International Journal of Mass Spectrometry 354355 (2013) 204210

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International Journal of Mass Spectrometry

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Infrared spectroscopy of trapped molecular dications below 4 K

Juraj Jask a , Jn Zabka a,b , Jana Roithov a, , Dieter Gerlich c,
a
Department of Organic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030/8, 12843 Prague 2, Czech Republic
b
J. Heyrovsky Institute of Physical Chemistry, Academy of Science of the Czech Republic, 182 23 Prague 8, Czech Republic
c
Department of Physics, University of Technology, 09107 Chemnitz, Germany

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

Article history: First results from a new ion trap instrument are presented. With this instrument, ions can be cooled to
Received 17 April 2013 temperatures below 4 K using helium buffer gas. Low temperatures and high densities lead to efcient
Received in revised form 12 June 2013 formation of helium-tagged ions allowing us to record infrared predissociation spectra of highly reactive
Accepted 12 June 2013
species. After a short description of the instrument and its special features, the rst IRPD spectrum of
Available online 24 June 2013
a small hydrocarbon dication, C7 H6 2+ , is presented. The spectral features observed between 2900 and
Dedicated to the memory of Detlef 3200 cm1 indicate that this dication corresponds to doubly ionized cycloheptatrienylidene. Several DFT
Schrder. methods and the MP2 method are applied to study the effect of helium tagging. The results suggest that
the effect of helium on the structure as well as on the IR spectrum of the dication is only minor; most
Keywords: probably in the range of the errors of the theoretical models.
Buffer gas cooling 2013 Elsevier B.V. All rights reserved.
Dications
Helium
Infrared predissociation spectroscopy
Linear wire quadrupole trap
Tagging

1. Introduction
Infrared spectroscopy of mass-selected gaseous ions has expe-
rienced a large boom in the last years. The main purpose consists
in acquiring additional structural information on mass-selected
ions aside from classical tools such as collision induced disso-
ciation. Hence, we are witnessing an increasing popularity of
infrared multiple-photon dissociation spectroscopy [1,2], but also
many instruments, optimized for single-photon spectroscopy, are
being developed. Methods based on infrared spectroscopy of ions
tagged by an innocent rare-gas atom (usually argon) [35] or a
molecule (hydrogen molecule [6], water [7], and others [8]) are
used to disentangle questions as complicated as the 3D-structure
of noncovalent complexes between a peptide catalyst and substrate
[9].
The use of rare-gas atoms as tags for studying the structure of
ions is based on the assumption that the perturbation caused by
the interaction with a rare-gas atom is minor. Hence, the primary
interest focuses on weakly bound complexes. Formation of such
complexes requires cooling of the internal degrees of freedom of
Corresponding author. Tel.: +420 221951322; fax: +420 221951326.
Corresponding author.
E-mail addresses: roithova@natur.cuni.cz (J. Roithov),
gerlich@physik.tu-chemnitz.de (D. Gerlich).
the ion of interest so that stable rare-gas complexes are formed
for further studies. This can be achieved in supersonic expansions
[3,10,11], by evaporative cooling of cluster ions [12,13], by cooling
the ions with buffer gas in an ion trap [14], or with other sophis-
ticated methods [15]. Here, we present a new instrument where
ions are conned in a linear radio frequency wire quadrupole trap
(rf w4PT) for cooling them below 4 K.
The buffer gas used for very cold conditions is helium. In addition
to cooling internal degrees of freedom, the buffer gas reduces also
the kinetic energy of ions and hence increases the efciency to accu-
mulate a large number of them in a trap. A big advantage of trapping
experiments is that the trapped ions are not only prepared for spec-
troscopic experiments, but also their reactivity can be probed under
various conditions. The simplest reaction is the formation of adduct
complexes. If a small admixture of H2 or Ar is added to the helium
buffer gas, the formation of complexes between the trapped ions
and H2 or Ar, respectively, can be observed [16]. The binding energy
between H2 or Ar and large organic ions (such as mono- or dian-
ions generated from dodecanedioic acid [17]) is usually so small
that vibrational excitation via IR radiation leads to the elimina-
tion of the H2 or Ar tag, respectively. This provides the grounds
for infrared predissociation spectroscopy [18]. In the case of highly
reactive ions, however, it is a question, how the mentioned tags
inuence the structure of the investigated ions. While H2 can react
with many substrates, Ar has a large polarizability which may have
non-negligible effects on the structure of the reactive ions. As an

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 J. Jask et al. / International Journal of Mass Spectrometry 354355 (2013) 204210
alternative, therefore, less polarizable rare-gas atoms should be
used for IRPD for highly reactive ionic species [4,19].
The properties of our newly constructed ion trap instrument
allow us to reach temperatures below 4 K. Under these conditions, it
is possible to generate helium-tagged ions. As helium is the weakest
bound rare gas, it is best suitable as a tag for the investigation of
the most reactive ionic species. Perturbation of vibrational modes
of the investigated ions is expected to be very low. To demonstrate
the advantage of helium tagging, we present here the rst infrared
pre-dissociation (IRPD) spectrum of doubly charged hydrocarbon
superelectrophiles [20].
There is only a handful of reports about ion spectroscopy of small
multiply charged ions because of several reasons. The rst one is the
difculty of generation of dications, which, however, can be usu-
ally surmounted, if the respective dications are at least kinetically
stable. The second one consists in the irradiation induced disso-
ciation of the dication itself. Fragmentation barriers for molecular
dications are usually rather high. It either leads to an exothermic
dissociation into two singly charged ions via the so-called Coulomb
barrier or the dication eliminates a neutral molecule in that the
bonding between a doubly charged ion and a molecule is usually
associated with a rather large binding energy. Clearly, the large
energy demands represent a problem for photodissociation using IR
instead of UV photons [21,22]. It also should be noted that the frag-
mentation process is becoming easier with increasing size of the
studied dications [23,24]. Even higher charge-states can be studied
if the size of the complex is large enough [25].
Using a tagging method for dications is also not straightfor-
ward. The binding energy between argon and small dications can
be rather large and actually it was shown that dications can form in
reaction with argon thermodynamically stable species with cova-
lently bound argon [2629]. For small metal complexes, several
argon atoms have to be used in order to get to a regime in which IR
irradiation is able to detach one argon atom [3032]. Clearly, if the
tagging atoms/molecules are bound rather tightly to the studied ion
then also the structure of this ion can be signicantly inuenced.
Hence, the only known infrared predissociation spectra of dicat-
ions correspond to water complexes of divalent metals with either
a large number of water ligands or four and more attached argon
atoms. There are also reports of large complexes of divalent metals
with ligands other than water, but clearly with increasing size of
the studied ion, the problem with the double charge diminishes and
the IRPD spectra can be obtained as comfortably as for the singly
charged ions [33,34].
The real challenge thus remains to probe spectroscopically
small highly reactive molecular dications. On contrary to metal
dications and their complexes which often have their second ion-
ization energy lower that the rst one of argon, small molecular
dications may easily undergo charge transfer with argon or make
covalent bonds [26,27]. Our aim is to spectroscopically character-
ize small and medium sized hydrocarbon dications. These species
are extremely reactive and, due to their twofold charge, they
can possess unusual structures. This pilot paper is focused on
the presentation of a new instrument, which allows formation
of complexes of dications with loosely bound helium atoms. The
spectroscopy will be shown for the C7 H6 2+ dication, which is the
model dication used in most of the reactivity studies made by Detlef
Schrder and coauthors during the last seven years [3542].
2. Experimental
The experiments were performed with the new instrument
ISORI (Ion Spectroscopy of Reaction Intermediates). This instrument
has been designed to trap mass-selected ions, cool them down to
a few K, let them interact with laser radiation or perform other
205
Fig. 1. Geometry of the ISORI instrument.
experiments provided by the trapping technique, and nally mass-
analyze the products of the interactions.
As illustrated in Fig. 1, ISORI is based on the combination
of a low-temperature ion trap with a commercial instrument
TSQ 7000 (Thermo Finnigan) which has, in its original design, a
quadrupoleoctopolequadrupole geometry [43]. In order to use
all commercial TSQ-compatible ion sources (EI/CI, ESI, API, APCI),
we have cut the TSQ manifold into two pieces. The front part serves
as a holder for the EI/CI source or as an interface with a trans-
fer quadrupole between the ESI source and the quadrupole stage
placed in the second differentially pumped volume of the case.
The front part is connected with the main instrument using a cus-
tomized ange with an O-ring tting in the side of the source
and serves in the ISORI instrument in the same way as in the
original TSQ. The following modules of the instrument are placed
in standard CF housings so that the vacuum chamber consists of
three differentially pumped regions: (1) the ion source region, (2)
the region with the rst quadrupole (4P1 ), the quadrupole bender
(QPB), and the octopole (8P), and (3) the region with the ion trap
(w4PT), the second quadrupole (4P2 ), and the detector.
The original TSQ electronics are used for controlling the ion
source, driving the rst and second quadrupole (4P1 , 4P2 ) and
the octopole ion guide 8P, and to provide the voltages for the
ion detector. The other parts of the instrument are controlled by
custom-made electronics. The Daly type detector is constructed
from the original parts of the TSQ mounted into a customized cham-
ber. We operate the detector (DeTech 2312) in the ion-counting
mode. The pulses are counted by a multichannel scaler (Becker &
Hickl PMS-400A, discriminator threshold 8 mV).
The central element, located between the TSQ 7000 based mod-
ules, is an rf ion trap mounted onto a cold head. Cooling of ions
with buffer gas is usually performed in multi-electrode traps (22-
pole or ring electrode traps, see [44]) which have least effects on
the kinetic energy distribution of the conned ions. Here, for heavy
ions in the light buffer gas, we have chosen a rather open linear
quadrupole geometry which has several advantages such as in situ
mass selection, better overlap with a laser beam, and optical access.
The design of the ion trap is shown in Fig. 2. The inner part of the
housing is made from a solid high-quality oxygen-free copper block
with a half-cylindrical inner bore. It is cooled by the 2nd stage of a
Sumitomo RDK-101E cold-head. As indicated in Fig. 1, this arrange-
ment is protected against the surrounding black-body radiation by
an aluminum shield cooled down to 41 K via the 1st stage of the
cold head. The temperatures of both stages are measured by silicon-
diode sensors (LakeShore DT-670B1-CU). The upper side of the trap
can be closed with a quartz window for observing photons emitted
from the trapped ions. In this experiment, however, an aluminum
foil has been used to protect the trap against the surrounding black-
body radiation in order to achieve the lowest possible temperature.
206 J. Jask et al. / International Journal of Mass Spectrometry 354355 (2013) 204210
Fig. 2. Design of the wire quadrupole ion trap mounted into a copper box. EN: entrance electrode, wire: electrodes of the w4PT, QW: quartz window, PCB: printed circuit
board, and TS: temperature sensor, Si diode. The indicated dimensions are in mm.
The entrance as well as the exit side of the trap is closed with two
identical printed circuit boards (PCB), made from a ceramic-lled
PTFE composite and coated with a copper layer (Rogers RO3003).
Using four screws they are attached to the cold body of the trap.
Suitable circuits, etched onto these boards and connected with lead
solder, provide the electrical contacts for the electrodes, i.e., for the
four groups of 6 wires as well as the entrance or exit electrode,
respectively.
In order to nd the optimum location of the 24 copper wires
(1 mm diameter) for approximating the ideal hyperbolic boundary
conditions of a linear quadrupole, the 2D Laplace equation has been
solved numerically using the Finite Element Method on a triangular
mesh. The geometry is shown in Fig. 3 together with the differ-
ence between the ideal potential, (r, ) = 0 (r/r0 )2 cos(2) with
0 = 103.4 V and r0 = 0.598 cm and the potential calculated for the
wire coordinates given in Fig. 2. Inspection reveals that the agree-
ment in the inner part of the trap is excellent while the contribution
of higher order multipoles becomes visible closer to the electrodes.
More details will be discussed in a forthcoming description of the
instrument.
Reaching the lowest possible temperature is of basic importance
for studying He-tagged ions. With our arrangement we reach 3.3 K
Fig. 3. Simulation of the potential of the w4PT. Contours show the difference
between the numerically calculated potential and the ideal quadrupole potential
in steps of 0.1 V, 1 V and 10 V. The surrounding cylinder (diameter of 27 mm) has
been set to 0 V.
without buffer gas and the cold head reaches 3.47 K at a load of
0.1 W according to the nal test sheet. The buffer gas is injected
with a custom-made piezo valve situated in vacuum. It is connected
directly to the trap with a straight 37 mm long Teon tube (inner
diameter 2 mm, entrance hole see the left side of the drawing with
dimensions in Fig. 2).
For determining the lling and residence time of He buffer gas,
we have made use of the fact that thermalized ions have a higher
overall detection efciency than the ions just passing through the
trap. Keeping the trap continuously open and running a continuous
ion beam through it leads to an increasing number of detected ions
if the neutral density is increasing (known as phase space compres-
sion). The linearity of this effect has not yet been checked; however,
the results, shown in Fig. 4a for a beam of N2 + , provide interesting
insight into the time dependence of the density of the buffer gas.
Fig. 4. (a) Helium density in the trap after exciting the piezo valve with a 200 s
pulse monitored as the number of detected N2 + ions (see the text). The inset shows
the sharp increase during the rst ms (supersonic jet). (b) Number of ions with
m/z = 32 (N2 He+ clusters and O2 + ) as a function of the temperature of the trap. Data
are averaged in 0.2 K bins.
 J. Jask et al. / International Journal of Mass Spectrometry 354355 (2013) 204210
The piezo valve has been opened with a 200 s pulse every 100 ms.
Very unexpected is the sharp and intense peak at 0.6 ms having a
width of only 150 s (full width at half maximum). This feature is
explained with the fact that the rst part of helium is injected into
the evacuated trap as a supersonic beam, crossing the ion beam.
The following slower increase of the helium density up to a maxi-
mum after 12 ms is due to the redistribution of the gas pulse in the
whole copper box and partly also due to condensation of He on the
3.8 K cold walls (cryopumping up to saturation). The time constant
for the decay (26 ms) is determined by the volume of the copper
box, and the conductance through the two cylindrical electrodes. It
is also inuenced by He slowly desorbing from the walls.
Another important test of the properties of a low temperature
ion trap is the formation of N2 He+ clusters which critically depends
on the ion temperature. Fig. 4b shows the decrease of the number of
clusters as a function of temperature. Clearly, the highest number
of clusters is formed at the lowest temperature (3.8 K). The steep
decrease toward 12 K is partly due to the temperature dependence
of the ternary rate coefcient but also due to the increase of the
conductance of the entrance and exit electrode with increasing
temperature. The re-increase of the number of ions with m/z = 32
above 15 K is caused by an efcient formation of O2 + via charge
transfer from evaporating traces of oxygen to the stored N2 + ions.
Further experimental tests were performed with mass-selected
C7 H6 2+ dications. These ions were generated in the electron ioniza-
tion source by dissociative ionization of toluene (pressure 0.1 mbar,
electron energy 150 eV). Fig. 5a shows the decay of the injected
C7 H6 2+ primary ions and the sequential formation of C7 H6 He2+ and
C7 H6 He2 2+ clusters as a function of the trapping time. The kinet-
ics are rather complicated due to the initial cooling of the injected
ions, the attachment of He via ternary collisions and the fact, that
the number density of He changes with time as shown in Fig. 4a.
This change nally leads to the stationary conditions after about
50 ms.
Fig. 5. (a) Formation of helium clusters C7 H6 Hex 2+ (x = 1 and 2) after the opening of
the piezovalve. (b) Mass spectrum of the ions formed after trapping mass selected
C7 H6 2+ . The numbers 15 indicate that up to 5 helium atoms are attached to C7 H6 2+ .
207
As can be seen in the mass spectrum, plotted in Fig. 5b, the reac-
tive C7 H6 2+ ion can form clusters with up to ve helium atoms. The
magnied part of the spectrum (10) also indicates that during
the lling procedure, several reactions take place such as fragmen-
tation of the dication into C2 H3 + + C5 H3 + , proton transfer to the
residual gas and also ternary addition of N2 . The very small traces
of impurity molecules are carried into the trap with the intense He
pulse.
In order to record infrared predissociation spectra of C7 H6 He2+ ,
the following sequence has been used. The C7 H6 2+ ions, formed in
the ion source, were mass-selected by the 4P1 , deected by the QPB,
and guided by the 8P to the w4PT (see Fig. 1). Simultaneously with
the ions, He buffer gas has been injected into the trap in order to col-
lisionally relax the translational, rotational and vibrational energy
of the ions. It is estimated that the He number density reaches up
to 1016 cm3 at the conditions used. The trapping time was set to
40 ms. During this time, He attachment to C7 H6 2+ takes place as
shown in Fig. 5a. Just before opening the trap exit for analyzing
its mass composition with the QP2 , the ion cloud is exposed to an
IR laser pulse. For reference, in the next cycle, the laser pulse is
red 1 ms after the ion extraction. The procedure of injecting ions,
cooling them, forming clusters and irradiating them before or after
extraction was repeated with a frequency of 10 Hz.
The tunable laser radiation is generated by an OPO/OPA LaserVi-
sion system pumped by a Nd:YAG laser (Continuum Surelite EX).
The OPO can be tuned from 2000 cm1 to 4680 cm1 with a
resolution of 5 cm1 . Above 2900 cm1 , it delivers up to 20 mJ
Fig. 6. (a) Infrared predissociation spectrum of C7 H6 He2+ . (bf) Theoretical IR spec-
tra of different isomers of C7 H6 2+ calculated at the B3LYP/cc-pVTZ level of theory.
The scaling factor is 0.96 [45].
208 J. Jask et al. / International Journal of Mass Spectrometry 354355 (2013) 204210

Fig. 7. Different isomers of C7 H6 He2+ and the most stable isomer of C7 H6 Ar2+ . The binding energies of helium as well as the selected geometrical parameters optimized at
various levels of theory can be found in Table 1.

per pulse. The laser beam is directed into the trap using silver-
coated mirrors. It enters the vacuum chamber through a fused silica
window mounted on the detector-side. A CaF2 lens (f = 1000 mm)
creates a focus in the trap region. The laser power is routinely mon-
itored by a power-meter (Coherent Fieldmax II with the sensor
Coherent J-25MB-LE).
3. Results and discussion
Fig. 6a shows an infrared predissociation spectrum of C7 H6 He2+ .
Since the OPO has been scanned continuously, the actual wavenum-
ber is each time recorded together with the number of the extracted

Fig. 8. (a) Infrared predissociation spectrum of C7 H6 He2+ and its comparison with Fig. 9. (a) Infrared predissociation spectrum of C7 H6 He2+ and its comparison with
theoretical IR spectra of C7 H6 He2+ (be) and C7 H6 Ar2+ (f) calculated at the B3LYP/cc- theoretical IR spectra of C7 H6 He2+ (bf) calculated at the MP2/cc-pVTZ level of the-
pVTZ level of theory. The scaling factor is 0.96 [45]. ory. The scaling factor is 0.949.
 J. Jask et al. / International Journal of Mass Spectrometry 354355 (2013) 204210 209

Table 1
Effect of the theoretical methoda on the geometries of the C7 H6 He2+ complexes and the binding energies (at 0 K) of helium in the complexes.

C7 H6 2+ 1 2 3 4 5 6 7 8
a
B3LYP
D0 (kJ mol1 ) 1.1 1.0 n.f. 0.6 n.f. 0.5 n.f. n.f.
( ) 161.0 160.6 161.1 161.1 161.1
r1 () 2.53 2.13 2.28 2.36

B97Da
D0 (kJ mol1 ) 2.61 2.11 2.31 n.f. 1.73 1.73 2.34 1.82
( ) 160.0 160.3 160.3 160.3 160.3 160.3 160.3
r1 () 2.66 2.21 2.38 2.47 2.33 2.57 3.52
r2 () 2.63 2.67 3.23
r3 () 3.58

M06-2Xa
D0 (kJ mol1 ) 2.2 n.f. 1.0 n.f. 1.1 n.f. 1.7 1.8
( ) 162.3 161.7 162.3 162.3 162.3 162.3
r1 () 2.39 2.47 2.56 2.58 3.31
r2 () 2.60 2.63 3.08
r3 () 3.32

MP2a
D0 (kJ mol1 ) 1.4 n.f. 1.0 n.f. 0.7 n.f. 0.6 0.8
( ) 162.9 162.6 162.9 162.9 162.9 162.9
r1 () 2.61 2.44 2.56 2.60 3.41
r2 () 2.61 2.64 3.15
r3 () 3.44

CCSDa
D0 (kJ mol1 ) 1.5b 0.7b 0.9b n.f. 0.7b n.f. 0.6b 0.6b
( ) 161.9 161.6 162.0 162.0 162.0 161.9 162.0
r1 () 2.58 2.25 2.46 2.57 2.60 3.48
r2 () 2.63 2.64 3.19
r3 () 3.53
a
The basis set was always cc-pVTZ.
b
The structures are optimized at the CCSD level of theory, but the zero-point energy is taken from the MP2 calculations.

C7 H6 He2+ ions. The results, accumulated over 10 periods, were
binned into the equidistant wavenumber channels. The net signal,
1 Ni /Ni,0 , is calculated from the number of ions, observed with
the laser irradiation before and after the extraction, Ni and Ni,0 ,
respectively. Such spectra were recorded 14 times, scanning the
OPO up and down. For the nal spectrum shown in Fig. 6a, the indi-
vidual contributions were added together without any smoothing
procedure.
Inspection of the experimental spectrum reveals that one can
distinguish four peaks with maxima at 2940 cm1 , 2962 cm1 ,
3004 cm1 and 3058 cm1 . In the following interpretation, we will
rst consider IR spectra of unperturbed C7 H6 2+ , i.e., without a
helium attached. The comparison with the ve possible structures
of C7 H6 2+ shown in Fig. 6bf clearly reveals that only the most stable
structure of cycloheptatrienylidene dication comes into question,
if all features in the theoretical spectrum should be accounted for.
We note in passing that we have considered only the singlet states
of the dications, because the triplet states lie signicantly higher in
energy [46].
The difference between the theoretical spectrum and the calcu-
lated spectrum of the cycloheptatrienylidene dication can be due
to the level of theory used or due to the tagging with helium. First,
we have investigated the effect of helium tagging on the structure
and the IR spectrum of the cycloheptatrienylidene dication. Fig. 7
shows all minima found for complexes between He and the C7 H6 2+
dication. The binding energy between helium and C7 H6 2+ amounts
to about 1 kJ mol1 (Table 1). The most stable isomer is formed
by binding helium to the carbene carbon atom (complex 1). The
stability of the remaining isomers largely depends on the theoret-
ical method used for their localization. While the B3LYP level of
theory predicts complexes bound via hydrogen atoms of the dica-
tion, optimizations at the MP2, CCSD as well as M06-2X levels of
theory lead to isomers, where He interacts with the C C bonds. In
any case, it is expected that helium clusters will be represented by
a dynamic equilibrium of all isomers located and all isomers will at
least partly contribute to the resulting photodissociation spectrum.
Hence, the next question is how much the helium tagging can affect
the IR spectra of the ions.
Here, only B3LYP and MP2 results will be discussed
(Figs. 8 and 9). The theoretical spectra on the other levels of theory
can be found in the Electronic Supplementary Material. Comparison
of the IRPD spectrum of C7 H6 He2+ with the theoretical spectra of all
isomers of the dication shows that while the effects of helium can
be observed in the spectra they are not substantial and correspond
to only a small perturbation of the structure of the dication by the
helium tagging. Analysis of the individual vibrational modes reveals
that the peaks at 2940 cm1 and 2962 cm1 correspond to the
stretching of the C(2) H and C(7) H bonds. The peak at 3002 cm1
is most probably associated with the vibrations of C(3) H
and C(6) H bonds and nally the small feature at 3058 cm1
corresponds to the vibrations of C(4) H and C(5) H bonds.
The biggest difference between the two most stable isomers
obtained at the B3LYP level of theory (cf. Fig. 8b and 8c) con-
sists in the position of the lowest lying band. As it corresponds to
the vibration of the C(2) H bond it is red-shifted in the complex,
where helium binds via this particular hydrogen atom (Fig. 8c).
This difference between the isomers could explain the broaden-
ing of the peaks at 2940 cm1 and 2962 cm1 . On the contrary,
the peak at 3002 cm1 corresponds to a band which has the same
position for all isomeric complexes. As a result, the band with a
low intensity at about 2990 cm1 probably represents a hot band.
The effects obtained at the MP2 level of theory are negligible (cf.
Fig. 9). The red shift of the lowest lying band with respect to the
theory would have been thus explained as an artifact of the the-
oretical models (all tested in this work). Similarly, all methods
used here predict the positions of the highest lying bands slightly
red-shifted with respect to the experimental results. Overall, how-
ever, we can conclude that the effect of helium tagging on the
210 J. Jask et al. / International Journal of Mass Spectrometry 354355 (2013) 204210
structure and consequently also on the IR spectra of dications is very
small. With respect to the uncertainties of the theoretical models
and the harmonic approximation, the effect can be most probably
neglected.
Finally, we want to demonstrate that tagging with argon is not
very valuable for such reactive species as hydrocarbon dications.
Attaching argon to C7 H6 2+ leads to a distortion of its geometry as
demonstrated nicely by the change of the C(7) C(1) C(2) bond-
ing angle (Fig. 7). The binding energy of argon in the most stable
isomer amounts to 37 kJ mol1 and the expected IR spectrum of
C7 H6 Ar2+ completely differs from that of the original C7 H6 2+ dica-
tion (cf Fig. 8a and 8f).
4. Conclusions
Combining the modules of a commercial mass spectrometer
with a modern temperature variable ion trap, we have constructed
a new instrument for infrared predissociation spectroscopy. The
linear quadrupole trap, made from wires, reaches temperatures
below 4 K. The low temperature and high number densities of the
buffer gas allows us to prepare helium-tagged ions. Here, we have
presented the rst IRPD spectrum of helium tagged hydrocarbon
dications. We demonstrate that tagging of such a reactive species
with argon (or any other more reactive atom/molecule) leads to
a distortion of its structure and thus the IRPD spectrum could
be hardly used to probe it. Helium tagging is hence the method
of choice for the investigation of highly reactive species. At the
same time, we have shown that already for a small system such
as C7 H6 He2+ many possible isomers can be found as far as the posi-
tion of helium is concerned and the energy differences between
them are very small. Consequently, also the effects in the theo-
retical IR spectra comparing the parent ion C7 H6 2+ and the tagged
ion C7 H6 He2+ are very small and probably smaller than the errors
imposed by the theoretical method used for their calculation. Effect
of the helium tag can be therefore probably neglected in the inves-
tigation of IRPD spectra of larger systems.
Finally, we have clearly shown that the structure of the
C7 H6 2+ dication corresponds to doubly ionized cyclohepta-
trienylidene as considered in all reactivity studies of dications
generated from toluene performed by Detlef Schrder in the past
seven years.
Acknowledgement
This work was supported by the ERC StG ISORI (No. 258299).
The authors also wish to thank to Dean Guyer for his help with the
OPO system and Jaromr Novk and Petr Verner for their help with
the TSQ instruments.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.ijms.2013.06.007.
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