International Journal of Mass Spectrometry 354–355 (2013) 292–302

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International Journal of Mass Spectrometry

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

Fragmentation, structure, and energetics of small sodium formate

clusters: Evidence for strong influence of entropic effects
Ágnes Révész a , Tibor András Rokob a , Gábor Maász b,c , László Márk b,c , Helga Hevér d ,
László Drahos a , Károly Vékey a,∗
a
Institute of Organic Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, Budapest 1025, Pusztaszeri út 59-67, Hungary
b
Department of Analytical Biochemistry, Institute of Biochemistry and Medicinal Chemistry, Medical School, University of Pécs, Pécs 7624, Szigeti út 12,
Hungary
c
János Szentágothai Research Center, University of Pécs, Pécs 7624, Ifjúság útja 20, Hungary
d
Gedeon Richter Plc., Budapest 1103, Gyömrői út 19-21, Hungary

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

Article history: The behavior of small cationic sodium formate clusters [NaOOCH]n Na+ was studied using a combination of
Received 3 May 2013 experimental and theoretical approaches. Energy-dependent tandem mass spectra were measured using
Received in revised form 25 June 2013 a triple quadrupole and an ion trap type instrument, while structure and energetics were obtained from
Accepted 26 June 2013
density functional theory calculations. Analysis of the relative abundances and fragmentation patterns
Available online 5 July 2013
indicate the existence of certain unstable cluster sizes, like the tetramer [NaOOCH]4 Na+ . This observation
Dedicated to the memory of Detlef is in contrast to alkali halides, where this species has enhanced stability. Surprisingly, this ‘anti-magic’
Schröder, an excellent scientist, mentor, sodium formate cluster is shown to be compact, energetically low-lying by quantum chemical calcula-
colleague, and friend. tions. The apparent contradiction can be explained by taking into account entropy effects as calculated
dissociation Gibbs free energy values show remarkably improved agreement with experimental trends.
Keywords: Fragmentation of these clusters is a good example of reactions that are predominantly directed by entropy
Sodium formate and not by energy constraints.
Cluster stability © 2013 Elsevier B.V. All rights reserved.
Magic number
Entropy
Tandem mass spectrometry
Quantum chemistry

1. Introduction
The investigation of clusters has gained special attention in the
last few decades for several reasons [1,2]. They represent an inter-
mediate state between the condensed matter and the gas phase
exhibiting size-dependent chemical and physical behavior. Their
properties usually differ from those of both the condensed and
the gas phase, caused by their individual and specific structures.
Therefore, the study of the clusters’ stability, reactivity and disso-
ciation in naked form, i.e. without additional solvent molecules,
may provide insight into the inherent features of the nucleation
and growth mechanism of crystal structures.
Alkali halides serve as examples for the simplest ionic crystal
structures, most of them having face-centered cubic lattices. These
compounds are inexpensive in their pure forms, and the genera-
tion of the gas-phase clusters can be easily achieved. As a result,
∗ Corresponding author. Tel.: +36 1 438 1157.
E-mail address: vekey.karoly@ttk.mta.hu (K. Vékey).
their clusters, both in neutral [AX]n and ionic [AX]n A+ or [AX]n X−
forms, have been extensively studied by several experimental and
computational techniques, including mass spectrometry [3–24].
Important advantages of this technique over other methods are
its sensitivity and mass selectivity, and the latter provides a
straightforward solution to size-dependent investigation. Mass
spectrometric (MS) measurements have been carried out in com-
bination with various ionization modes, e.g., field desorption [10],
secondary ion mass spectrometry [11–18], and, more recently,
the soft electrospray ionization (ESI) [19–23]. ESI has enabled the
access of clusters with relatively high values of n. Relative MS
abundances and MS/MS fragmentation data can typically be linked
to energetics, i.e., thermodynamic stability of the clusters [25],
whereas ion-mobility mass spectrometry provides structural infor-
mation [24,26,27]. Early ESI-MS measurements of ionic alkali halide
clusters were aimed at the investigation of the electrospray ion
formation mechanism itself [3,6,7]. Later, the main focus shifted
to the characterization of the cluster ions in the gas phase, and it
was found for various alkali halides (NaF [20], LiCl [19,22], NaCl
[9,19,21,22], KCl [19,22], RbCl [19,22], CsCl [9,19], NaI [9,11], KI

1387-3806/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ijms.2013.06.029
 Á. Révész et al. / International Journal of Mass Spectrometry 354–355 (2013) 292–302
Fig. 1. 3 × 3 × 1, 3 × 3 × 3 and 3 × 3 × 5 fragments cut out from the crystal lattice of
NaCl (a–c) [42]; crystal structure of NaOOCH [43,44] (d). Cations are black, anions
are white. The lines connecting the ions within planes are only drawn to guide the
eye and have no special chemical meaning. Gas phase structures of [NaCl]n Na+ for
the magic numbers n = 4, 13 and 22 have very similar geometry to the parts of the
crystal shown here in subfigures a–c, respectively.
[11], RbI [11] and CsI [9,11,12,23]) that [AX]n A+ clusters with spe-
cific values of n, e.g., 4, 13, 22 etc., have increased intensity in the
mass spectra and higher stability against dissociation compared to
the other cluster sizes. In some cases, also [AX]n X− species were
examined, resulting in the same observations. On the other hand,
monotonically decreasing abundance with increasing size was pub-
lished in a study for CsCl [22], and different favored values of n were
found and interpreted for CsI [24]. The appearance of magic clusters
was attributed to their compact structure, corresponding to regu-
lar fragments of the rock-salt crystal lattice (depicted in Fig. 1a–c).
Quantum chemical calculations on singly charged NaCl clusters
[27–33] and other related systems [33–36] confirmed the assumed
preferred structures, as did ion-mobility mass spectrometric exper-
iments [26,27]. Interestingly, [CsX]n Cs+ (X = Cl, I) clusters exhibit
the same magic numbers as other alkali halides although CsCl and
CsI have different crystal structure from most other alkali halides
(body-centered vs. face-centered cubic). Computations suggested
that the CsCl-type structure starts to be preferred energetically over
the rock-salt-type only above a fairly large cluster size of several
hundred atoms [37]. On the other hand, for neutral LiF species,
hexagonal or octogonal nanotube structures were calculated to
compete in stability with cubic forms [38]. Further, [NaCl]n Na2 2+
dications also show size-dependent stability [39,40], and in this
respect, the computations agreed well with the mass spectrometric
results [41].
Although alkali halides have been studied in detail, the mass
spectrometric literature of other ionic clusters is rather scarce. The
mass spectra of NaOOCH and NaOOCCH3 solutions, containing sim-
ple but notably anisotropic anions, were recorded up to m/z 4000,
showing that, for these salts, the normal magic numbered species
do not dominate the spectra [19]. However, no tandem mass spec-
trometric investigation has been carried out, and the possible gas
phase cluster structures have not been explored yet. Concerning
the solid phase, the crystal structure of NaOOCH [43,44] belongs
293
to the monoclinic crystal system, but in spite of the different sym-
metry properties of the anions and the crystals, the unit cells of
NaOOCH and NaCl show remarkable similarity with respect to the
arrangement of the ions (compare Figs. 1b and d). In light of these
similarities and differences, a closer study of the cluster ions of
NaOOCH seems of interest.
In the present work, we investigate the structure, energetics
and fragmentation properties of small [NaOOCH]n Na+ clusters by
MS and MS/MS techniques combined with computational methods.
Our aim is to unravel the differences between the alkali halide and
sodium formate clusters and to examine the origin for the absence
of magic numbers in the case of the latter.
2. Methods
2.1. Mass spectrometry
Mass spectrometric investigations were carried out by sev-
eral types of instruments. First, collision-induced dissociation
(CID) experiments were performed using a Bruker Esquire HCT
quadrupole ion trap (IT-MS) mass spectrometer (Bruker Dalton-
ics, Bremen, Germany) equipped with a conventional electrospray
(ESI) source. The [NaOOCH]n Na+ clusters were prepared by
spraying a 1:1:8 mixture of 0.1 mol/dm3 NaOH solution/10%
HCOOH/acetonitrile with a flow rate of 10 ␮l/min. The solution
was infused through a heated capillary, set to a voltage of 3500 V;
the drying gas temperature was kept at 280 ◦ C, and the pressure
of the ion trap was 8.8 × 10−6 mbar. Note that this is uncorrected
gauge, and the real pressure is known to be 2–3 orders of magnitude
higher [45]. He was used as collision gas. The CID was performed
by application of an AC voltage to the end caps of the trap to induce
collisions of the isolated [NaOOCH]n Na+ (n = 2–8) cluster ions with
the helium buffer gas. The excitation period lasted 20 ms using an
excitation width of 4 m/z units.
The second set of MS/MS experiments was carried out on a triple
quadrupole (QqQ) type instrument; namely, a Micromass Quattro
micro mass spectrometer (Waters, Manchester, UK) bearing an ESI
source was used. The clusters under study were generated by infus-
ing the solution described above with a flow rate of 10 ␮l/min. The
capillary voltage was 3 kV, and nitrogen was used as desolvation
gas, kept at 250 ◦ C. The cone voltage was set to 25 V, which provided
high enough intensity and resulted in little or no in-source frag-
mentation. Mass-selected sodium formate clusters collided with
argon gas having a pressure of 3.1 × 10−3 mbar in the collision
cell. The dissociation studies were also probed on a Waters QTOF
Premier mass spectrometer with analogous source and collision
conditions. It was found that practically the same results can be
obtained on the QTOF equipment as on the triple quadrupole instru-
ment, which is explained by the similar construction of the two
mass spectrometers with respect to collision induced dissociation.
For this reason, only the QqQ results are presented in detail in this
paper.
2.2. Quantum chemical calculations
To obtain global minimum structures of cluster ions, sev-
eral global optimization techniques have been employed in the
recent literature, such as simulated annealing [34,46], basin hop-
ping [36], or genetic algorithm [14,28,47]. For the relatively small
species treated in the present work, we adopted the simpler
approach of selecting a large number of random starting geome-
tries and optimizing them first by molecular mechanics (MM) and
then by density functional theory (DFT). Specifically, 1000 (for
[NaOOCH]n Na+ or [NaOOCH]n with n ≤ 2) or 10,000 (for 3 ≤ n ≤5)
starting structures were generated by placing sodium and formate
294 Á. Révész et al. / International Journal of Mass Spectrometry 354–355 (2013) 292–302
ions at random positions and with random orientation into a cubic
box with an edge length of 3–5 Å, avoiding atom–atom contacts
shorter than 1.5 Å. These structures were then subjected to full
molecular mechanics minimization using the Cornell force field
[48], with charges fitted to reproduce the electrostatic potential on
the formate ion (see the Supplementary Material for details). From
the obtained optimized geometries, distinct structures having an
MM energy within 0.5 eV from that of the lowest lying isomer were
input to geometry optimization at the M05-2X/6-31G(d) level of
DFT [49–53]. For the DFT-optimized structures, all computed har-
monic frequencies were real, confirming that true minima have
been found. Again, for distinct structures with electronic energy
within 0.4 eV from that of the lowest lying isomer, more accurate
single-point electronic energy was computed with the same func-
tional and the 6-311++G(3df,3pd) basis set [54–57]. This value was
combined with a zero-point energy calculated from the M05-2X/6-
31G(d) frequencies, scaled by a factor of 0.958 [58], to obtain the
total energy at 0 K.
For the isomers considered for the large-basis-set electronic
energy computation, gas-phase Gibbs free energy was also esti-
mated by determining the thermal and entropic contributions
using the standard ideal gas – rigid rotor – harmonic oscillator
approximation. No frequency scaling was applied. The activa-
tion Gibbs free energies for the dissociations were considered to
be equal to the dissociation free energies, which corresponds to
approximating the transitional modes as free product translations
and rotations. Part of the dissociation free energy, namely, the
entropy contribution from the free translation, depends on the
pressure. As we are trying to approximate the transition state of a
unimolecular dissociation, there is no reason to identify this pres-
sure with the actual pressure in the mass spectrometer. It may be
rather considered as an adjustable parameter, connected with the
looseness of the transition states. Changing the pressure alters all
dissociation free energies by an additive constant of RT ln p2 /p1 ;
hence, the dissociation free energy trends are not affected by any
specific choice. Concerning the absolute magnitudes, it was found
that, with dissociation free energies at p = 1 atm, reasonable rate
constants at reasonable temperatures can be obtained for the ion
trap experiments. Specifically, we determined the temperature for
each cluster at which the dissociation rate as obtained from the
computed dissociation Gibbs free energy via transition state the-
ory corresponds to 50% fragmentation after 20 ms. The average of
these temperatures was ∼500 K. Therefore, we report Gibbs free
energy data for T = 500 K and p = 1 atm throughout.
For the energetically lowest-lying isomer of all species, test cal-
culations with the spin-component scaled MP2 (SCS-MP2) [59]
with the G3Large triple-␨ basis set [60] were also carried out (results
shown in the Supplementary Material). All trends and conclusions
based on the DFT data are also supported by the SCS-MP2 results,
and even the agreement between the numerical values from the
two methods is very good.
In order to find approximate isomerization and dissociation
pathways, the potential energy surface was mapped using relaxed
scans at the B97-D/def2-TZVP [61–63] level of DFT. For each
point of a scan, harmonic potentials with force constants of
∼100–500 eV/Å2 were employed to restrain certain atom–atom
distances at specific values, and the geometry was relaxed in 10–25
optimization cycles. The restraint distances were then repeatedly
shifted by small amounts, typically ±0.05–0.1 Å, to obtain the sub-
sequent points. The pathways located in this way do not correspond
to the minimum energy pathways of the isomerization or disso-
ciation processes, but they do provide an upper estimate of the
involved barriers.
The M05-2X and SCS-MP2 calculations were done with Gaussian
09 [64], while for B97-D, Turbomole 5.10 was employed [65]. The
“ultrafine” and the “m3” grids were chosen for the M05-2X and
Fig. 2. Positive ion mode ESI-MS spectrum of sodium formate solution in the m/z
range of 20–700 measured on the QTOF instrument. Note the general trend of
decreasing intensity with size, and the deviations from the trend at n = 2–3 and
n = 4–5.
B97-D computations, respectively. The B97-D calculations were
done with the resolution-of-identity approximation [66–68].
Molecular graphics were drawn using Molden [69] and CYLview
[70].
3. Results and discussion
3.1. Behavior of sodium formate clusters in a mass spectrometer
The positive ion ESI-MS spectrum of sodium formate solution
measured on the QTOF instrument in the m/z range of 20–700 is
presented in Fig. 2. The appearance of peaks at m/z = 91, 159, 227,
295, 363, 431, 499, 567, 635 clearly points to the formation of clus-
ter ions of the type [NaOOCH]n Na+ (n = 1–9). The relative intensity
is essentially monotonously decreasing with cluster size, i.e., with
increasing n, which is in agreement with the previously published
results and stems partially from the higher instrumental sensitiv-
ity toward lower m/z values. However, it is in marked contrast with
the ESI-MS of alkali halide clusters, where magic numbered clus-
ters, including the n = 4 species, are present with very high relative
abundance in the spectra. Peaks with somewhat increased inten-
sity also appear in the case of sodium formate, but these correspond
to the cluster cations with n = 3 and 5, i.e., having m/z = 227 and
363. However, the overall appearance of the spectra can be better
described by stating that the [NaOOCH]4 Na+ and [NaOOCH]2 Na+
cluster ions have somewhat decreased abundance compared to the
neighboring elements of the cluster series. The mass spectra mea-
sured on the IT and QqQ instruments show identical trends. The
observed remarkable difference in the mass spectrum induced by
the change of halide anion to the anisotropic formate prompted us
to further investigate the stability and fragmentation properties of
small sodium formate cluster ions by tandem mass spectrometric
methods.
In order to obtain a more detailed picture, the MS/MS exper-
iments were carried out on two different instruments: on an ion
trap and on a triple quadrupole. In both cases, parameters influenc-
ing the amount of energy introduced into the ions were varied. In
particular, the fragmentation amplitude on the IT and the collision
voltage in the collision cell on the QqQ were varied. The motivation
for employing two setups stems from the differences [71] between
the excitation processes occurring in the two types of MS. The most
relevant one is that, in IT instruments, the parent ion is selectively
energized, i.e., the fragmentation of daughter ions is uncommon.
In QqQ mass spectrometers, all ions are excited, facilitating con-
secutive dissociations. Further, in IT instruments, the energy of the
actually dissociating ions practically does not change with increas-
ing excitation; it is always slightly above the dissociation threshold.
 Á. Révész et al. / International Journal of Mass Spectrometry 354–355 (2013) 292–302
Increasing the fragmentation amplitude only leads to more and
more precursor ions fragmenting. This property of IT is the conse-
quence of the large number of collisions with small kinetic energy,
i.e., the so-called “slow heating” [72–74]. In QqQ instruments, sig-
nificantly higher excess energy can be deposited in the ions before
fragmentation. Finally, the time frame of the experiment also dif-
fers, being ∼10−2 s in an IT whereas only 10−5 –10−4 s in a QqQ.
In experiments on both IT and QqQ instruments, the
[NaOOCH]n Na+ (n = 2–8) clusters show losses of various numbers
of sodium formate units (e.g., monomer loss: m = 68, dimer loss:
m = 136, etc.) at elevated collision energies, resulting in smaller
clusters. From the tandem mass spectra recorded at various colli-
sion energies, the breakdown diagrams, i.e., the relative abundance
of precursor and fragment ions as a function of the extent of exci-
tation, were constructed. These data are shown in Fig. 3, and the
branching ratios at high excitation on the IT are collected in Table 1.
Upon inspection of the curves obtained on the IT instrument,
depicted in Fig. 3 in the left column, several conclusions can
be drawn. First, the preferred fragmentation process varies from
cluster to cluster. For example, the [NaOOCH]3 Na+ cluster loses
mainly monomer and dimer in an approx. 4:1 ratio, resulting in
[NaOOCH]2 Na+ and [NaOOCH]Na+ fragments. For the next larger
[NaOOCH]4 Na+ ion, one major fragment appears belonging to
monomer loss ([NaOOCH]3 Na+ ), whereas the [NaOOCH]5 Na+ clus-
ter does not dissociate by losing a monomer; rather, [NaOOCH]3 Na+
and [NaOOCH]2 Na+ fragment ions are observable, which cor-
respond to the leaving of neutral dimer and trimer units. By
considering all the obtained breakdown diagrams, it can be con-
cluded that the clusters usually tend to lose smaller neutral
fragments, e.g., monomer, dimer. Thus, the extra sodium ion, and
therefore the charge, remains on the larger cluster fragment. There
is one notable exception, namely, the [NaOOCH]4 Na+ cluster ion is
not observable as fragment in considerable amount for any of the
investigated clusters. [NaOOCH]5 Na+ dissociates mainly via dimer
loss instead, and, in the case of [NaOOCH]6 Na+ , even the com-
plementary [NaOOCH]2 Na+ is somewhat larger in intensity than
the [NaOOCH]4 Na+ fragment. [NaOOCH]7 Na+ produces the com-
plementary [NaOOCH]3 Na+ cluster in roughly the same intensity as
the other two major fragments, [NaOOCH]6 Na+ and [NaOOCH]5 Na+ ,
and no [NaOOCH]4 Na+ is formed. The same holds true for the one
unit bigger cluster, [NaOOCH]8 Na+ , as well. A comparison of the
breakdown curves of [NaOOCH]4 Na+ with the other clusters reveals
that this ion is not extraordinarily prone to dissociation; instead,
its formation seems unfavored. Hence, in contrast to alkali halides,
where n = 4 is a magic number, it has rather an anti-magic character
in case of sodium formate clusters, resulting in the [NaOOCH]4 Na+
cluster ion not only having slightly lower intensity in the normal
ESI mass spectrum but also being practically absent as fragment in
the CID of larger cluster ions. It is to be noted that the employed
mass spectrometers are not designed for the sampling of low mass
ions and might thus significantly discriminate against the bare Na+
ion. Therefore, we decided not to monitor this fragment at all and
recorded the spectra only from m/z = 50. On the basis of our com-
putational results, discussed below, preference for the formation of
Na+ seems improbable for n ≥ 3.
At first sight, the measurements carried out on the triple
quadrupole mass spectrometer (Fig. 3, right column) notably dif-
fer due to the presence of consecutive dissociation channels. They
demonstrate very clearly the significance of consecutive reactions
in a QqQ instrument, in contrast to their unfavored nature in IT
instruments, which is the expected behavior. In spite of the con-
siderable differences with respect to ion activation, the identity of
primary fragments, as well as their relative ratio at the 50% survival
yield, agrees well in the two sets of experiments. In particular, the
unfavored [NaOOCH]4 Na+ cluster is not produced in the QqQ type
instrument either; even the consecutive dissociation processes do
295
not lead to this fragment ion. These results further support that
the observed phenomena are not artifacts linked to a specific type
of instrument, but they reflect the inherent behavior of sodium
formate clusters.
3.2. Calculated structural features
The above experimental analysis highlighted the preferred frag-
mentation pathways and the notably different behavior of NaOOCH
clusters from that of NaCl. For alkali halides, it was usually found in
the literature that the computed structures and dissociation ener-
gies or average binding energies can account well for the observed
magic numbers [29–32,34,35]. Hence, we also turned to compu-
tational chemistry to obtain an atomic-level description of the
involved sodium formate species and to correlate the observed
stabilities in the spectrometer with the energetics of the clusters.
Density functional theory was used to optimize geometries and
derive zero-kelvin internal energies, as a measure of the inherent
stability, for the lowest-lying isomers of the involved ions and neu-
tral species. The unbiased choice of initial structures was ensured
by a random starting geometry generation. The M05-2X exchange-
correlation functional was chosen on the basis of its high accuracy
for the thermochemistry of main-group compounds. Specifically, a
mean unsigned error of 0.17 eV was reported in the literature for a
set of diverse chemical transformations [75]. Considering the sim-
ple electronic structure of the sodium formate clusters and the error
cancelation in the relative energetics of species of similar nature,
we expect the maximum errors in the energetics described below
not to exceed 0.2–0.3 eV, and the errors in differences in stability or
dissociation energy to be even smaller. This assumption is further
supported by test calculations using the SCS-MP2 wavefunction-
based method (shown in the Supplementary Information), which
do not differ more than 0.2 eV from the DFT results and predict the
same trends in dissociation energies as DFT.
The computations were carried out for the [NaOOCH]n Na+
(n = 1–5) ions and for the neutral fragmentation products
[NaOOCH]n (n = 1–4). The most stable structures, computed via
M05-2X to lie within a 0.1 eV energy window, are shown in
Fig. 4 and compared below with literature results on [NaCl]n
[29,30,32,47,76–78] and [NaCl]n Na+ [29–32].
The smallest neutral species, the NaOOCH ion pair, shows the
expected in-plane coordination of the Na+ to both oxygens of the
formate anion. The Na–O distances are 2.18 Å; for larger clusters,
the distances between Na and O directly in contact show some
variation (∼2.0–2.7 Å). This ion pair can be considered as the basic
building block of the crystal structure of solid NaOOCH, consisting
of layers of NaOOCH ion pairs, with parallel alignment within lay-
ers and antiparallel between neighboring layers (see Fig. 1d). The
most stable structure of [NaOOCH]2 is the planar antiparallel dimer,
in complete analogy with [NaCl]2 or other alkali halides. Related
arrangement of two NaOOCH units from two neighboring layers
can also be identified in the crystal structure although interaction
with surrounding ions leads to marked deviation from planarity. In
contrast to the monomer and the dimer, the neutral trimer shows
a compact, truly three-dimensional structure, which is not similar
to any part of the crystal. Apparently, the absence of the crystal
packing forces allows the system to avoid the less favorable H· · ·Na
contacts and to keep the number of O· · ·Na contacts high. Indeed, 6
oxygens from 5 formates coordinate a single Na+ in the crystal, but
even in the smallest clusters, 3–4 oxygens around Na+ are typical.
As a quite general consequence, the occurrence of a Na+ coordi-
nated to both oxygens of two or more formates (a “multiple-double
coordination”) is a typical feature for small clusters, but in the crys-
tal, each Na+ is in close contact with both oxygens of only a single
formate. For [NaCl]3 , the most stable structures are the planar six-
atom ring and the planar 2 × 3 × 1 fragment of the crystal structure.
296 Á. Révész et al. / International Journal of Mass Spectrometry 354–355 (2013) 292–302

Fig. 3. Breakdown curves of [NaOOCH]n Na+ (n = 3–8) clusters constructed from the tandem mass spectra measured on the ion trap instrument (left column) and on the
triple quadrupole instrument (right column). Note that the fragment Na+ (m/z = 23) was not taken into account. Furthermore, the [NaOOCH]2 Na+ cluster produces only the
daughter ion [NaOOCH]Na+ (m/z = 91); thus, its diagram is not shown.
 Á. Révész et al. / International Journal of Mass Spectrometry 354–355 (2013) 292–302 297

Table 1
Branching ratios of dissociation processes of [NaOOCH]n Na+ clusters as obtained from the ion trap measurements. The percentages denote the relative abundance of the
different channels at high extent of excitation, i.e., when equilibrium has already been reached between the various losses.

m/z Composition Relative abundance of losses in %

Monomer Dimer Trimer Tetramer Pentamer Hexamer Heptamer

+
159 [NaOOCH]2 Na 100
227 [NaOOCH]3 Na+ 77 23
295 [NaOOCH]4 Na+ 88 11 1
363 [NaOOCH]5 Na+ 0 75 25 0
431 [NaOOCH]6 Na+ 31 4 48 17 0
499 [NaOOCH]7 Na+ 25 36 1 31 7 0
567 [NaOOCH]8 Na+ 6 41 26 2 22 2 0

Their NaOOCH analogs were also found by our calculations, but exhibit a cubic arrangement of the ions, with minor variation due
they lie 0.30 eV and 0.22 eV higher in energy than the most sta- to the versatility of formate coordination mode. However, the gas-
ble isomer, respectively. The similarity to NaCl is partially restored phase [NaCl]4 cube directly corresponds to a 2 × 2 × 2 fragment of
for the tetramer [NaOOCH]4 , where all located low-lying isomers the crystal, while the orientation of formates in all shown isomers

Fig. 4. Computationally identified isomers of [NaOOCH]n and [NaOOCH]n Na+ within an energy window of 0.1 eV from the most stable structure. Cations are black, anions
are white. Relative zero-kelvin energies with respect to the lowest-lying structure are given in eV. Dashed and dotted lines separate smaller fragments that make up certain
larger structures (see text for details).
298 Á. Révész et al. / International Journal of Mass Spectrometry 354–355 (2013) 292–302
of [NaOOCH]4 is markedly different from that in the solid-phase
structure.
In the investigated size range, the positively charged clusters
tend to have more low-lying isomers than the neutral species.
Already for [NaOOCH]Na+ , we could identify two essentially isoen-
ergetic structures, as a result of the competing preferences for Na
coordination to both oxygens and for increased Na· · ·Na distances.
[NaOOCH]2 Na+ is exceptional, having a single isomer within the
0.1 eV window, containing a central Na+ over the middle of a six-
membered Na–OO–Na–OO ring. The remarkable stability of this
“dome” arrangement is corroborated by its appearance as the build-
ing block of larger clusters, but it does not appear as element of
the crystal. A low-lying related structure for [NaCl]2 Na+ is an equi-
lateral triangle of three Na+ with chlorides above and below the
center, but the “dome” contains rather an isosceles Na3 triangle
with one markedly longer side. The analogs of other [NaCl]2 Na+
structures, i.e., the linear chain (5 × 1 × 1 fragment of the crystal)
or the [NaCl]2 square with a pendant Na+ at one corner, are more
than 0.5 eV higher for sodium formate. For the next larger cluster,
[NaOOCH]3 Na+ , we found two types of isomers. A central Na+ inter-
acting with five or six oxygens of an almost planar nine-membered
ring is the characteristic of the more stable isomers (A and B). These
are conceptually similar to the most stable geometry of [NaCl]3 Na+
although the latter is much less planar due to the small size of chlo-
ride. Somewhat higher in energy, variations of the “dome” structure
with an attached [NaOOCH] unit appear (C and D, consider the
dashed lines). For all these geometries, the presence of “multiple-
double” coordination excludes the analogy with the solid-phase
structure.
For sodium chloride, the cationic n = 4 cluster was found to be
a “magic” one, with a planar structure corresponding to a 3 × 3 × 1
slab of the rock-salt lattice. Related local minima for [NaOOCH]4 Na+
appear to be missing; instead, the most stable structure (A) is
remarkably compact, and it can be described either as the com-
bination of two “domes” with a common Na+ (consider the dashed
line), or as a [NaOOCH]4 cube with an extra, “quadruply-doubly”
coordinated Na+ in the middle (see the dotted line). The size of
the formate ion seems to play key role in allowing an extra cation
inside the cube; for [NaCl]4 Na+ , only isomers with Na+ attached to a
[NaCl]4 cube via one or two anions from outside were found. A “cube
plus cation outside” arrangement is exhibited by B-[NaOOCH]4 Na+
(consider the dashed line), but it is somewhat less stable than the
“combined domes” structure. B-[NaOOCH]4 Na+ can also be inter-
preted as a folded B-[NaOOCH]3 Na+ structure with an attached
[NaOOCH] ion pair (see the dotted line).
The [NaOOCH]5 Na+ cluster has a less well-defined structure,
with several similar stable isomers. This feature, as well as the
actual geometries, is reminiscent to [NaCl]5 Na+ . Structures A, B,
and D can be best described as a [NaOOCH]4 cube with an attached
A-[NaOOCH]Na+ unit, while C and E better correspond to A-
[NaOOCH]3 Na+ with an attached [NaOOCH]2 dimer (dashed lines);
nevertheless, alternative “assignments” exist, and a clear-cut clas-
sification to two families cannot be made.
3.3. Calculated energetics of the fragmentation processes
Having located the most stable isomers for all involved
species, one can calculate the energies required to dissociate the
[NaOOCH]n Na+ clusters to a smaller cationic cluster and a neu-
tral [NaOOCH]k fragment. We assume “adiabatic” dissociations, i.e.,
we suppose that the fragmentation starts from the lowest-lying
structure of the parent ion and yields the most stable isomers of
the daughter ion and the neutral part. The results are shown in
Table 2 (see the non-parenthesized numbers). In agreement with
the expectations, loss of a smaller neutral fragment is typically pre-
ferred; hence, the monomer loss channel is either the energetically
most favored one, or it is very close to being the most favored. The
monomer loss energies seem to converge to a value around 1.95 eV
with increasing cluster size, but a definite conclusion in this respect
would necessitate the study of a larger size interval.
The computational results reveal that the small [NaOOCH]n Na+
clusters with even n values are more stable, i.e., they require more
energy for dissociation, than species with odd n. This might be the
energetic consequence of the well-defined and compact structures
for the even-n species. Interestingly, our MS studies showed that
the n = 4 (m/z 295) and the n = 2 (m/z 159) cluster ions have low
abundance, and in MS/MS, the m/z 295 ion is not produced from the
fragmentation of the mass-selected higher clusters. On the basis of
the correlation of the computed energetic stability with structural
features and the above-discussed expected accuracy of the com-
putations, we consider it very unlikely that the computed trends
would be in error. It can thus be concluded that the observed behav-
ior is not determined solely by the energies, but other factors also
play an important role.
3.4. Investigation of fragmentation pathways
One possible reason for the disagreement between the trends
in experiments and in the calculated adiabatic dissociation ener-
gies is that some dissociations may not be able to produce directly
the lowest energy isomer, and the involved rearrangements may
pose significant energetic barriers. In order to provide a detailed
description of all dissociation processes, a full map of the cor-
responding potential energy surface would be necessary. Related
studies exist in the literature in which the isomerization PES was
explored in detail for [LiF]4 [46] and [NaCl]35 Cl− [79]. Such calcu-
lations are beyond the scope of the present work; however, we
carried out simple PES scans to examine whether there are sig-
nificant potential energy barriers hindering the dissociations of the
most stable isomers of the clusters to the most stable isomers of the
next smaller cluster and a [NaOOCH] fragment. The energy profiles
are shown in the Supplementary Information, only a brief summary
is given here. As already apparent from its structure, [NaOOCH]2 Na+
can directly dissociate into [NaOOCH] and A-[NaOOCH]Na+ , and no
barrier higher than the endothermicity of the reaction was found.
For A-[NaOOCH]3 Na+ , a rearrangement via a barrier of ∼0.8 eV
can occur, which leads to a structure consisting of the “dome” of
[NaOOCH]2 Na+ and a [NaOOCH] unit connected via its edge. This
structure, ∼0.4 eV higher than the most stable isomer, can then
directly lose [NaOOCH], again without a barrier higher than the
endothermicity. The compact A-[NaOOCH]4 Na+ can interconvert
with B-[NaOOCH]4 Na+ in a process with an activation energy of
∼0.7 eV. In accordance with expectations based on its structure,
the direct dissociation of B-[NaOOCH]4 Na+ to A-[NaOOCH]3 Na+
and [NaOOCH] is again feasible without extra barrier. Hence, for
n = 2–4, the monomer loss can always proceed with a critical
energy equal to the adiabatic dissociation energy. For n = 5, i.e.,
A-[NaOOCH]5 Na+ , we only examined a reaction pathway toward B-
[NaOOCH]4 Na+ , as this route seemed to be easier to follow with the
employed computational technique. Indeed, we found that simul-
taneous rearrangement and expulsion of a [NaOOCH] fragment
can connect A-[NaOOCH]5 Na+ with B-[NaOOCH]4 Na+ . Although B-
[NaOOCH]4 Na+ is 0.10 eV higher than the most stable n = 4 cluster
A-[NaOOCH]4 Na+ , this result is sufficient to prove that for n = 5, the
monomer loss is still preferred energetically over the dimer loss
(1.90 + 0.10 < 2.14), and it occurs at smaller threshold energy than
the monomer loss from n = 4 (1.90 + 0.10 < 2.04).
In short, we found that rearrangements seem indeed necessary
for the “adiabatic” dissociations, but the involved barriers are low.
The threshold energies of the dissociations are not influenced to an
extent which would explain, most importantly, the experimentally
observed preference for the dimer loss from n = 5, and thereby, the
 Á. Révész et al. / International Journal of Mass Spectrometry 354–355 (2013) 292–302
Table 2
0 K dissociation energies and 500 K dissociation Gibbs free energies (the latter in parentheses) of [NaOOCH]n Na+ clusters for the loss of neutral [NaOOCH]k species, computed
at the M05-2X/6-311++G(3df,3pd)//M05-2X/6-31G(d) level as the difference between the energies of the most stable isomers of the fragments (according to the corresponding
energy scale). The lowest energy channels are emphasized with boldface numbers.
m/z Composition Computed 0 K dissociation energy (500 K Gibbs free energy) (eV)
Monomer loss
+
91 [NaOOCH]Na 1.77 (1.40)
159 [NaOOCH]2 Na+ 2.17 (1.16)
227 [NaOOCH]3 Na+ 1.85 (1.37)
295 [NaOOCH]4 Na+ 2.04 (0.71)
363 [NaOOCH]5 Na+ 1.90 (1.14)
existence of the “anti-magic” cluster n = 4. From the calculations,
it thus seems that neither the thermochemical stability, nor the
related energetic barriers can explain the observed abundance and
fragmentation patterns of sodium formate clusters.
3.5. Computational estimation of entropic effects
Deviation from the stability pattern predicted from dissociation
energies was found in the literature for the fission of metastable
Nan 2+ clusters [80], and for [NaF]n Na+ clusters produced by the
gas aggregation technique [36]. In these studies, statistical (i.e.,
entropic) effects were proposed to play important role in determin-
ing cluster stabilities and preferred fragmentation pathways, and
such effects may also be involved in the case of sodium formate. A
rigorous analysis of the influence of entropy in a mass spectromet-
ric experimental setting would require a master equation modeling
of the time-dependent internal energy distribution of the dissoci-
ating ions. Reasonable models would be required for the density of
states arising from the coupled, anharmonic internal motions, for
the energy exchange upon energizing collisions, and for the energy-
dependent unimolecular rate constants (e.g., RRKM theory). As the
goal of the present study was only to assess the importance of
entropic effects, we decided to employ several approximations.
First, a thermal equilibrium situation was assumed, implying that
one can use free energy values to characterize the dissociations.
This is probably a realistic assumption in the case of ion trap instru-
ments [72]. Second, we considered the activation free energy for the
fragmentation to be equal to the dissociation free energy, corre-
sponding to the completely separated fragments. In contrast, the
true transition state in terms of free energy is located at some
finite value of the dissociation reaction coordinate. Our assump-
tion is equivalent to treating the transitional degrees of freedom
as free translation and rotation of the products, which definitely
introduces error. Rearrangements may also represent significant
entropic bottlenecks even if they are not associated with energetic
barriers. Third, we employed the rigid-rotor-harmonic-oscillator
(RRHO) approach to model the molecular motions. An error of 1–2%
in total entropies may be typical for the RRHO procedure even for
rigid molecules [81], leading to errors on the order of 0.1 eV in the
free energies at the present temperature and molecule sizes. The
more strongly anharmonic low-frequency modes of larger clusters
may further increase the error bar. Nevertheless, an inspection of
the structures shows that these modes are still probably better
treated as vibrations than as hindered internal rotations, for which
the RRHO approach would yield large inaccuracies [82–84]. Some
error compensation upon calculating the free energy differences
can also be expected. For these reasons, we refrained from the com-
putationally intensive estimation of hindered rotor or anharmonic
corrections [85]. While all these approximations limit the accuracy
of the treatment of entropic effects, we still expect that the free
energies computed in this way can correctly reflect many qualita-
tive trends that could be obtained from a more rigorous treatment
within a microcanonical framework.
299
Dimer loss Trimer loss Tetramer loss
2.14 (1.42)
2.21 (1.40) 2.32 (2.07)
2.09 (0.94) 2.60 (1.38) 2.53 (1.87)
2.14 (0.71) 2.33 (1.36) 2.66 (1.61)
Using the discussed protocol, we estimated the Gibbs free ener-
gies of all considered isomers of the [NaOOCH]n Na+ ions and the
[NaOOCH]k neutral fragments. A single temperature value was
employed throughout, chosen such that the resulting predicted dis-
sociation free energies yield rate constants that roughly correspond
to the experimental time scale of the fragmentations in the ion trap
experiments. The obtained value, 500 K, is somewhat low but not
unrealistic for activated ions in the ion trap.
In line with the suggestions for [NaF]n Na+ , our computational
results highlight that the entropy notably alters the stability
order of the isomers of a given cluster. As a general trend, more
extended (“less ordered”) structures become favored, particularly
for larger cluster sizes. For the neutral [NaOOCH] and [NaOOCH]2 ,
the structure with the lowest Gibbs free energy is the still same
as that with the lowest zero-kelvin internal energy. However, for
[NaOOCH]3 , a flatter, looser structure a-[NaOOCH]3 (see Fig. 5)
has the lowest G, 0.06 eV below [NaOOCH]3 in Fig. 4. The cubic
structure is preferred also in terms of G for [NaOOCH]4 , but the
most stable isomer becomes the more open B-[NaOOCH]4 . For
the charged [NaOOCH]Na+ , there is no change in the order of iso-
mers, but G between A and B is 0.11 eV, significantly larger than
the zero-kelvin energy difference. The “dome” of [NaOOCH]2 Na+
remains favored in G as well. For n = 3 and n = 4, the symmetri-
cal planar B-[NaOOCH]3 Na+ and the “cube plus cation outside”
B-[NaOOCH]4 Na+ become the lowest-lying structures, respectively.
Finally, for n = 5, entropic effects lead to the preference for the
extended a-[NaOOCH]5 Na+ isomer (Fig. 5), surmounting a E0K of
0.29 eV.
Having located the structures with lowest G, we can calculate
the appropriate free energy differences to obtain the dissociation
G values of the [NaOOCH]n Na+ ions, again in the “adiabatic”
sense. The values are reported in Table 2 (numbers in parentheses).
Apparently, the trends differ notably from those of the zero-kelvin
internal energies and can account for some of the experimental
observations. Accordingly, the monomer loss has the lowest bar-
rier for all clusters, except for [NaOOCH]5 Na+ , which is correctly
predicted to strongly prefer dimer loss, avoiding the anti-magic
n = 4 cluster upon fragmentation. However, the monomer loss still
Fig. 5. Lowest Gibbs free energy isomers of [NaOOCH]3 and [NaOOCH]5 Na+ .
300 Á. Révész et al. / International Journal of Mass Spectrometry 354–355 (2013) 292–302
Fig. 6. MassKinetics modeling of the breakdown curves of [NaOOCH]5 Na+ . Circles
are experimental data, crosses show results from the fitting. Thermal model was
used, with a reaction time of 20 ms; a single set of activation parameters for the
whole figure, and an individual temperature value at each fragmentation amplitude
were fitted.
appears as the second most favorable channel, while experimen-
tally, trimer loss is observed instead. Furthermore, the absolute
values of the dissociation free energies of the lowest-G chan-
nels show significant variation (0.71–1.40 eV). Specifically, the n = 3
cluster seems to have a larger free energy barrier than n = 4 and n = 5,
while experimentally, there is no significant difference between the
amount of excitation necessary to fragment these clusters. In short,
there are several indications that our calculations do not model
accurately the actual conditions in the ion source and during dis-
sociation, but the consideration of the Gibbs free energies instead
of zero-kelvin energies still significantly improves the qualitative
agreement with experiments. As the computed 500 K enthalpies
(data in Supplementary Information) exhibit essentially the same
behavior as the zero-kelvin energies, we can conclude that entropic
effects play a key role in shaping the observable stability pattern of
sodium formate clusters.
3.6. Experimental estimation of activation free energy differences
Activation parameters of processes occurring in the mass
spectrometer can be estimated by fitting rate theories to the exper-
imental data although errors can easily reach ∼20% [86]. In order to
provide a preliminary data analysis of the dissociation processes,
we employed the MassKinetics [87] software to model the disso-
ciation of [NaOOCH]5 Na+ (m/z 363) in the ion trap experiments. In
accordance with the slow-heating property, a thermal equilibrium
was assumed in the modeling. The monomer, dimer, and trimer
loss processes were considered, producing the fragments with m/z
295, 227, 159, respectively. In the quantum chemical investigation
of a series of dissociations, we always found rearrangement barri-
ers to be notably lower than the dissociation energies (see above).
Therefore, we think it is reasonable to suppose the potential energy
barriers of these three losses to be equal to the computed zero-
kelvin dissociation energies (i.e., data from Table 2). The activation
entropy for the dimer loss was estimated using the computed
harmonic frequencies, but in this case, transitional modes were
treated as low-frequency vibrations instead of free translations and
rotations, which corresponds to lower activation entropies. Indi-
vidual temperature values corresponding to each fragmentation
amplitude, and the activation entropies of the other two processes
(more precisely, frequencies of the 6 transitional modes in the
two transition states; common at all amplitudes) were adjusted
to obtain the best fit of the experimentally observed branching
ratios. It was found that the relative abundances can be well fitted
at each considered fragmentation amplitude (see Fig. 6). The result-
ing temperature monotonously increases and then levels off with
increasing fragmentation amplitude (not shown), thus exhibiting
qualitatively correct behavior. The temperature values were in the
range of 550–700 K depending on the extent of activation, expec-
tedly higher than the 500 K obtained from the quantum chemical
treatment due to the assumption of tighter transition states. At
650 K, which roughly corresponds to a 50% survival yield of the
parent ion, the absence of the monomer loss in the experiments
can only be reproduced if the activation free energy of this chan-
nel is larger than 1.66 eV, corresponding to an activation entropy
at least ∼60 J/mol K less than that of the dimer loss channel. For the
dimer and trimer loss channels, activation free energies of 1.48 eV
and 1.55 eV were obtained from the fit, respectively. The corre-
sponding quantum chemical dissociation free energies for 650 K
are 0.98 eV, 0.37 eV and 1.11 eV. These values are understandably
lower than those from the fit; more importantly, the preference
for the dimer loss is exaggerated, and the monomer loss is incor-
rectly predicted as the secondary channel, most probably due to
inaccuracy of entropy estimation. Nevertheless, the conclusion is
clear from both the experimental and computational approaches:
The monomer loss channel does not appear due to its entropically
unfavored nature.
4. Conclusions
In the present work, cationic sodium formate clusters
([NaOOCH]n Na+ ) were subjected to a combined experimental (ESI-
MS, MS/MS) and computational study. As the crystal structure of
sodium formate is similar to the extensively investigated alkali
halides, we expected to find many analogies, but we found marked
differences instead. Here, we summarize the main findings in a
qualitative manner, focusing on the tetramer, which is probably
the most characteristic example.
Accurate quantum chemical computations show that minimum
energy conformations of small neutral and cationic sodium formate
clusters are often much different from those expected based on
the crystal structure and also from analogous alkali halide clus-
ters. Specifically, the structure of [NaCl]4 Na+ resembles a planar
3 × 3 × 1 slice of the crystal, with a sodium atom in the center,
while [NaOOCH]4 Na+ exhibits a compact, cubic arrangement of the
ions, with one sodium in the middle. At the same time, their ener-
getic properties are similar. [NaCl]4 Na+ is a stable configuration,
resistant to mass spectrometric fragmentation, which results in a
‘magic’ cluster. According to quantum chemistry, fragmentation of
[NaOOCH]4 Na+ also requires high critical energy, higher than that
of either the trimer or the pentamer. This would suggest that, in
mass spectrometry, this species would also be a particularly stable,
i.e., magic, cluster.
To investigate the behavior experimentally, we measured the
electrospray ionization mass spectrum of the [NaOOCH]n Na+
clusters and also studied their collision-induced dissociation. Frag-
mentation of the charged clusters takes place by the loss of a
neutral monomer or oligomer unit, providing useful information
on the stability of the clusters: Which clusters are stable, and
which fragment easily, and among parallel processes, which ones
are predominant. For [NaOOCH]4 Na+ , experiments show the exact
opposite of what was expected from calculations: (1) in the ESI
spectrum, the tetramer has smaller intensity than either the trimer
or the pentamer. (2) Fragmentation of higher oligomers avoids the
tetramer product; e.g., the pentamer loses a neutral dimer and
not a monomer unit. All of these indicate that [NaOOCH]4 Na+ is
less stable than neighboring clusters, behaving as an ‘anti-magic’
cluster.
The seeming contradiction between calculation and experi-
ments can be resolved by considering entropy effects. Fragmen-
tation of sodium formate clusters requires ca. 2 eV of energy. To
drive fragmentation in the timeframe of the mass spectrometric
experiments, one has to put a significant amount of internal energy
 Á. Révész et al. / International Journal of Mass Spectrometry 354–355 (2013) 292–302
into the clusters. In ion trap instruments, this can be reasonably
described by a temperature, which has to be on the order of ∼500 K
according to our calculations. At this temperature, entropic dif-
ferences provide a sizable contribution to Gibbs free energy. One
can expect, and calculations did show, that the energetically stable,
compact [NaOOCH]4 Na+ cluster is entropically strongly unfavored,
as compared to, e.g., the flat and extended [NaOOCH]3 Na+ . As a
result, the energetically very stable [NaOOCH]4 Na+ cluster becomes
unstable on the Gibbs free energy scale. This explains why this clus-
ter is avoided in the fragmentation of larger ones, and why it has a
small intensity in ESI spectra.
In short, sodium formate cluster fragmentation is dominated not
by energy, but entropy effects, in contrast to alkali halides. Although
energetically preferred, the tetramer becomes an ‘anti-magic’ clus-
ter in the ESI spectrum and in dissociation processes due to its low
entropy.
Acknowledgments
Useful discussions with Dr. András Stirling are gratefully
acknowledged. T.A.R. was supported by the János Bolyai Research
Scholarship of the Hungarian Academy of Sciences. Financial
support was received from TIOP 1.3.1-10/1-2010-0008, TIOP 1.3.1-
07/1, TÁMOP-4.2.2.A-11/1/KONV-2012-0053, and PTE AOK KA
2009, 2011, 2013.
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.2013.06.029.
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