, an-
thracene, pyrene, and coronene). First estimates of the total ionization and fragmentation cross
sections in ion–PAH collisions display markedly different size dependencies for pericondensed and
catacondensed PAH species, reflecting differences in their first ionization energies. The dissociation
energies show that the PAHq+ -molecules are thermodynamically stable for q ≤ 2 (naphthalene,
biphenylene, and anthracene), q ≤ 3 (pyrene), and q ≤ 4 (coronene). PAHs in charge states above
these limits may also survive experimental time scales due to the presence of reaction barriers as de-
duced from explorations of the potential energy surface regions for H+ -emissions from all five PAHs
and for C2 H+2 -emission from naphthalene – the smallest PAH. © 2011 American Institute of Physics.
[doi:10.1063/1.3541252]

I. INTRODUCTION To our knowledge, the previous most detailed theoret-

ical work on PAH fragmentation have been devoted to the
Polycyclic aromatic hydrocarbons (PAHs) are
azulene and naphthalene cations, where the potential energy
widespread atmospheric pollutants produced by, e.g., fuel
surfaces associated with emissions of neutral fragments (H,
burning, and are therefore, of major concern in environmental
H2 , C2 H2 , and C4 H2 ) were explored.19 It was then found
and health sciences. PAHs are also omnipresent in the
that H- and C2 H2 -loss are the lowest energy channels, while
interstellar medium as manifested by strong contributions to
H2 -loss becomes more important with increasing internal
the infrared spectrum of many interstellar sources.1–3 The
temperatures.19 These results are consistent with experimen-
electronic properties, structures, stabilities, and reactivities
tal results4–9, 14–18 and other theoretical findings suggesting
of PAHs have thus been studied in great detail for a number
that: (i) H-loss is favored over H2 -loss;20 (ii) all H atoms in
of years. In the present work, we have used the density
a PAH molecule have similar binding energies21 with values
functional theory to calculate single and multiple ionization,
almost independent of the PAH size;22, 23 and (iii) C2 H2 -loss
and the charge-state dependent fragmentation, of three
is close in energy to the H-loss channel for naphthalene and
catacondensed and two pericondensed PAHs – naphthalene
anthracene.5
C10 H8 , biphenylene C12 H8 , anthracene C14 H10 , pyrene
It has recently been realized that keV ions which are
C16 H10 , and coronene C24 H12 (see Fig. 1). The stabilities of
present in solar or stellar winds also may, on the side of pho-
these five PAHs have been investigated experimentally using
tons, play important roles in astrophysical environments when
techniques such as, e.g., photodissociation,4–13 collision
interacting with PAH molecules.24–27 This was a part of the in-
induced dissociation,14, 15 electron impact ionization,16, 17
spiration for the first studies of the interactions between keV
and fast atom bombardment.18 Most of these studies have
ions and PAH monomers28, 29 and clusters.30 The mass spectra
been devoted to neutral and singly charged molecules
recorded for monomers (anthracene, pyrene, and coronene)
demonstrating that the most prominent decay pathways are
display similar behaviors as with other ionizing and excitation
independent of the PAH size and normally correspond to the
methods (cf. above), but with stronger preferences for produc-
loss of hydrogen atoms, H2 molecules, and/or the loss of an
tions of multiply charged intact and fragment species espe-
acetylene molecule C2 H2 . For high energy deposits, small
cially for projectile ions in high charge states. In such cases,
hydrocarbons Cn Hz+ x (z = 0, 1, . . .) may also be produced. multicoincidence measurements of fragments will be partic-
Formation and fragmentation of highly charged PAHs by
ularly useful in order to determine branching ratios for the
intense femtosecond laser pulses have also been studied,9–13
various fragmentation channels. This has been done earlier
and it has recently been shown that quadruply charged
for highly charged ion–fullerene collisions,31–35 which also
2,3-benzofluorene (C17 H12 ) and triphenylene (C18 H12 ) may
inspired detailed theoretical studies of the stabilities and de-
survive on microsecond timescales.13
cays of multiply charged fullerenes. 36–38
Here, we present theoretical studies of the competition
a) Author to whom correspondence should be addressed. Electronic mail: between the main decay channels for neutral, singly, and
henning@fysik.su.se. multiply charged PAH molecules, and the results are used

0021-9606/2011/134(4)/044301/7/$30.00 134, 044301-1 © 2011 American Institute of Physics

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 044301-2 Holm et al.
FIG. 1. The five PAHs considered in the present work. No carbon atom in a
catacondensed PAH (upper row) has more than two rings in common, while
at least one carbon atom in a pericondensed PAH (lower row) has three rings
in common.
as inputs for a simple electrostatic model through which ab-
solute cross sections for electron transfer processes may be
estimated. In Sec. II, we will briefly describe the present
computational details. In Sec. III, we present the theoretical
results on the vertical and adiabatic ionization energies and
on the dissociation energies for H-, H+ -, C2 H2 -, and C2 H+2-
emissions as functions of the parent PAH charge state. We
then discuss how the ionization energies may be used in, e.g.,
electrostatic models to estimate the combined total ionization
and fragmentation cross sections in ion–PAH collisions. The
dissociation energy results are discussed in view of transi-
tion structure calculations associated with the C2 H+
2 -emission
from multiply charged naphthalene and with the H+ -emission
from PAHq+ .
II. COMPUTATIONAL DETAILS
The results presented in this work are based on den-
sity functional theory calculations as implemented in the
GAUSSIAN 03 package.39 The B3LYP functional, combining
Beckes three parameter nonlocal hybrid exchange potential40
with the nonlocal correlation functional of Lee et al.,41
was used. This functional provides excellent descriptions
of the electronic properties of carbon clusters,42 multiply
charged fullerenes,36–38 and, in particular, neutral and singly
charged PAHs.2, 19, 43 Thus, we have chosen this theoretical
approach for the present study which also includes multi-
ply charged PAH molecules. All the geometries have been
optimized using the 6-31G(d) basis set without any sym-
metry constraint, followed by frequency calculations in or-
der to determine the local minima (all real frequencies) and
transition structures (one imaginary frequency). Connections
between transition structures and their corresponding local
minima were confirmed by intrinsic reaction coordinate cal-
culations. In addition, the most stable structures have been
optimized using the 6-311++G(2d,p) basis set, followed by
frequency calculations. The zero-point vibrational energies
were multiplied by the empirical scaling factor 0.9877
(Ref. 44) in order to compensate for the vibrational anhar-
monicity and incomplete descriptions of electron correlation.
It should be noted that these corrections do not influence the
present conclusions regarding the general trends of ionization
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J. Chem. Phys. 134, 044301 (2011)
and dissociation energies as functions of PAH charge states.
The trends are also very similar for the small [6-31G(d)] and
the larger basis set [6-311++G(2d,p)], and thus, only the re-
sults from the larger basis set calculations are presented here,
except for the transition structure calculations (Sec. III C)
which were carried out using the smaller basis set only.
The molecular orbitals from which the electrons are ver-
tically removed are rather well separated in energy for all
neutral PAH systems considered in the present work, except
for coronene which has a doubly degenerated highest occu-
pied molecular orbital (HOMO) and a doubly degenerated
HOMO-1 orbital. According to Hund’s rule, one would thus
expect that the triplet states of doubly and sextuply charged
coronene are lower in energies than the corresponding singlet
states. In all other cases we have only considered the lowest
spin states. This seems to be a well-justified approach to pre-
dict the correct trends of ionization and dissociation energies
as functions of charge state, since we found that excluding the
higher spin states for all charge states of naphthalene and its
dissociation products gave a maximum error of 0.04 eV only.
III. RESULTS AND DISCUSSION
A. Ionization energies and electron transfer
cross sections
We extract the adiabatic ionization energies by subtract-
ing the zero-point energy corrected B3LYP/6-311++G(2d,p)
energies of PAHq+ and PAH(q+1)+ in their optimum ge-
ometries and the vertical ionization energies from the cor-
responding (noncorrected) energy differences with PAHq+
and PAH(q+1)+ in the optimum geometries of the neu-
tral systems. The calculated first and second ionization en-
ergies and the sum of these energies (double ionization
energies) are shown in Table I together with the most
recent experimental results45, 46 as given by the NIST Chem-
istry WebBook47 and in the theoretical database of polycyclic
aromatic hydrocarbons.48 The ionization energies agree rather
well with the experimental results, where the adiabatic values
are only slightly lower than the vertical ones indicating that
the PAH structures do not change significantly when these
molecules are singly or doubly ionized. The present results
are also in agreement with other theoretical results for neu-
tral and singly charged PAHs,48, 49 justifying the choice of the
present theoretical approach. Note that the present results sug-
gest that the second vertical and adiabatic ionization energies
of coronene corresponds to a triplet state in agreement with
the Hund’s rule for a doubly degenerated HOMO level.
For higher PAH charge states, there are to our knowledge
no corresponding data available in the literature. The adia-
batic and vertical ionization energies as a function of PAH
charge state q are shown in Fig. 2 and in Tables II and III
(Appendix). These follow linear dependencies along the ion-
ization sequence, as illustrated by the solid curves obtained
from linear fits (IEq + 1 = A + Bq) to the present theoretical
results. The fitting parameters ( A and B) summarized in
Table IV (Appendix) may be very useful for simple estimates
of the ionization energy sequences, and similar expres-
sions have been used earlier in, e.g., electrostatic models
 044301-3 Dissociation and ionization of five PAHs J. Chem. Phys. 134, 044301 (2011)

TABLE I. Calculated first (IE1 ), second (IE2 ), and double ionization energies (IE1 + IE2 ), where the superscripts denote the adiabatic (a) and the vertical (v)
values. The cases when triplet states are lower in energy than the corresponding singlet states are denoted by superscript t (the corresponding energies for the
singlet states within parenthesis). The most recent experimental results for the first ionization energies (Ref. 45) and the double ionization energies (Ref. 46)
are shown for comparisons. All values are in eV.

Naphthalene Biphenylene Anthracene Pyrene Coronene

IEa1 theory 7.86 7.29 7.09 7.13 7.00
IEv1 theory 7.95 7.42 7.15 7.20 7.11
IE1 experiment 8.144 ± 0.001 7.58 ± 0.03 7.439 ± 0.006 7.426 ± 0.001 7.29 ± 0.03
IEa2 theory 13.19 12.11 11.71 11.61 10.81t (10.91)
IEv2 theory 13.50 12.61 11.90 11.83 10.77t (11.08)
IEa1 + IEa2 theory 21.05 19.40 18.81 18.74 17.81t (17.91)
IEv1 + IEv2 theory 21.45 20.03 19.05 19.03 17.88t (18.19)
IE1 + IE2 experiment 21.5 ± 0.2 19.7 ± 0.2 19.8 ± 0.2 18.7 ± 0.20

describing electron transfer processes in keV ion-
collisions.50–54 The slope (B) is related to the capacitance
(and radius in the case of a spherical cluster/molecule) and
the intercept (A) is related to the surface work function
(i.e., the ionization energy for an object with large exten-
sion). The capacitance, in turn, is related to the molecular
polarizability and, may thus, be used to build more realistic
ion–molecule interaction potentials where polarization
effects are taken into account. This is rather straightforward
for collisions between (multiply) charged ions and spherical
objects (as, e.g., the fullerenes) as the potential barrier
experienced by the active electron only depends on the
radial distance to the sphere center.50, 51 A similar approach
using the present results for modeling ion-PAH collisions
would become more involved since the PAH orientation has
to be taken into account. However, we have chosen to use
the classical over-the-barrier model in its simplest form,55 in
which the target molecule is assumed to be point formed, for
first estimates of the total ionization and fragmentation cross
1/2
sections as σtot = π R21 . Here, R1 = [2q p + 1]/IE1 is the
critical distance for capturing the first electron. We expect the
σtot -values to be higher when the actual collision geometries
are taken into account, since the electron may then be
captured at larger distances from the center of the molecule
due to its geometrical size and polarization effects.50, 51 For a
highly charged projectile, the present much simpler approach
is, however, rather reasonable as the critical distances, R1 , for
electron removal are considerably larger than the dimensions
of the molecules.
The σtot -values as functions of the number of carbon
atoms n in PAH molecules Cn Hm are shown in Fig. 3. Here,
we have used a projectile charge, q p = 20, and the verti-
cal rather than the adiabatic ionization energies as these bet-
ter represent the conditions when PAH monomers28, 29 and
clusters30 are interacting with keV ions on subfemtosecond
timescales. The molecular structures may thus be regarded as
frozen during the interaction process. In addition, the first ion-
ization energies for catacondensed tetracene (C18 H12 ), pen-
tacene (C22 H14 ), and hexacene (C26 H16 ), and pericondensed
circumpyrene (C42 H16 ) and circumcoronene (C54 H18 ) were
extracted from single point calculations at the B3LYP/6-
311++G(2d,p) level using the structures from Ref. 48 op-
timized at the B3LYP/6-31+G* level. With these values
included in Fig. 3, it becomes clear that catacondensed PAHs
(naphthalene, anthracene, tetracene, pentacene, and hexac-
ene) have a much steeper trend compared to pericondensed
ones (pyrene, coronene, circumpyrene, and circumcoronene).
These results suggest different ionization and fragmentation
behaviors for catacondensed and pericondensed species, even
when they contain the same number of carbon atoms. This is
because the impact parameter regions for multiple electron

FIG. 2. The adiabatic (upper panel) and the vertical ionization energies
(lower panel) as functions of the PAH charge state q for the catacondensed
(closed symbols) and pericondensed (open symbols) PAHs considered in the
present work. The solid curves are linear fits to ionization energy sequences.
FIG. 3. The total ionization and fragmentation cross sections in keV ion-
PAH collisions (cf. text) as functions of the number of carbon atoms n in
PAHs Cn Hm , calculated by means of the classical over-the-barrier model
(Ref. 55) using the present vertical ionization energies (cf. text). The results
for the pericondensed (open circles) and catacondensed PAH species (solid
circles) display markedly different trends as functions of n.

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 044301-4 Holm et al. J. Chem. Phys. 134, 044301 (2011)

removal are markedly different in the two cases. To our

knowledge, there are to date no measurements of absolute ion-
ization and fragmentation cross sections in keV ion–PAH col-
lisions reported in the literature, and therefore, such measure-
ments would be of great interest in order to test the present
theoretical predictions. We should stress though that such
measurements could be difficult due to the poor knowledge
of vapor pressures as functions of temperature, and there-
fore, also of target densities in the experiments. However, Fig.
3 also indicates that the relative fragmentation probabilities
should be greater for peri- than for catacondensed PAHs as
the projectile has to come closer to pericondensed PAHs to
capture electrons and this may be easier to check in experi-
ments. In the following, the dissociation mechanisms of mul-
tiply charged PAHs will be discussed in more detail.

B. Dissociation energies
Previous theoretical and experimental studies have un-
ambiguously shown that the lowest energy dissociation chan-
nels are single hydrogen (H)-loss and loss of one acetylene
molecule (C2 H2 ) from neutral and singly charged PAHs. As
the PAH charge state increases the loss of charged fragments
become important, mainly through the C2 H+ 2 -loss channel.
56

In the present work, we study the competition between losses

of H, H+ , C2 H2 , and C2 H+
2 as functions of the PAH charge
state. Schematics of the structures of the five intact PAH
molecules and their fragment structures after C2 H2 - and
C2 H+2 -loss are shown in Fig. 4. In the case of napthalene,
there are two isomers competing for the lowest dissociation
energy channel (cf. Fig. 4) as functions of the charge state.
Experiments57 and theoretical work19, 58–60 have shown that
FIG. 5. Dissociation energies for H-loss (solid squares), C2 H2 -loss (solid tri-
angles), H+ -loss (open squares), and C2 H+ 2 -loss (open triangles) as functions
of the PAH charge state. The vertical dotted lines indicate the thermodynam-
ical stability limits. Lines between the data points are to guide the eye.

the lowest energy isomer (C8 H+ 6 ) for the cation is benzo-

FIG. 4. Schematics showing the structures of the lowest energy isomers after
C2 H2 - and C2 H+
2 -loss from the multiply charged PAHs considered in the
present work. The adiabatic dissociation energy channels are indicated by the
PAH charge state (q) in the naphthalene case where there are two competing
fragment isomers.
cyclobutadiene, however, in close competition with pheny-
lacetylene (cf. Fig. 4). For anthracene the lowest energy
isomer (C12 H+ 8 ) is acenaphthylene, but the measured activa-
tion barrier for C2 H2 -loss from the monocation58 indicates
that biphenylene is formed. In the following, we will only
show the results for the most stable isomer as functions of
the PAH charge state (adiabatic values).
The adiabatic dissociation energies shown in Fig. 5 dis-
play similar trends as functions of the PAH charge state q
and agree well with those previously obtained for neutral
and singly charged PAHs.8, 19, 22, 61 The dissociation energies
remain more or less constant (at ∼5 eV) for H-loss and in-
crease slightly with q for C2 H2 -loss. In contrast, the disso-
ciation energies for H+ and C2 H+ 2 decrease rather dramat-
ically and determine when fragmentation become exoergic
(negative dissociation energies), and thus, the thermodynamic
stability limit. The multiply charged species become ther-
modynamically unstable for q = 3 (naphthalene, bipheny-
lene, and anthracene), q = 4 (pyrene), and q = 5 (coronene).
There are differences in the relations between the dissocia-
tion energy sequences, which may play important roles for the

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 044301-5 Dissociation and ionization of five PAHs
FIG. 6. Calculated energy levels (in eV) associated with the fission barriers
for C2 H+ 2 -losses from multiply charged naphthalene (q = 3,4,5), together
with the corresponding molecular structures for q = 3. The energy levels
for all the three intact species (q = 3,4,5) are arbitrarily set to zero for easy
comparisons.
competition between different decay pathways. For low
charge states, the dissociation energies corresponding to H-
loss and C2 H2 -loss are similar for the smallest PAHs (naph-
thalene, biphenylene), while the lowest energy channels cor-
respond to C2 H2 -loss for anthracene and to H-loss for pyrene
and coronene (small q). Emission of charged fragments
become competitive for q = 2 (naphthalene, biphenylene,
anthracene, and pyrene), and q = 3 (coronene). Here, C2 H+ 2-
loss correspond to the lowest energy channel up to the ther-
modynamical stability limits. Note, however, that the H+ -loss
channel is very similar in energy in that region for pyrene and
anthracene.
C. Fission barriers
The stabilities of multiply charged molecules may be
governed by fission barriers preventing thermodynamically
unstable species from decay on experimental timescales of
microseconds. Thus, in order to determine branching ratios
for competing channels and to predict the ultimate Coulomb
stability limits of multiply charged PAHs, reaction barriers
need to be taken into account. Dyakov et al. 19 have stud-
ied the reaction pathways for singly charged naphthalene by
means of ab initio structure and Rice–Ramsperger–Kassel–
Marcus rate constant calculations. Such systematic and de-
tailed explorations of the potential energy surfaces are be-
yond the scope of the present work dealing with larger PAH
systems in high charge states. Instead, we make a first ap-
proach where we investigate how the charge state affect the
fission barriers for C2 H+
2 -loss from naphthalene assuming that
the reaction pathways are similar as for C2 H2 -loss from the
napthalene cation.19 There,19 it was found that there are two
possible pathways yielding the different C8 H+ 6 isomers shown
in Fig. 4. The initial steps in the lowest barrier route involve
hydrogen shifts to neighboring carbons, followed by a ring
opening from which C2 H2 is finally eliminated via interme-
diates on the potential energy surface.19 Here, we simply cal-
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J. Chem. Phys. 134, 044301 (2011)
FIG. 7. The fission barriers as functions of the charge state for proton emis-
sion from the five PAHs considered in the present work (solid symbols),
together with the corresponding fission barriers for C2 H+ 2 -emission from
napthalene (open squares). Lines are to guide the eye.
culate the transition structures for the last step corresponding
to the highest barrier in this reaction. The B3LYP/6-31G(d)
results for charge states q = 3,4,5 are illustrated in Fig. 6,
where the energies of the intact species are set to zero in
all three cases (q = 3,4,5). The fission barrier is positive for
q = 3,4 and it is negative for q = 5. Thus, the ultimate stabil-
ity limit for this channel is q = 4 at this level of theory, which
is two units of charge higher than the thermodynamical sta-
bility limit (cf. Fig. 5).
In order to investigate how the PAH size influences the
height of the fission barrier, we carried out the most sim-
ple transition structure calculations corresponding to H+ -loss
from all five PAHs in the present study. The B3LYP/6-31G(d)
fission barriers for H+ -loss are shown in Fig. 7 and are sig-
nificantly higher than the corresponding dissociation energies
(cf. Fig. 5). As expected, the larger PAHs appear to be able to
accommodate more charge (higher ultimate stability limits).
Note, however, that the fission barriers for C2 H+ 2 -loss from
napthalene (open squares in Fig. 7) are lower than the ones for
H+ -loss from the same molecule. These result suggest that the
C2 H+ 2 -loss channel determines the ultimate stability limits of
multiply charged PAHs, and that the stability limits are a few
charge states higher than what is indicated by the correspond-
ing thermodynamical stability limits. PAHs in charge states
exceeding their thermodynamical stability limits have indeed
been produced using highly charged ions and femtosecond
laser pulses, as, e.g., triply charged naphthalene,12, 13 triply
charged anthracene,9–11 and quadruply charged pyrene29 have
been observed. This shows that the lifetimes determined by
the fission barrier heights are comparable with the experimen-
tal timescales (microseconds) or longer.
IV. SUMMARY AND CONCLUSIONS
In this work, we have performed density functional the-
ory calculations for five polycyclic aromatic hydrocarbon
molecules (naphthalene, biphenylene, anthracene, pyrene,
and coronene) as functions of their charge state q. The cal-
culated dissociation energies for losses of H, H+ , C2 H2 , and
C2 H+2 show similar trends as functions of q, but with differ-
ent slopes suggesting that they are thermodynamically stable
for q ≤ 2 (naphthalene, biphenylene, and anthracene), q ≤ 3
(pyrene), and q ≤ 4 (coronene). Thus PAHs in slightly higher
charge states produced by femtosecond laser pulses9–13 and
 044301-6 Holm et al. J. Chem. Phys. 134, 044301 (2011)

by highly charged ion impact29 are most likely metastable TABLE IV. The fitting parameters ( A and B) obtained from linear fits to
with lifetimes of microseconds or longer. These findings are the sequences of the adiabatic (IEqa + 1 = Aa + B a q) and the vertical (IEqv + 1
= Av + B v q) ionization energies. All values are in eV.
further supported by the present transition structure calcula-
tions revealing significant fission barriers for C2 H+ +
2 - and H - A B
emissions from multiply charged metastable PAHs. Naphthalene 7.65 ± 0.23v 5.83 ± 0.07v
The vertical and adiabatic ionization energies follow lin- 8.04 ± 0.21a 5.26 ± 0.07a
ear dependencies along the ionization sequences and may Biphenylene 7.33 ± 0.07v 5.39 ± 0.02v
serve as important model parameters, as illustrated by first 7.50 ± 0.37a 5.02 ± 0.12a
estimates of the total ionization and fragmentation cross sec- Anthracene 7.18 ± 0.19v 4.91 ± 0.06v
tions in keV ion–PAH collisions based on the classical over- 7.36 ± 0.35a 4.63 ± 0.11a
the-barrier model in its simplest form.55 These results show Pyrene 7.02 ± 0.18v 4.84 ± 0.04v
7.53 ± 0.32a 4.42 ± 0.08a
that electron transfer distances are markedly different for
Coronene 6.70 ± 0.30v 4.05 ± 0.06v
catacondensed and pericondensed species containing similar
7.15 ± 0.22a 3.81 ± 0.04a
number of carbon atoms, which will influence the relative
ionization yields and the energy deposited in the collisions, TABLE V. The adiabatic dissociation energies for losses of H, C2 H2 , H+ ,
and lead to clear differences in the ionization and fragmenta- and C2 H+ 2 from naphthalene (C10 H8 ), biphenylene (C12 H8 ), anthracene
tion behaviors for these two classes of PAH molecules. The (C14 H10 ), pyrene (C16 H10 ), and coronene (C24 H12 ). All values are in eV.
relative fragmentation yields for electron transfer collisions
q Pathway C10 H8 C12 H8 C14 H10 C16 H10 C24 H12
will be considerably smaller for cata- than for pericondensed
0 –H 4.7 4.7 4.7 4.7 4.7
PAHs.
–C2 H2 4.0 3.5 2.7 6.9 8.0
ACKNOWLEDGMENTS 1 –H 4.8 5.0 5.3 5.1 5.2
–C2 H2 4.6 4.3 3.3 6.4 7.3
We acknowledge generous financial support from the –H+ 10.5 11.1 11.3 11.3 11.4
Swedish Research Council, the ITS-LEIF Project (RII3 - –C2 H+ 7.4 7.5 6.9 11.0 12.3
2
026015), and the Danish Council for Independent Research
2 –H 4.5 5.1 5.0 5.0 4.7
| Natural Science. –C2 H2 4.5 5.8 4.4 5.7 6.8
–H+ 5.3 6.6 7.2 7.2 8.0
APPENDIX: IONIZATION AND DISSOCIATION –C2 H+
2 2.7 3.5 2.8 6.1 7.6
ENERGIES 3 –H 4.2 4.2 4.1 4.5 5.2
–C2 H2 6.2 7.1 5.2 6.8 7.9
–H+ −0.6 0.8 1.6 2.0 4.0
TABLE II. The vertical ionization energies for naphthalene C10 H8 , –C2 H+
2 −3.0 −1.0 −1.4 0.4 3.7
biphenylene C12 H8 , anthracene C14 H10 , pyrene C16 H10 , and coronene
4 –H 4.2 4.0 3.7 4.3 5.0
C24 H12 . All values are in eV.
–C2 H2 7.8 8.5 6.4 8.2 8.4
q C10 H8 C12 H8 C14 H10 C16 H10 C24 H12 –H+ −6.2 −5.2 −4.1 −3.0 0.5
0 7.95 7.42 7.14 7.20 7.11 –C2 H+
2 −6.6 −4.8 −5.4 −3.1 0.8
1 13.50 12.60 11.90 11.83 10.77 5 –H 4.2 4.1 4.1 4.4 4.4
2 18.90 18.12 17.18 16.64 14.76 –C2 H2 8.8 10.1 8.1 9.2 7.9
3 24.92 23.48 22.28 21.53 18.49 –H+ −11.4 −10.1 −8.5 −7.6 −4.2
4 30.91 28.80 26.54 26.08 23.08 –C2 H+
2 −10.2 −7.9 −8.2 −6.1 −3.2
5 37.09 34.35 31.73 31.60 27.05 6 –H 4.7 4.5 4.2 3.8 4.1
6 35.70 30.91 –C2 H2 11.6 12.9 10.4 10.5 7.7
7 41.21 35.88 –H+ −16.1 −14.3 −12.3 −12.2 −8.8
8 38.72 –C2 H+
2 −13.9 −10.7 −10.7 −9.8 −7.7
9 43.47 7 –H 4.3 4.7
–C2 H2 12.1 8.8
TABLE III. The adiabatic ionization energies for naphthalene C10 H8 , –H+ −16.4 −12.2
biphenylene C12 H8 , anthracene C14 H10 , pyrene C16 H10 , and coronene –C2 H+
2 −12.0 −11.0
C24 H12 . All values are in eV.
8 –H 4.9 4.5
q C10 H8 C12 H8 C14 H10 C16 H10 C24 H12 –C2 H2 14.1 9.7
0 7.86 7.29 7.09 7.13 7.00 –H+ −19.9 −15.7
1 13.19 12.11 11.71 11.61 10.81 –C2 H+
2 −14.5 −14.1
2 18.77 18.03 17.03 16.60 14.54 9 –H 4.9
3 24.03 23.09 21.87 21.17 18.38 –C2 H2 10.7
4 29.30 27.73 25.90 25.57 22.88 –H+ −19.3
5 33.95 32.05 30.05 30.26 26.45 –C2 H+
2 −16.5
6 33.78 30.38 10 –H 5.1
7 37.82 34.1 –C2 H2 11.9
8 37.43 –H+ −22.2
9 40.80 –C2 H+
2 −18.9

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