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International Journal of Mass Spectrometry 354355 (2013) 204210

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International Journal of Mass Spectrometry

journal homepage: www.elsevier.com/locate/ijms

Infrared spectroscopy of trapped molecular dications below 4 K

Juraj Jask a , Jn Zabka a,b , Jana Roithov a, , Dieter Gerlich c,
Department of Organic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030/8, 12843 Prague 2, Czech Republic
J. Heyrovsky Institute of Physical Chemistry, Academy of Science of the Czech Republic, 182 23 Prague 8, Czech Republic
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.
Infrared predissociation spectroscopy
Linear wire quadrupole trap

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

1387-3806/$ see front matter 2013 Elsevier B.V. All rights reserved.
J. Jask et al. / International Journal of Mass Spectrometry 354355 (2013) 204210 205

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 Fig. 1. Geometry of the ISORI instrument.
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 experiments provided by the trapping technique, and nally mass-
dissociation into two singly charged ions via the so-called Coulomb analyze the products of the interactions.
barrier or the dication eliminates a neutral molecule in that the As illustrated in Fig. 1, ISORI is based on the combination
bonding between a doubly charged ion and a molecule is usually of a low-temperature ion trap with a commercial instrument
associated with a rather large binding energy. Clearly, the large TSQ 7000 (Thermo Finnigan) which has, in its original design, a
energy demands represent a problem for photodissociation using IR quadrupoleoctopolequadrupole geometry [43]. In order to use
instead of UV photons [21,22]. It also should be noted that the frag- all commercial TSQ-compatible ion sources (EI/CI, ESI, API, APCI),
mentation process is becoming easier with increasing size of the we have cut the TSQ manifold into two pieces. The front part serves
studied dications [23,24]. Even higher charge-states can be studied as a holder for the EI/CI source or as an interface with a trans-
if the size of the complex is large enough [25]. fer quadrupole between the ESI source and the quadrupole stage
Using a tagging method for dications is also not straightfor- placed in the second differentially pumped volume of the case.
ward. The binding energy between argon and small dications can The front part is connected with the main instrument using a cus-
be rather large and actually it was shown that dications can form in tomized ange with an O-ring tting in the side of the source
reaction with argon thermodynamically stable species with cova- and serves in the ISORI instrument in the same way as in the
lently bound argon [2629]. For small metal complexes, several original TSQ. The following modules of the instrument are placed
argon atoms have to be used in order to get to a regime in which IR in standard CF housings so that the vacuum chamber consists of
irradiation is able to detach one argon atom [3032]. Clearly, if the three differentially pumped regions: (1) the ion source region, (2)
tagging atoms/molecules are bound rather tightly to the studied ion the region with the rst quadrupole (4P1 ), the quadrupole bender
then also the structure of this ion can be signicantly inuenced. (QPB), and the octopole (8P), and (3) the region with the ion trap
Hence, the only known infrared predissociation spectra of dicat- (w4PT), the second quadrupole (4P2 ), and the detector.
ions correspond to water complexes of divalent metals with either The original TSQ electronics are used for controlling the ion
a large number of water ligands or four and more attached argon source, driving the rst and second quadrupole (4P1 , 4P2 ) and
atoms. There are also reports of large complexes of divalent metals the octopole ion guide 8P, and to provide the voltages for the
with ligands other than water, but clearly with increasing size of ion detector. The other parts of the instrument are controlled by
the studied ion, the problem with the double charge diminishes and custom-made electronics. The Daly type detector is constructed
the IRPD spectra can be obtained as comfortably as for the singly from the original parts of the TSQ mounted into a customized cham-
charged ions [33,34]. ber. We operate the detector (DeTech 2312) in the ion-counting
The real challenge thus remains to probe spectroscopically mode. The pulses are counted by a multichannel scaler (Becker &
small highly reactive molecular dications. On contrary to metal Hickl PMS-400A, discriminator threshold 8 mV).
dications and their complexes which often have their second ion- The central element, located between the TSQ 7000 based mod-
ization energy lower that the rst one of argon, small molecular ules, is an rf ion trap mounted onto a cold head. Cooling of ions
dications may easily undergo charge transfer with argon or make with buffer gas is usually performed in multi-electrode traps (22-
covalent bonds [26,27]. Our aim is to spectroscopically character- pole or ring electrode traps, see [44]) which have least effects on
ize small and medium sized hydrocarbon dications. These species the kinetic energy distribution of the conned ions. Here, for heavy
are extremely reactive and, due to their twofold charge, they ions in the light buffer gas, we have chosen a rather open linear
can possess unusual structures. This pilot paper is focused on quadrupole geometry which has several advantages such as in situ
the presentation of a new instrument, which allows formation mass selection, better overlap with a laser beam, and optical access.
of complexes of dications with loosely bound helium atoms. The The design of the ion trap is shown in Fig. 2. The inner part of the
spectroscopy will be shown for the C7 H6 2+ dication, which is the housing is made from a solid high-quality oxygen-free copper block
model dication used in most of the reactivity studies made by Detlef with a half-cylindrical inner bore. It is cooled by the 2nd stage of a
Schrder and coauthors during the last seven years [3542]. 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
2. Experimental cold head. The temperatures of both stages are measured by silicon-
diode sensors (LakeShore DT-670B1-CU). The upper side of the trap
The experiments were performed with the new instrument can be closed with a quartz window for observing photons emitted
ISORI (Ion Spectroscopy of Reaction Intermediates). This instrument from the trapped ions. In this experiment, however, an aluminum
has been designed to trap mass-selected ions, cool them down to foil has been used to protect the trap against the surrounding black-
a few K, let them interact with laser radiation or perform other 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 without buffer gas and the cold head reaches 3.47 K at a load of
identical printed circuit boards (PCB), made from a ceramic-lled 0.1 W according to the nal test sheet. The buffer gas is injected
PTFE composite and coated with a copper layer (Rogers RO3003). with a custom-made piezo valve situated in vacuum. It is connected
Using four screws they are attached to the cold body of the trap. directly to the trap with a straight 37 mm long Teon tube (inner
Suitable circuits, etched onto these boards and connected with lead diameter 2 mm, entrance hole see the left side of the drawing with
solder, provide the electrical contacts for the electrodes, i.e., for the dimensions in Fig. 2).
four groups of 6 wires as well as the entrance or exit electrode, For determining the lling and residence time of He buffer gas,
respectively. we have made use of the fact that thermalized ions have a higher
In order to nd the optimum location of the 24 copper wires overall detection efciency than the ions just passing through the
(1 mm diameter) for approximating the ideal hyperbolic boundary trap. Keeping the trap continuously open and running a continuous
conditions of a linear quadrupole, the 2D Laplace equation has been ion beam through it leads to an increasing number of detected ions
solved numerically using the Finite Element Method on a triangular if the neutral density is increasing (known as phase space compres-
mesh. The geometry is shown in Fig. 3 together with the differ- sion). The linearity of this effect has not yet been checked; however,
ence between the ideal potential, (r, ) = 0 (r/r0 )2 cos(2) with the results, shown in Fig. 4a for a beam of N2 + , provide interesting
0 = 103.4 V and r0 = 0.598 cm and the potential calculated for the insight into the time dependence of the density of the buffer gas.
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
Reaching the lowest possible temperature is of basic importance
for studying He-tagged ions. With our arrangement we reach 3.3 K

Fig. 4. (a) Helium density in the trap after exciting the piezo valve with a 200 s
Fig. 3. Simulation of the potential of the w4PT. Contours show the difference pulse monitored as the number of detected N2 + ions (see the text). The inset shows
between the numerically calculated potential and the ideal quadrupole potential the sharp increase during the rst ms (supersonic jet). (b) Number of ions with
in steps of 0.1 V, 1 V and 10 V. The surrounding cylinder (diameter of 27 mm) has m/z = 32 (N2 He+ clusters and O2 + ) as a function of the temperature of the trap. Data
been set to 0 V. are averaged in 0.2 K bins.
J. Jask et al. / International Journal of Mass Spectrometry 354355 (2013) 204210 207

The piezo valve has been opened with a 200 s pulse every 100 ms. As can be seen in the mass spectrum, plotted in Fig. 5b, the reac-
Very unexpected is the sharp and intense peak at 0.6 ms having a tive C7 H6 2+ ion can form clusters with up to ve helium atoms. The
width of only 150 s (full width at half maximum). This feature is magnied part of the spectrum (10) also indicates that during
explained with the fact that the rst part of helium is injected into the lling procedure, several reactions take place such as fragmen-
the evacuated trap as a supersonic beam, crossing the ion beam. tation of the dication into C2 H3 + + C5 H3 + , proton transfer to the
The following slower increase of the helium density up to a maxi- residual gas and also ternary addition of N2 . The very small traces
mum after 12 ms is due to the redistribution of the gas pulse in the of impurity molecules are carried into the trap with the intense He
whole copper box and partly also due to condensation of He on the pulse.
3.8 K cold walls (cryopumping up to saturation). The time constant In order to record infrared predissociation spectra of C7 H6 He2+ ,
for the decay (26 ms) is determined by the volume of the copper the following sequence has been used. The C7 H6 2+ ions, formed in
box, and the conductance through the two cylindrical electrodes. It the ion source, were mass-selected by the 4P1 , deected by the QPB,
is also inuenced by He slowly desorbing from the walls. and guided by the 8P to the w4PT (see Fig. 1). Simultaneously with
Another important test of the properties of a low temperature the ions, He buffer gas has been injected into the trap in order to col-
ion trap is the formation of N2 He+ clusters which critically depends lisionally relax the translational, rotational and vibrational energy
on the ion temperature. Fig. 4b shows the decrease of the number of of the ions. It is estimated that the He number density reaches up
clusters as a function of temperature. Clearly, the highest number to 1016 cm3 at the conditions used. The trapping time was set to
of clusters is formed at the lowest temperature (3.8 K). The steep 40 ms. During this time, He attachment to C7 H6 2+ takes place as
decrease toward 12 K is partly due to the temperature dependence shown in Fig. 5a. Just before opening the trap exit for analyzing
of the ternary rate coefcient but also due to the increase of the its mass composition with the QP2 , the ion cloud is exposed to an
conductance of the entrance and exit electrode with increasing IR laser pulse. For reference, in the next cycle, the laser pulse is
temperature. The re-increase of the number of ions with m/z = 32 red 1 ms after the ion extraction. The procedure of injecting ions,
above 15 K is caused by an efcient formation of O2 + via charge cooling them, forming clusters and irradiating them before or after
transfer from evaporating traces of oxygen to the stored N2 + ions. extraction was repeated with a frequency of 10 Hz.
Further experimental tests were performed with mass-selected The tunable laser radiation is generated by an OPO/OPA LaserVi-
C7 H6 2+ dications. These ions were generated in the electron ioniza- sion system pumped by a Nd:YAG laser (Continuum Surelite EX).
tion source by dissociative ionization of toluene (pressure 0.1 mbar, The OPO can be tuned from 2000 cm1 to 4680 cm1 with a
electron energy 150 eV). Fig. 5a shows the decay of the injected resolution of 5 cm1 . Above 2900 cm1 , it delivers up to 20 mJ
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 Fig. 6. (a) Infrared predissociation spectrum of C7 H6 He2+ . (bf) Theoretical IR spec-
the piezovalve. (b) Mass spectrum of the ions formed after trapping mass selected tra of different isomers of C7 H6 2+ calculated at the B3LYP/cc-pVTZ level of theory.
C7 H6 2+ . The numbers 15 indicate that up to 5 helium atoms are attached to C7 H6 2+ . 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- 3. Results and discussion
coated mirrors. It enters the vacuum chamber through a fused silica
window mounted on the detector-side. A CaF2 lens (f = 1000 mm) Fig. 6a shows an infrared predissociation spectrum of C7 H6 He2+ .
creates a focus in the trap region. The laser power is routinely mon- Since the OPO has been scanned continuously, the actual wavenum-
itored by a power-meter (Coherent Fieldmax II with the sensor ber is each time recorded together with the number of the extracted
Coherent J-25MB-LE).

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
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

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

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

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

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
The basis set was always cc-pVTZ.
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 a dynamic equilibrium of all isomers located and all isomers will at
binned into the equidistant wavenumber channels. The net signal, least partly contribute to the resulting photodissociation spectrum.
1 Ni /Ni,0 , is calculated from the number of ions, observed with Hence, the next question is how much the helium tagging can affect
the laser irradiation before and after the extraction, Ni and Ni,0 , the IR spectra of the ions.
respectively. Such spectra were recorded 14 times, scanning the Here, only B3LYP and MP2 results will be discussed
OPO up and down. For the nal spectrum shown in Fig. 6a, the indi- (Figs. 8 and 9). The theoretical spectra on the other levels of theory
vidual contributions were added together without any smoothing can be found in the Electronic Supplementary Material. Comparison
procedure. of the IRPD spectrum of C7 H6 He2+ with the theoretical spectra of all
Inspection of the experimental spectrum reveals that one can isomers of the dication shows that while the effects of helium can
distinguish four peaks with maxima at 2940 cm1 , 2962 cm1 , be observed in the spectra they are not substantial and correspond
3004 cm1 and 3058 cm1 . In the following interpretation, we will to only a small perturbation of the structure of the dication by the
rst consider IR spectra of unperturbed C7 H6 2+ , i.e., without a helium tagging. Analysis of the individual vibrational modes reveals
helium attached. The comparison with the ve possible structures that the peaks at 2940 cm1 and 2962 cm1 correspond to the
of C7 H6 2+ shown in Fig. 6bf clearly reveals that only the most stable stretching of the C(2) H and C(7) H bonds. The peak at 3002 cm1
structure of cycloheptatrienylidene dication comes into question, is most probably associated with the vibrations of C(3) H
if all features in the theoretical spectrum should be accounted for. and C(6) H bonds and nally the small feature at 3058 cm1
We note in passing that we have considered only the singlet states corresponds to the vibrations of C(4) H and C(5) H bonds.
of the dications, because the triplet states lie signicantly higher in The biggest difference between the two most stable isomers
energy [46]. obtained at the B3LYP level of theory (cf. Fig. 8b and 8c) con-
The difference between the theoretical spectrum and the calcu- sists in the position of the lowest lying band. As it corresponds to
lated spectrum of the cycloheptatrienylidene dication can be due the vibration of the C(2) H bond it is red-shifted in the complex,
to the level of theory used or due to the tagging with helium. First, where helium binds via this particular hydrogen atom (Fig. 8c).
we have investigated the effect of helium tagging on the structure This difference between the isomers could explain the broaden-
and the IR spectrum of the cycloheptatrienylidene dication. Fig. 7 ing of the peaks at 2940 cm1 and 2962 cm1 . On the contrary,
shows all minima found for complexes between He and the C7 H6 2+ the peak at 3002 cm1 corresponds to a band which has the same
dication. The binding energy between helium and C7 H6 2+ amounts position for all isomeric complexes. As a result, the band with a
to about 1 kJ mol1 (Table 1). The most stable isomer is formed low intensity at about 2990 cm1 probably represents a hot band.
by binding helium to the carbene carbon atom (complex 1). The The effects obtained at the MP2 level of theory are negligible (cf.
stability of the remaining isomers largely depends on the theoret- Fig. 9). The red shift of the lowest lying band with respect to the
ical method used for their localization. While the B3LYP level of theory would have been thus explained as an artifact of the the-
theory predicts complexes bound via hydrogen atoms of the dica- oretical models (all tested in this work). Similarly, all methods
tion, optimizations at the MP2, CCSD as well as M06-2X levels of used here predict the positions of the highest lying bands slightly
theory lead to isomers, where He interacts with the C C bonds. In red-shifted with respect to the experimental results. Overall, how-
any case, it is expected that helium clusters will be represented by 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

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Appendix A. Supplementary data
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