Milovanovic 2017

View Article Online
View Journal
PCCP
Physical Chemistry Chemical Physics
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: M. Z. Milovanovic,
S. Velikovi, F. Veljkovi and S. Jerosimi, Phys. Chem. Chem. Phys., 2017, DOI: 10.1039/C7CP04181K.
Volume 18 Number 1 7 January 2016 Pages 1–636 This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
PCCP
Physical Chemistry Chemical Physics Accepted Manuscripts are published online shortly after
www.rsc.org/pccp
acceptance, before technical editing, formatting and proof reading.

Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the

author guidelines.
Please note that technical editing may introduce minor changes

to the text and/or graphics, which may alter content. The journal’s
ISSN 1463-9076 standard Terms & Conditions and the ethical guidelines, outlined
PERSPECTIVE
in our author and reviewer resource centre, still apply. In no
Darya Radziuk and Helmuth Möhwald
Ultrasonically treated liquid interfaces for progress in cleaning and
separation processes
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
rsc.li/pccp
Page 1 of 46 Physical Chemistry Chemical Physics
View Article Online
DOI: 10.1039/C7CP04181K
1
Structure and Stability of Small Lithium-Chloride
Physical Chemistry Chemical Physics Accepted Manuscript

LinClm(0,+1) (n ≥ m, n = 1-6, m = 1-3) Clusters
Published on 30 October 2017. Downloaded by University of Windsor on 30/10/2017 11:56:51.
Milan Milovanović *a), Suzana Veličković b), Filip Veljković b), Stanka Jerosimić a)
a)
University of Belgrade, Faculty of Physical Chemistry, Studentski trg 12-16, P.O.Box 47,
PAC 105305, 11158 Belgrade, Republic of Serbia

b)
University of Belgrade, Vinča Institute of Nuclear Sciences P. O. Box 522, 11001
Belgrade, Republic of Serbia
KEYWORDS. lithium-chloride clusters; mass spectrometry; cluster stability; charge
distribution; electronic structure calculations; B3LYP; RCCSD(T).
ABSTRACT. In the present study, we report the results of a detailed theoretical investigation
along with the experimental observations of chlorine-doped small lithium clusters. The
cluster ions of the type LinClm+ (n ≥ m, n = 1-6, m = 1-3) were obtained by the evaporation of
LiCl from the Knudsen cell as a chemical reactor in the temperature range between 1800-
2700 K. Heterogeneous clusters with more than one Cl atom are produced and detect for the
first time, experimental conditions for formation and stability are examined. The structural
characteristics and stabilities of neutral and positively charged LinClm species are analyzed by
using quantum chemistry methods. Doping lithium clusters with chlorine increase their
stability, although there is a typical closed-shell – open-shell alternation in stability.
Calculated dissociation energies are the best indicator of cluster stability of experimentally
detected clusters. Heterogeneous lithium-chloride clusters can be viewed as species consisted
of m negative Cl− ions and positively charged Lin(+1,+2) “cage”; upon ionization electron
Physical Chemistry Chemical Physics Page 2 of 46
View Article Online
DOI: 10.1039/C7CP04181K
2
departures the lithium cage. An important reason for higher stability of closed-shell clusters is
the delocalization of electrons over lithium cage, which is more energetically favored than

localization of electrons between two lithium atoms. According to their ionization energies,
the titled clusters can be classified as “superalkalis”.

I INTRODUCTION
One of the main reasons why the field of cluster science continues to expand is in
establishing the connection with nanoscale science where clusters could serve as building
blocks for new materials, with tailored properties.1
Among such clusters, two important types are “superalkalis“ and “superhalogens“.
Since 1981, when Gutsev and Boldyrev2,3 introduced the terms 'superalkalis' and
'superhalogens' for species possessing lower ionization energies (IE) than alkali metal and
higher electron affinities (EA) than halogens, respectively, a great number of theoretical and
experimental investigations have been carried out to understand the physical and chemical
properties of these clusters.4–11 One of the most common alkali metal that form superalkali
clusters is lithium. Theoretical studies on systems with lithium include, for example, boron-
lithium clusters,12–16 aluminium doped lithium clusters,17,18 mixed silicon-lithium clusters,19,20
LinGe,21,22 LinO23 and (Li2O)n clusters,24 small lithium halide,25 LinFn–1 clusters,26,27 or neutral
and cationic LinI(0,+1) (n = 1-6).28,29 Tong et. al. investigated in detail series of polynuclear
superalkali cations with various functional groups, YLi3+ (Y= O2, O4, O5, CO3, CO4, C2O4,
C2O6, CO3, SO3 and SO4,),30,31 as well as M2Li2k+1+ (M = F, O, N, C, and B for k= 1-5).32,33
Regarding lithium halide clusters LinX (X = F, Cl, Br, and I; n > 1), they were experimentally
detected and examined through the mass spectrometry and ionization energy
measurements.28,34–40 Neutral LinCl (n = 1-7) species were also theoretically investigated.41
Most recently, the smallest superalkali clusters, M2X (M= Li, Na; X=F, Cl), have been
View Article Online
DOI: 10.1039/C7CP04181K
3
reinvestigated by using ab initio MP2 and QCISD methods.42 These clusters were classified
as the electrides (compounds in which alkali metals ionize to form bound alkali cations and

excess electrons) that have significant non-linear optical (NLO) properties and concluded that
M2X would be the smallest clusters possessing such exceptional properties.

An important use of superalkalis and superhalogens, as building blocks for novel
compounds, with enhanced stability, has been proven. These compounds are called
supersalts, and can be viewed as non-traditional salts, with preferred dissociation to ionic
superatom fragments, (superalkalis and superhalogens), which distinguish them from
traditional salts. One of the examined supersalts were BLi6 – X (X= F, LiF2, BeF3, BF4)
species.43 Recently, supersalts of the type Li3X3 (X = F, Cl, Br, I) have been theoretically
examined,44,45 and it has been shown that these supersalts could be designed by interaction of
superalkalis (Li2X) and superhalogens (LiX2).
Formation of charged clusters was investigated in series of experiments by Knudsen
effusion cell coupled with a mass spectrometer (KCMS). Generally, during the last 60 years,
the KCMS represents a powerful method in the field of high-temperature chemistry since it
gives the qualitative and quantitative information about gaseous species effusing from the
Knudsen cell such as thermal stability, volatility under different conditions, oxidation
resistance, reactivity, etc. A large number of clusters have been identified along with their
thermodynamic properties using this method, for example, homo- and heterometal clusters
(Ge, Sn, Os, Bi, alkali metals, PdSn, Ge4Sn(g)), fullerenes and their derivatives (C60, C70-106,
C60F45–, C60F48+).46–57
The KCMS is also important method for studying superalkalis clusters in gas phase.
The first identification and measurement of the atomization energies of homogeneous metal
clusters of lithium were made by the KCMS. Furthermore, this method combined with the
View Article Online
DOI: 10.1039/C7CP04181K
4
electron impact ionization was successfully applied for generation and characterization of the
small heterogeneous lithium clusters of different types LinX and LinXn–1 (X –

nonmetal).38,39,58–63
The main subject of the present article are small superalkalis – neutral and cationic
clusters, LinClm(0,+1) (n ≥ m, n = 1-6, m = 1-3). Although some information about these
clusters (those with one chlorine atom) have been already reported,39,41 systematic report on
geometries of all isomers, their growth mechanism, stability and electronic structure were not
reported thus far. On the other hand, the aim of the experimental part of the current study was
to get more reliable data about conditions for the predominant formation of these clusters,
and to compare them with previous reports, as well as the theoretical predictions performed
herein.
The present paper is structured as follows: the next section II will present the details
of experimental detection. The following section III will provide the details of the quantum
chemical calculations. Section IV will present the Results and Discussion: the equilibrium
geometries and energies of structural isomers of neutral and positively charged LinClm
clusters, obtained by the combination of a stochastic procedure and density functional theory
(DFT) optimizations; further, stability of these clusters will be discussed by investigating
binding energies per atom, HOMO-LUMO gaps, chemical potential and hardness,
dissociation energies, adiabatic and vertical ionization energies. Section V will finally present
our present conclusions.
II EXPERIMENTAL DETECTION
The experiments were performed with a single focusing magnetic sector mass
spectrometer, capable to acquire electron impact mass spectra and equipped with the
Knudsen effusion cell. The electrons emitted from a rhenium cathode, were collimated to
View Article Online
DOI: 10.1039/C7CP04181K
5
interact with the vapor molecules in the ionization chamber and guided to an electron trap
cup. The formed ions were accelerated and separated by a sector magnetic field according to

mass/charge ratio and then analyzed with channeltron multiplier analyzer. Typical operating
pressures in the ion sources region were approximately 10–7 mbar.

The Knudsen cell was composed of a tantalum cylinder (the height was 7 mm, the
outside diameter was 6 mm) capped with a tantalum lid that had an orifice diameter of 0.1
mm in the center. To minimize the distance between the cell orifice and electron beam, the
Knudsen cell was placed into the ionization chamber of the mass spectrometer, which is
approximately 2 mm. The benefit of this method is that identification of all gaseous species
formed over condensed phases in the Knudsen cell is far better than in conventionally
configured KCMS.38
In the standard experimental conditions, the temperature of cell is uniform throughout
the inner cavity, i.e. the heater was wrapped around the outer wall of the cell, while in current
experimental setup tungsten heater was placed at the bottom of the Knudsen cell.
Temperature was measured both by thermocouple and optical pyrometer, specifically the
temperature of the cell’s cylinder by Pt-Pt/Rh thermocouple attached to its outer wall (within
± 10 K) while the temperature of heater by optical pyrometer (a temperature stability ±20 K).
The maximum temperature of heater was 2700 K.
The sample of LiCl salt was placed into the cell at atmospheric pressure. The cell with
the substance was maintained at a constant temperature in the mass spectrometer for several
hours in order to remove possibly adsorbed moisture. The designed apparatus allowed
detection of the neutral species using the electron impact ionization and ionic components of
the vapor. Each cluster ion in the mass spectrum was identified according to its mass/charge
ratio and the natural isotopic abundances of elements, which for lithium is 92.59 % 7Li, 7.41
View Article Online
DOI: 10.1039/C7CP04181K
6
% 6Li, and for chloride is 75.53 % 35Cl, 24.47 % 37Cl. The lithium chloride salt was used in
current experiments, since reliable data on the composition of its vapor are available from our

previous study, namely, the formation of positive ions LinCl = 2-6 has been recognized in this
system.39
III COMPUTATIONAL METHODS
The structures of low-lying isomers of clusters were obtained by using a random-kick
procedure, which is a derivative of the stochastic search method, first reported by Saunders,64
and later modified by Nguyen et. all65 to increase percentage of completed optimizations. In
the random-kick procedure, each atom of an initial structure, with Cartesian coordinates (xi,
yi, zi), is kicked to randomly move within a sphere of a radius r to a new position (xi+dx,
yi+dy, zi+dz). The constructed structures are then inputs for following geometry optimizations
with electronic structure methods. For controlled variable we used the “moving radius” of the
atoms, r, and the minimum distance of atoms (Dmin = [(xi–xj)2 + (yi–yj)2 + (zi–zj)2]1/2). The
initial structures were the structures with all atoms placed at the origin (xi = yi = zi = 0); After
being randomly kicked within a sphere of several different radii r = 2.0-4.0 Å, and Dmin= 1 Å,
the resulting structures were submitted to geometry optimization and frequency calculations
using B3LYP functional66,67 in the cc-pVDZ68,69 basis set.
The local minima structures were further refined using the same functional in the
correlation-consistent polarized valence quadruple-zeta basis set cc-pVQZ.68,69 Zero-point
vibrational energy (ZPVE) corrections were found by computing harmonic vibrational
frequencies at the same level of theory.
In order to test the changes of structural parameters with the basis sets, geometry
optimizations of LiCl(0,+1) and Li2Cl were performed in the triple-zeta [(aug-)cc-pVTZ] and
quadruple-zeta [(aug-)cc-pVQZ] basis sets68,69 at the B3LYP, RCCSD, and RCCSD(T)levels.

View Article Online
DOI: 10.1039/C7CP04181K
7
RCCSD abbreviates the restricted open-shell singles and doubles coupled-cluster with
restricted Hartree-Fock wave function as a reference.70,71 RCCSD(T) abbreviates the same

method with perturbative inclusion of the triple excitations.72 In the computations, RCCSD
and RCCSD(T) included the correlation of all electrons. The same methods were used in
conjunction with the triple- and quadruple-zeta core-valence correlation-consistent basis sets,
(aug-)cc-pwCVXZ.73
In Supporting Information (Table S1), we show equilibrium bond distances of LiCl
and LiCl+ calculated at different levels of theory. The experimental equilibrium bond length
for LiCl of (2.02067±0.00006) Å,74 is very well predicted with both B3LYP functional and
RCCSD method already in the cc-pVQZ basis set. The coupled cluster (CC) methods that
involve only the correlation of valence electrons give incorrect values, therefore, in the
present work we used only the CC computations that involved the correlation of all electrons.
Further, the inclusion of triple perturbations in RCCSD did not change the results;
consequently, the convergence with respect to the correlation method was achieved already at
the RCCSD level. Speaking of one-electron space, the impact of the augmentation of the
basis functions cc-pVQZ with diffuse functions for both neutral and cation species, was
negligible; the same is true for the inclusion of core functions (cc-pwCVQZ). When
compared with time-consuming ab initio RCCSD(T)/aug-cc-pwCVQZ method, the
B3LYP/cc-pVQZ gave very similar results (and these are similar to the RCCSD/cc-pVQZ
results). As far as frequencies are concerned, the experimental LiCl frequency of 643 cm–1
(Ref75) is quite good predicted with B3LYP/cc-pVQZ (641 cm–1).
Additionally, also in Supporting Information, in Tables S2 and S3, we present
theoretical predictions for bond lengths and angles of Li2Cl and Li2Cl2, and experimental
values76 for Li2Cl2. A difference between theoretical DFT and experimental results for Li2Cl2
View Article Online
DOI: 10.1039/C7CP04181K
8
is reasonable. Likewise, with the change of basis sets only small changes of geometrical
parameters is obtained.

Based on the results for above mentioned small species, we use DFT at the B3LYP
level in the cc-pVQZ basis set for geometries and frequencies of all investigated clusters,
because it provides relatively good agreement with the experimentally obtained bond lengths,
and provides good agreement with the corresponding results of time-consuming RCCSD(T)
method.
In order to calculate the binding, ionization, and dissociation energies of the title
species, single-point RCCSD(T)/cc-pwCVTZ calculations were performed at the B3LYP-
optimized geometries for the most stable isomers of all species. Additionally, to obtain the
chemical potential and hardness of neutral clusters, we use B3LYP/aug-cc-pVQZ single point
calculations of cation, neutral an anionic species at the geometries of the most stable neutrals.
The computations were carried out using MOLPRO 2012.077 program package.
Geometry optimizations at the B3LYP level employed the analytical gradient method;78
optimizations using CCSD(T) employed the numerical gradient calculations.79 For harmonic
vibrational frequencies and normal modes, the Hessians have been numerically approximated
using central energy differences.80 Default convergence criteria were used. In addition, the
natural bond orbital analysis was performed at the B3LYP/cc-pVQZ level with NBO
software81 implemented in Gaussian03.82
IV RESULTS AND DISCUSSION
IV A. Experimental results
The positive dilithium and threelithium chloride cluster ions were obtained earlier,
and their ionization energies were determined using the triple filament technique surface
View Article Online
DOI: 10.1039/C7CP04181K
9
ionization mass spectrometry. These cluster ions were formed when a solution of a mixture of
LiCl/LiI salts and a solution of C60/toluene were deposited on the side filaments and central

filament, respectively.36 When the side filaments were replaced by a cylinder, the surface
ionization of LiCl salt (pressed into a ring shape and placed next to cylinder’s inner wall),
was studied. In this condition, the positive LinCl+, n = 2-6 cluster ions were formed, and the
order of their ion intensities was Li2Cl+ ˃ Li6Cl+ ˃ Li4Cl+ ˃ Li5Cl+ ˃ Li3Cl+.39
Herein, the sample, LiCl salt, was loaded in the Knudsen cell, and directly heated by
tungsten heater placed on the bottom of the cell. In this experimental setup, the temperature
of cell is not uniform throughout the inner cavity. It was found that optimal range of heater’s
temperature for the formation of cluster ions were between 1800-2700 K. The neutral species
were not detected, while cationic species were drawn out from the cell by a weak electrostatic
fields, and following type of cluster ions LinCl+ (n = 2-6), LinCl2+ (n = 4-7), and LinCln–1+ (n =
3 – 5) were obtained. These cluster ions can be formed on several ways which do not exclude
one another. For example, since these ions have values of ionization energies below 7 eV,
they can be formed by surface ionization both from the heater and from the inner metal
surface of the Knudsen cell. Also, alkali metal salts are the strongest ion emitters, hence ion
emission from the surface of lithium chloride salt was possible. Suzuki and coworkers have
shown that ionization process involves not only ionization from metal but also direct
ionization by dissociative ionization of the compounds which are present in the vapor.83 In
our case, dissociative ionization of these cluster ions due to both collision and unimolecular
processes was possible, too. General, due to the complexity of the lithium chloride vapor the
various processes may overlap, consequently to determine the precursor for the cluster ions is
a very difficult task.
The obtained results indicate that the various types of cluster ions could be formed in
View Article Online
DOI: 10.1039/C7CP04181K
10
different range of temperatures. Namely, the positive LinCln–1+ (n = 3-5) and LinCl2+ (n = 4-7)
cluster ions were detected together in the vapor of the sample only in the temperature range

of 2184 K-2272 K. Their mass spectrum at 2218 K, is given in Figure 1.
Figure 1. The mass spectrum of positive LinCln–1+ (n = 3, 4 and 5) and LinCl2+ (n = 4, 5, 6,
and 7) cluster ions obtained by evaporating the salt of lithium chloride at 2218 K using the
KCMS.
The mass peaks at m/z = 91, 133, and 177 are assigned to Li3Cl2+, Li4Cl3+, and
Li5Cl4+, while m/z = 98, 105, 112, and 119 correspond to Li4Cl2+, Li5Cl2+ , Li6Cl2+, and
Li7Cl2+, respectively.
In this range of temperatures, Li3Cl2+, Li4Cl3+, Li5Cl4+ had highest ion intensities in
the vapor of the sample. It was observed that the most intensive peaks in the spectrum
correspond to Li3Cl2+; which were about two and six times higher than the intensities of
Li4Cl3+ and Li5Cl4+ peaks, respectively. For LinCl2+ clusters, the ion intensities mildly
increase in the sequence (Li4Cl2+ - Li5Cl2+ - Li6Cl2+ - Li7Cl2+), but their intensities were ten
View Article Online
DOI: 10.1039/C7CP04181K
11
times lower than of Li3Cl2+ ion. Clusters LinCl2+ were the most difficult to measure since they
have low intensities, short time of evaporation, and narrow observation of temperature range

(2184 K-2272 K).
Under this evaporation condition, clusters of the type LinCl+, such as Li3Cl+ and
Li5Cl+ are formed at the temperatures slightly above 2272 K, while the Li6Cl+ ions under
2184 K. Since the mass spectrum for the LinCl+ (n = 2-6) ions is very similar with the results
obtained in previous study,39 it is not presented. However, in Supporting Information (Table
S4), both the range of heater’s temperature and the range of intensities of the most abundant
isotope, for clusters of the type LinCl+ (n = 2-6), LinCln–1+ (n = 3-5) and Li+ ion is given.
It has been observed that at the beginning and during the reaction, the intensity of Li+
ion was higher than the intensities of other cluster ions. It is well known that complete
dissociation of LiCl could be performed at temperatures above 1800 K, however, here the
intensity of Li+ increases with the rising of the heater’s temperature. The obtained result
suggests that the dissociative ionization of the cluster ions in the vapor may occur as a
powerful process, which can be the explanation for the high intensity of the Li+ ion.
All the intensities of these cluster ions increase with the enhancement of the
temperature of the heater.
The Li2Cl+ and Li3Cl2+ cluster ions appear to be highly stable having the highest
intensity and longest range of heater’s temperature (1837 K-2676 K), and (1953 K-2576 K),
respectively. It should be emphasized that the maximum of intensity of the most abundant
isotope clusters was 50000 a.u., and 16200 a.u., for Li6Cl+, and Li4Cl+, respectively, and that
Li6Cl+ was more stable than Li4Cl+. Comparing the maximum of the intensities of the most
abundant isotopes of LinCl+ (n = 3 and 5) and LinCln–1+ (n = 4 and 5), the LinCl+ have more
than two times higher intensities than the LinCln–1+ ions. However, the evaporating time of
View Article Online
DOI: 10.1039/C7CP04181K
12
LinCln–1+ clusters is longer than for LinCl+ (n = 3 and 5) clusters. In current experimental
setup, according to the range of heater’s temperature, Li6Cl+, Li4Cl+, Li4Cl3+, Li5Cl4+ belong

to the group of medium-stable clusters, while clusters Li3Cl+ and Li5Cl+ to unstable.
According to the presented results, the proposed modification of Knudsen cell

presents an effective and simple method for obtaining the ‘non-stoichiometric’ clusters. The
predominant ion emission mechanism cannot be experimentally determined by apparatus
designed in this manner, but the results of performed experiments might be a guide for future
strategy for the preparation of lithium chloride clusters.
IV B. STRUCTURAL ISOMERS
The structures of clusters determine many of their measurable properties, so finding
possible isomers and their relative energies is an important issue. The potential energy
surfaces of the ground states of these clusters are fairly flat and there are many local minima
with similar energies. When calculating energies of the isomers, the zero point energy
(vibrations at zero K) is added to the pure electronic energy, therefore all theoretical results in
this paper refer to the temperature of 0 K, and we present clusters with precisely defined
geometrical structures. However, the impact of thermal fluctuations on properties of small
lithium clusters was investigated earlier,84,85 and it was shown that quantum effects at 10 K,
induced by zero-point motion, change the bond lengths for about 5%. Therefore, this motion
is strong enough to completely change internuclear distances, while overall structural shape
of the clusters is preserved. The same was confirmed for thermal fluctuations at 100 K. Yet,
for clusters at higher temperatures (few hundreds K or even thousands as in our experiment),
structural changes are possible. However, it was noted that electronic structure of lithium
clusters is little affected by the changes of bond lengths, because 2s and 2p atomic orbitals
are very diffuse, and their overlaps slightly vary with the distance of nuclei. Hence, we may
View Article Online
DOI: 10.1039/C7CP04181K
13
conclude that at higher temperatures, the properties of clusters can be essentially derived
from the most stable isomers, despite of certain changes in chemical bonds.

The geometries of all isomers of neutral and cationic clusters (LinClm(0,+1), n ≥ m, n =
1-6, m = 1-3) are displayed in Figures 2-7. Conventionally, each structure is denoted by the
label n.m.x.y, in which n and m stand for the number of lithium and chlorine atoms, x denotes
the charge state (n for neutral and c for cation), and y denotes the y-th lowest-lying isomer
obtained for that cluster. Since all structures are generated by a random displacement,
consequently they were treated assuming the C1 point group symmetry. However, further
geometry optimizations lead to the structures that may have higher symmetries, and all
isomers are labeled by their symmetry.
In Figures 2-7 we thus show global and local minima structures on the potential
energy hypersurfaces of the ground electronic states of the titled species. Relative energies of
structural isomers, defined as energies (with ZPVE correction) of relaxed isomers in respect
to the equilibrium geometry of the corresponding lowest energy isomer, are also presented. In
Tables S5 and S6 of the Supporting Information, we show relative energies, zero-point
vibrational frequencies, and low/imaginary frequencies.
Isomers of neutral clusters with one chlorine atom (Fig. 2) are already published by
Senturk41 at the B3LYP/6-311g+(2d,2p) level of theory. Using the same functional and the
chosen cc-pVQZ basis set, we obtained analogues structures. Isomer 2.1.n.2 (linear Li-Li-Cl)
lie about 77 kJ mol–1 above the corresponding global minima structure that is bent. Li3Cl,
Li4Cl and Li5Cl prefer planar geometries. Li6Cl has a 3D compact structure. Isomers 6.1.n.2
and 6.1.n.3 are almost degenerate. When we compare neutral isomers with one Cl atom with
lithium-iodide clusters published earlier,29 it can be concluded that they are very similar:
heteroatoms are always located externally; the change from planar to 3D structures takes
View Article Online
DOI: 10.1039/C7CP04181K
14
place at six atoms (Li6X, X=Cl, I, have 3D compact structures); they have the same number
of low-lying isomers (except Li5Cl has only two isomers and Li5I has four).

Contrary to neutral clusters, in many cationic structures with one chlorine atom, the
chlorine atom occupies an internal position: this is the case of the lowest energy isomers of
Li2Cl+ and Li3Cl+, and in all 3D open structures of other cationic species. We can see that the
compact 4.1.c.1 isomer is similar to 4.1.n.2, and not to the lowest 4.1.n.1. isomer.
In Figs. 4 and 5, where the species with two chlorine atoms are displayed, it is
obvious that cationic species have many 3D open structures also. The number of isomers is
large, i.e. in charged clusters with 6 atoms, the number is 8 in the energy range up to about 60
kJmol–1, and in clusters with 7 atoms the number is 11 in the energy range up to the 75
kJmol–1. Except Li2Cl2 and Li2Cl2+ that have similar structures (but not identical), all other
lowest-energy neutral and corresponding cation clusters do not have similar geometries.
Analogous situation is in the case of Li3Cl3 and Li4Cl3 neutral and cation clusters (Figs. 6 and
7).
Consequently, following ionization, the geometries of the resulting cationic clusters
are significantly distorted as compared to those of their corresponding neutral species, except
for 4.1.n.2→ 4.1.c.1, 2.2.n.1 → 2.2.c.1, 3.2.n.3 → 3.2.c.2, and 5.2.n.4 → 5.2.c.1. It should be
noted that structures that have vibrational modes with frequencies around zero (with a range
of about 50 cm−1 to 50i cm−1) are presented as the structural isomers for two reasons: if these
stationary points are mildly saddle-shaped, they are not very different from a minimum; and
the second, these frequency values are essentially zero within the numerical accuracy of
computations for fairly flat potential energy surfaces. Thus, structures 4.1.n.2, 5.2.n.10,
4.3.n.4, 3.3.c.5, and 4.3.c.3 have low imaginary frequencies of 26i, 18i, 21i, 4i, and 29i cm−1,
respectively. Final conclusion requires additional calculations at higher level of theory.

View Article Online
DOI: 10.1039/C7CP04181K
15

Figure 2. The lowest-lying structural isomers of the neutral LinClm (n = 1-6, m = 1)
clusters. Relative energies (with ZPVE corrections) are calculated at the B3LYP/cc-pVQZ
level.
View Article Online
DOI: 10.1039/C7CP04181K
16

Figure 3. The lowest-lying structural isomers of cationic LinClm+1 (n = 1-6, m = 1)
level.
View Article Online
DOI: 10.1039/C7CP04181K
17

level.
View Article Online
DOI: 10.1039/C7CP04181K
18

Figure 5. The lowest-lying structural isomers of the cationic LinClm+1 (n = 2-5, m = 2)
level.
View Article Online
DOI: 10.1039/C7CP04181K
19

level.
View Article Online
DOI: 10.1039/C7CP04181K
20

Figure 7. The lowest-lying structural isomers of the cationic LinClm+1 (n = 3-4, m = 3)
level.
IV C. GROWTH MECHANISM
View Article Online
DOI: 10.1039/C7CP04181K
21

Figure 8. Schematic depiction of growing of the neutral LinClm clusters up to seven
atoms (the most stable isomers are presented).

View Article Online
DOI: 10.1039/C7CP04181K
22

Figure 9. Schematic depiction of growing of the cationic LinClm+1 clusters up to seven
atoms (the most stable isomers are presented).
Considering only geometrical motifs presented in Figs. 8 and 9, formation of all
neutral and charged clusters LinClm(0,+1) could be described in two directions: first is the
growth of heterogeneous clusters with the addition of one or more atoms (in Figs. 8 and 9 it
corresponds to a vertical direction), and the second is the formation of clusters with exchange
of one or more lithium atoms with chlorine atoms (a horizontal direction). Regarding the first
View Article Online
DOI: 10.1039/C7CP04181K
23
direction (the addition), we notice three possible ways: 1) forming of the LinClm(0,+1) clusters
by adding one lithium atom to the Lin–1Clm(0,+1) sequence, when m is fixed; 2) forming of

LinClm(0,+1) clusters by adding one chlorine atom to the LinClm–1(0,+1) sequence, when n is
fixed; 3) forming of the LinClm(0,+1) clusters by the addition of m chlorine atoms (m is fixed)
to the sequence of pure lithium Lin(0,+1) clusters. On the other hand, formation of clusters by
exchanging lithium atoms with chlorine atoms could occur in two ways: 1) forming
LinClm(0,+1) clusters by the exchange of one Li atom in Lin+1Clm–1(0,+1) with the one Cl atom; 2)
we can look at LinClm(0,+1) clusters as being distorted versions of analogous pure lithium
clusters Lin+m(0,+1), where m lithium atoms are exchanged with m chlorine atoms.
Looking at the Figure 8, it can be concluded that all the most stable isomers LinClm
can be obtained from the most stable Lin+1Clm–1 clusters by the exchange of one Li atom with
the one Cl atom, in this case there is no significant deformation of structure – all planar
structures remain planar (Li3Cl → Li2Cl2; Li4Cl → Li3Cl2; Li5Cl → Li4Cl2 → Li3Cl3); while
3D structures of the clusters with seven atoms are a bit distorted (Li6Cl → Li5Cl2 → Li4Cl3).
The another way of forming, when one Cl atom is being added to the LinClm–1 cluster, can be
perceived when cluster Li2Cl2 is forming from Li2Cl, and Li3Cl3 from Li3Cl2, in that case
there is no considerable changes of the structures. Nevertheless, looking at the sequences
Li2Cl → Li3Cl → Li4Cl → Li5Cl → Li6Cl, Li2Cl2 → Li3Cl2 → Li4Cl2 → Li5Cl2 and Li3Cl3 →
Li4Cl3, we can conclude that the best way to describe the growth of the neutral clusters is by
adding lithium atoms. Transition from planar to the 3D structures takes place in a cluster with
seven atoms.
Concerning cationic lithium-chlorine clusters (Fig 9), the lowest isomers of LinClm+
can be obtained from the lowest isomers of Lin+1Clm–1 by exchanging of one Li atom with the
one Cl atom, but only for clusters with 6 or 7 atoms, when there is no significant deformation
View Article Online
DOI: 10.1039/C7CP04181K
24
of structure (sequence Li5Cl+ → Li4Cl2+ → Li3Cl3+ and Li6Cl+ → Li5Cl2+ → Li4Cl3+). In
clusters with 4 atoms, the exchange of one Li atom in linear 3.1.c.1 with the chlorine atom,

gives the linear isomer 2.2.c.2, which is by 48 kJmol−1 higher that the lowest 2.2.c.1. For
clusters with 5 atoms situation is similar, the exchange of one Li atom in 4.1.c.1 by the
chlorine atom gives the 3.2.c.2 isomer, however energetic distance of this 2nd isomer to the
lowest isomer is considerably smaller (9.2 kJmol−1). The another way of forming, by adding
of one Cl atom to the LinClm–1, lead to significant structural changes from linear Li2Cl+ and
Li3Cl2+ to the planar and 3D Li2Cl2+ and Li3Cl3+, respectively. In sequences Li2Cl2+ → Li3Cl2+
→ Li4Cl2+ → Li5Cl2+ and Li3Cl3+ → Li4Cl3+, we can see that 3D structures occur in clusters
with 6 atoms, however, we can note a small difference in energy between linear 3.2.c.1 and
3D 3.2.c.2 of 9.2 kJmol−1. Similarly to the neutral clusters, the addition of one lithium atom is
the good method for describing the growth of charged clusters, but only for species with at
least 6 atoms.
In conclusion, for neutral species, the good way of describing the formation of
clusters LinClm are all the ways presented in Figure 8: the addition of one lithium or one
chlorine atoms, or exchange of one Li with the Cl in Lin+1Clm–1 for all cluster sizes; in cationic
clusters, this is valid starting from the clusters with 6 atoms.
IV D. STABILITY OF CLUSTERS
In the present subsection, we shall present and discuss stability of the most stable
isomers of lithium-chloride clusters.
IV D.1 Binding energy per atom
The binding energy per atom is explicitly defined as follows (energies E of molecular
species include ZPVE corrections):

View Article Online
DOI: 10.1039/C7CP04181K
25
nE ( Li) + mE (Cl ) − E ( LinClm )

Eb ( LinClm ) =
(n + m)
(n − 1) E ( Li) + E ( Li + ) + mE (Cl ) − E ( LinClm + )
Eb ( LinClm + ) =

( n + m)
Values calculated at two levels of theory, B3LYP/cc-pVQZ and RCCSD(T)/cc-

pwCVTZ// B3LYP/cc-pVQZ are presented in Table 1. The results obtained with two
methods are in good agreement (within less than 0.1 eV). Also, the recently published
theoretical BE value for Li2Cl,42 obtained at the MP2/aug-cc-pVTZ level, is of 1.97 eV, and
again is in accord with our results (1.93 and 1.94 eV).
We can see that binding energies per atom in lithium-chloride clusters with the same
number of Cl atoms decrease with the addition of Li atoms. Exceptions are cations with the
equal number of lithium and chlorine atoms (LinCln+, n = 1-3) that have lower stability than
their neighbors. Even though there is a trend of decreasing stability, some species (LiCl,
Li2Cl2, Li3Cl3, Li2Cl+, Li4Cl+, Li3Cl2+ and Li4Cl3+) have enhanced BE values. All of them
have an even number of electrons, so one can see a slight preference for such systems (the
odd-even alternation).
Furthermore, we notice that exchanging of one lithium atom with the chlorine atom
produces enhancement of stability for all clusters sizes (exceptions are again Li2Cl2+ and
Li3Cl3+).This can be rationalized by the comparison of energies for Li-Li bond (101
kJ/mol86) and Li-Cl bond (467 kJ/mol86). Thus, the largest values of the binding energy have
the neutral LinCln and cationic Lin+1Cln+1 clusters. However, given the energy of the Cl-Cl
bond is of 239 kJ/mol,86 we can conclude that after binding energy reaches the maximum for
LinCln clusters, it would decrease with the further addition of Cl atoms.

View Article Online
DOI: 10.1039/C7CP04181K
26
Table 1. Binding energy per atom (in eV) for the most stable lithium-chloride
clusters.

LinCl1 BE / eV LinCl2 BE / eV LinCl3 BE / eV
LiCl 2.36 a) 2.35 b)

Li2Cl 1.93 a) 1.94 b)
Li3Cl 1.76 a) 1.82 b) Li2Cl2 2.88 a) 2.91 b)
Li4Cl 1.54 a) 1.60 b) Li3Cl2 2.44 a) 2.47 b)
Li5Cl 1.47 a) 1.54 b) Li4Cl2 2.24 a) 2.29 b) Li3Cl3 3.00 a) 3.03 b)
Li6Cl 1.39 a) 1.48 b) Li5Cl2 2.01 a) 2.09 b) Li4Cl3 2.66 a) 2.73 b)
… … …
LiCl+ 0.28 a) 0.26 b)
Li2Cl+ 2.32 a) 2.31 b)
Li3Cl+ 1.92 a) 1.93 b) Li2Cl2+ 1.95 a) 1.89 b)
Li4Cl+ 1.82 a) 1.86 b) Li3Cl2+ 2.66 a) 2.67 b)
Li5Cl+ 1.67 a) 1.70 b) Li4Cl2+ 2.37 a) 2.40 b) Li3Cl3+ 2.37 a) 2.36 b)
… … …
a)
B3LYP/cc-pVQZ,
View Article Online
DOI: 10.1039/C7CP04181K
27
b)
Single point RCCSD(T)/cc-pwCVTZ at B3LYP/cc-pVQZ geometries and ZPVE corrections

However, with only this criterion for the stability of clusters, we cannot successfully
explain the experimentally obtained stability of cations (Section IVA). Our most stable Li2Cl+
and Li3Cl2+ ions have 2.31 and 2.67 eV binding energies per atom, respectively, which is
large. However, the largest value of 2.92 eV (presented in Table 1) has Li4Cl3+ and it is a
medium-stable cluster in our experiment with much lower intensity than e.g. Li4Cl+ ion or
Li6Cl+ ions that have significantly lower binding energies. Further, in the sequence LinCl+,
the binding energy gradually decreases, however after Li2Cl+, we have the highest intensity
for Li6Cl+, then Li4Cl+, and the lowest for Li3Cl+ and Li5Cl+ and that cannot be explained by
the binding energies per atom. The binding energies of the sequences LinCln–1+ and LinCl2+
are also growing in other direction than their intensities.
IV D.2 Dissociation energy
Dissociation energies (De) for the most stable lithium-chloride clusters, calculated at
two levels of theory, B3LYP/cc-pVQZ and RCCSD(T)/cc-pwCVTZ//B3LYP/cc-pVQZ, are
presented in Table 2 for reactions in which the product is the lithium atom or Li+. For all
reactions De has a positive value. De for reactions in which the product is the chlorine atom
have much larger values, e.g., for reaction Li3Cl2 → Li3Cl + Cl, De equals 5.05 eV, or for
reaction Li4Cl3 → Li4Cl2 + Cl De equals 5.35 eV, and thus are not thermodynamically
favored. Previous results for De calculated at the MP2/aug-cc-pVTZ level,42 are: 1.06 eV
(Li2Cl → LiCl + Li), 5.18 eV (Li2Cl → Li2 + Cl) and 6.36 eV (Li2Cl → Li2+ + Cl–); The
value for the first reaction is in very good agreement with the results presented herein.
View Article Online
DOI: 10.1039/C7CP04181K
28
For cationic clusters, two paths for dissociation are presented also in Table 2, the first
is with a neutral Li atom as a product and the second is with Li+ cation. The second path is

thermodynamically favorable only for the Lin+1Cln+ sequence and LiCl+.
Table 2. Dissociation energy (in eV) for the most stable lithium-chloride clusters.
LinCl1 De / eV LinCl2 De / eV LinCl3 De / eV
LinClm = Lin–1Clm + Li
LiCl 4.73 a) 4.71 b)
Li2Cl 1.06 a) 1.10 b)
Li3Cl 1.28 a) 1.49 b) Li2Cl2 /
Li4Cl 0.66 a) 0.69 b) Li3Cl2 0.67 a) 0.72 b)
Li5Cl 1.10 a) 1.28 b) Li4Cl2 1.23 a) 1.39 b) Li3Cl3 /
Li6Cl 0.91 a) 1.06 b) Li5Cl2 0.68 a) 0.86 b) Li4Cl3 0.67 a) 0.91b)
LinClm+ = Lin–1Clm+ + Li
LiCl+ 7.99 a) 7.87 b)
Li2Cl+ 6.40 a) 6.42b)
Li3Cl+ 0.74 a) 0.78 b) Li2Cl2+ /
Li4Cl+ 1.40 a) 1.58 b) Li3Cl2+ 5.49 a) 5.79 b)
Li5Cl+ 0.90 a) 0.93 b) Li4Cl2+ 0.91 a) 1.06 b) Li3Cl3+ /

View Article Online
DOI: 10.1039/C7CP04181K
29
LinClm+ = Lin–1Clm + Li+

LiCl+ 0.55 a) 0.52 b)
Li2Cl+ 2.23 a) 2.23 b)
Li3Cl+ 1.92 a) 1.91 b) Li2Cl2+ /
Li4Cl+ 2.04 a) 2.00 b) Li3Cl2+ 1.79 a) 1.71 b)
Li5Cl+ 2.28 a) 2.25 b) Li4Cl2+ 2.03 a) 2.05 b) Li3Cl3+ /
a)
B3LYP/cc-pVQZ
b)
Single point RCCSD(T)/cc-pwCVTZ at B3LYP/cc-pVQZ geometries and ZPVE corrections.
In our previous experimental study concerning only LinCl+ sequence,39 and in this
study, we obtained that the most prominent species are the Li2Cl+ and Li6Cl+ clusters, then
Li4Cl+, while the Li3Cl+ and Li5Cl+ had the lowest intensities; More general, intensities of the
LinCl+ ions with an even number of lithium atoms (Li2Cl+, Li4Cl+, Li6Cl+) were higher than
those with an odd number of lithium atoms (Li5Cl+, Li3Cl+). As we mentioned before,
regarding species with more than one Cl atom, the most intensive peaks in the spectrum
correspond to Li3Cl2+; the species Li4Cl3+ and Li5Cl4+ were also observed; and for the
sequence with two Cl atoms, LinCl2+, the intensities is much lower but they slightly increase
in the sequence Li4Cl2+ - Li5Cl2+ - Li6Cl2+ - Li7Cl2+.

View Article Online
DOI: 10.1039/C7CP04181K
30
In fact, these experimental findings are in good agreement with theoretical predictions
for dissociation energies. Primarily, the alternation of dissociation energy for clusters with

odd and even number of electrons is noticeable for both neutral and cationic LinClm(0,+1)
species. If we examine dissociation energies of cations (Table 2), we can notice the
following: a) distinctly high energies of dissociation and therefore high stability of Li2Cl+
(6.42 or 2.23 eV), Li3Cl2+ (5.79 or 1.71 eV), and Li4Cl3+ (6.28 or 2.29 eV) (from these results
we still cannot explain the relatively low intensity of Li4Cl3+); b) the lowest energy
correspond to Li3Cl+ (0.78 eV) and Li5Cl+ (0.93 eV), which can explain low intensities of
these species; c) larger values for Li4Cl+ and Li6Cl+ relative to Li3Cl+ and Li5Cl+ (however,
we still cannot explain higher intensity of Li6Cl+ than of Li4Cl+); d) regarding the sequence
LinCl2+ (n = 4-7), Li5Cl2+ is more stable than Li4Cl2+, which can give an explanation of
enhancement of their intensities. Therefore, theoretical results for dissociation energies could
indicate, at least qualitatively, the cluster stability even at high temperatures.
IV D.3 Ionization energy
The adiabatic ionization energy (AIE) is computed as the difference in Eel + ZPVE of
a pair of the relaxed cationic and neutral lowest-energy isomers. The vertical ionization
energy (VIE) is calculated as the total energy difference between the electronic energy of the
cation having the same geometry as the neutral and the neutral cluster (Eel + ZPVE).
The adiabatic (AIE) and vertical (VIE) ionization energies for the most stable
LinClm(0,+1) clusters, obtained at the B3LYP/cc-pVQZ and RCCSD(T)/cc-
pwCVTZ//B3LYP/cc-pVQZ levels, together with experimental values, are presented in Table
3. Additionally, the AIE for clusters that are not significantly distorted upon ionization
(4.1.n.2→ 4.1.c.1, 2.2.n.1 → 2.2.c.1, 3.2.n.3 → 3.2.c.2, and 5.2.n.4 → 5.2.c.1.) are also
presented.
View Article Online
DOI: 10.1039/C7CP04181K
31
In the case of LiCl, AIE values of 9.57 eV [RCCSD(T)] matches the experimental
value obtain by photoionization.87 For Li2Cl2 and Li3Cl3, our RCCSD(T) values differ about

8% from experimental values. Experimental values for LinCl (n = 2-6) were determined by
thermal ionization source.39 As can be seen, theoretical AIE values for Li2Cl, Li4Cl and Li6Cl
are closed to experimental values; while Li3I, and Li5I are not. Comparing MP2/aug-cc-pVTZ
result42 for AIE of Li2Cl (4.20 eV) with our RCCSD(T) value, we can see a good matching.
The general trend is decreasing of ionization energies with the number of Li atoms,
however in the case of Li3Cl, Li5Cl and Li4Cl2, the value of ionization energy is higher due to
higher stability of these clusters. Further, it is noticeable the presence of very high IEs for
clusters with the same number of Li and Cl atoms. The typical odd-even alternation is
evident, i.e. neutrals with closed-shell ground states (Li3Cl, Li5Cl, and Li4Cl2) have higher
IEs than clusters with an odd number of electrons (Li2Cl, Li4Cl, Li6Cl, Li3Cl2, Li5Cl2, and
Li4Cl3), which on the contrary have more stable closed-shell cations. For all LinClm clusters,
except Li6Cl and LiCl molecule, there is a significant structural rearrangement upon
formation of the cations, and as a result the difference between the adiabatic and vertical IEs
is prominent.
It is important to emphasize that all clusters, LinClm(0,+1) with n > m, have lower
(adiabatic) ionization energies than Li atom (5.39 eV) and can be classified as "superalkalis".
Table 3. Computed adiabatic (AIE), vertical (VIE), and experimental ionization
energies (in eV) for lithium-chloride clusters.
LinClm AIE / eV VIE / eV Exp.
LiCl 1.1.n.1 → 1.1.c.1 9.80 a) 9.57 b) 1.1.n.1 1Σ+→ 2Π 9.82 b) 10.01 ± 0.02 c)
View Article Online
DOI: 10.1039/C7CP04181K
32
10.0, 9.57 d)
Li2Cl 2.1.n.1 → 2.1.c.1 4.45 a) 4.25 b) 2.1.n.1 2A1→ 1A1 5.02 b) 3.98 ± 0.25 e)

Li3Cl 3.1.n.1 → 3.1.c.1 4.98 a) 4.96 b) 3.1.n.1 1A1→ 2A1 5.54 b) 4.10 ± 0.25 e)
Li4Cl 4.1.n.1 → 4.1.c.1 4.24 a) 4.07 b) 4.1.n.1 2A'→ 1A' 4.70 b) 3.90 ± 0.25 e)
4.1.n.2 → 4.1.c.1 4.11 a) 3.97 b)
Li5Cl 5.1.n.1 → 5.1.c.1 4.45 a) 4.42 b) 5.1.n.1 1A1→ 2B1 5.05 b) 4.01 ± 0.25 e)
Li6Cl 6.1.n.1 → 6.1.c.1 4.00 a) 3.95 b) 6.1.n.1 2A'→ 1A' 4.02 b) 4.09 ± 0.25 e)
Li2Cl2 2.2.n.1 → 2.2.c.1 9.32 a) 9.47 b) 2.2.n.1 1Ag→ 2B2g 10.59 b) 10.70 c)10.20d)
Li3Cl2 3.2.n.1 → 3.2.c.1 4.50 a) 4.39 b) 3.2.n.1 2A1→ 1A1 5.74 b)
3.2.n.3 → 3.2.c.2 4.19 a) 3.92 b)
Li4Cl2 4.2.n.1 → 4.2.c.1 4.82 a) 4.72 b) 4.2.n.1 1A1→ 2A1 5.77 b)
Li5Cl2 5.2.n.1 → 5.2.c.1 3.95 a) 3.87 b) 5.2.n.1 2A'→ 1A' 4.16 b)
5.2.n.4 → 5.2.c.1 3.83 a) 3.69 b)
Li3Cl3 3.3.n.1 → 3.3.c.1 9.37 a) 9.37 b) 3.3.n.1 1A1'→ 2A1'' 10.93 b) 10.17 d)
Li4Cl3 4.3.n.1 → 4.3.c.1 4.09 a) 4.01 b) 4.3.n.1 2A1→ 1A1 4.84 b)
a)
B3LYP/ cc-pVQZ
View Article Online
DOI: 10.1039/C7CP04181K
33
b)
Single point RCCSD(T)/cc-pwCVTZ at B3LYP/cc-pVQZ geometries and ZPVE corrections.
c)
VIE from Ref.88 d)
AIE from Ref.87 e)
Ref.39

IV D.4 HOMO-LUMO gaps, chemical potential and hardness
The HOMO-LUMO gap can be regarded as a measure of stability: a large gap
suggests a relatively high stability. The chemical potential (µ) is equal to the first derivative
of the energy of a chemical system with respect to the number of electrons, and signifies the
direction of electron transfer from one system to another. Chemical hardness (η) is
proportional to the second derivative of the total energy of a chemical system with respect to
changes in the number of electrons at a fixed nuclear environment. Essentially, chemical
hardness measures the resistance to change in the electron distribution; therefore, larger
stability of chemical system is directly related to the higher values of hardness. Based on the
finite differences approximation and Koopman’s theorem, these quantities are defined as
follows:89
µ = − (VIE + VEA)/2
η = (VIP – VEA)/2,
where VEA is the vertical electron affinity of the corresponding neutral species. HOMO-
LUMO gaps of all closed-shell species, obtained at the B3LYP/cc-pVQZ level of theory,
together with the chemical potential and chemical hardness of all neutrals, obtained at the
B3LYP/aug-cc-pVQZ level, are presented in Table 4. Again, the values of all these quantities
clearly show a very pronounced stability of neutral species with an equal number of Li and Cl
atoms. Also, in the case of cationic species, LinCln−1+ clusters possess very large HOMO-
LUMO gaps. Further, the absolute values of chemical potentials, values of HOMO-LUMO
gap and hardness generally decrease with increasing number of Li atoms in clusters with the
View Article Online
DOI: 10.1039/C7CP04181K
34
same number of Cl atoms. However, values of chemical hardness for closed-shell species
(Li3Cl, Li5Cl and Li4Cl2) are higher than for open-shell clusters.

Table 4. The computed HOMO-LUMO gap (in eV) for closed-shell neutral and cationic
species at the B3LYP/cc-pVQZ level; chemical potential µ (in eV) and chemical hardness η
(in eV) for all neutrals at the B3LYP/aug-cc-pVQZ level.
HOMO – LUMO µ / LinClm HOMO – LUMO

LinClm η / eV
+
Gap / eV eV Gap / eV
LiCl 5.30 –5.37 4.67
Li2Cl –2.94 2.26 Li2Cl+ 7.48
Li3Cl 2.45 –3.01 2.53
Li4Cl –2.81 1.97 Li4Cl+ 2.87
Li5Cl 2.15 –2.78 2.09
Li6Cl –2.44 1.62 Li6Cl+ 2.23
Li2Cl2 6.75 –5.22 4.84
Li3Cl2 –3.32 2.53 Li3Cl2+ 7.08
Li4Cl2 2.73 –3.14 2.64
Li5Cl2 –2.44 1.78 Li5Cl2+ 3.09
Li3Cl3 7.26 –5.17 4.81
Li4Cl3 –2.81 2.11 Li4Cl3+ 7.68
… …
IV E. THE ELECTRONIC STRUCTURE

View Article Online
DOI: 10.1039/C7CP04181K
35
The electronic structure and chemical bonding phenomena of the titled clusters were
analyzed using natural atomic orbitals analysis (NAO) and natural bond orbital analysis

(NBO).90 Natural atomic orbitals are localized 1-center orbitals that can be described as the
effective "natural orbitals of atom" in the molecular environment. The detailed result of NAO
analysis, i.e. the occupation numbers (ON) of valence s and p natural atomic orbitals (we did
not present the very small occupancies of d and f natural orbitals) for all chlorine and lithium
atoms, are presented in Table S7 of Supporting Information, along with natural electron
configurations (NEC) that can be defined as the sum of occupation numbers of valence
orbitals. Further, the results obtained from natural bond orbital (NBO) analysis for the
lowest-energy isomers of neutral species are summarized in Figure 10 (the results for cationic
species are presented in Figure S1 of Supporting Information).
For all clusters with at least one Li atom more than Cl atom [LinClm(0,+1) (n > m)], the
NEC of all chlorine atoms is almost the same and could be idealized as [core]3s23p6, where
[core] represent all non-valence electrons. Because the electronic configuration of the neutral
Cl atom is [core]3s23p5, we can conclude that the chlorine atom is in anionic form (Cl−) both
in neutral and cationic clusters, which is in agreement with obtained substantial negative
NBO charge (Figures 10 and S1). Further conclusion from this analysis is that upon
ionization, an electron is detached from the group of lithium atoms. Thus, generally,
heterogeneous lithium-chloride LinClm(0,+1) (n > m) clusters can be viewed as species
consisted of negative m Cl− ions and positively charged Lin(+1,+2) motifs. This is in accordance
with earlier Schleyer et al.91 description of bonding in LinX (n > 1, X halogen) as electrostatic
interaction between negatively charged X− ion and positively charged lithium “cage”.
Lithium-chloride (LiCl) and its cation (LiCl+) are ionic salts, hence their properties
are different from other species discussed here. In LiCl, there is a negatively charged Cl− and
View Article Online
DOI: 10.1039/C7CP04181K
36
a positively charged Li+ ion; while LiCl+ is an electron deficient species with very small
stability. For clusters with the same number of lithium and chlorine atoms, Li2Cl2(0,+1) and

Li3Cl3(0,+1), one cannot talk about separation to halogen and lithium motifs. These species
could be seen as homogeneous clusters of the (LiCl)n(0,+1) (n = 2, 3) type. As originally
proposed by Misra et. al.,44 the cluster Li3Cl3 can be view as a supersalt made of a superalkali
Li2Cl and a superhalogen LiCl2 connected by ionic interaction. In that sense, LiCl is a
traditional salt and Li2Cl2 is a compound made of a superalkali Li2Cl and a chlorine atom.
In (LiCl)n(0,+1) and Lin+1Xn+ (n = 1, 2, 3) species, all valence electrons are localized at
chlorine atoms, hence bonding in these clusters could be regarded as ionic. In all other
species, there are “excess electrons” on Li atoms [n – m electrons in neutral LinClm, and n – m
– 1 electrons in cationic LinClm+ clusters]. To this respect, clusters LinClm (n ≥ 2, m = 1-3, n >
m) and LinClm+ (n ≥ 3, m = 1-3, n > m+1) could be classified as "hyperlithiated" clusters. This
term was proposed by Schleyer et al.91 Hyperlithiated clusters are those clusters with at least
one excess electron, which originate from lithium atoms, and which isn’t transferred to
halogen atoms – for neutral clusters these conditions are fulfilled when there is at least one Li
atom more than Cl, while for cationic clusters it has to be at least two Li atom more than Cl.
This is the explanation of the prefix “hyper”.
The closed-shell ionic species (for m=1 these are LiCl and Li2Cl+; for m = 2 these are
Li2Cl2 and Li3Cl2+; and for m = 3 these are Li3Cl3 and Li4Cl3+) have the largest binding
energies; while ionic species that are electron deficient (for m = 1 this is LiCl+; for m = 2 this
Li2Cl2+; and for m = 3 this is Li3Cl3+) have the lowest binding energies. Hyperlithiated
clusters have binding energies between the most and the last stable ionic species.
Regarding NBO charge distributions of the most stable isomers of LinClm(0,+1) clusters
(Figures 10 and S1), it can be seen that in all species the chlorine atom has a partial negative
View Article Online
DOI: 10.1039/C7CP04181K
37
charge, with very small decrease of charge with cluster size (from −0.95 to −0.87, hence
close to −1). Exceptions are electron deficient LiCl+ with partial charge that can be round to

zero, and Li2Cl2+ and Li3Cl3+ with partial charges on Cl atoms being approximately −0.5.
Further, in all neutral hyperlithiated clusters, Li atoms which are furthest from the chorine
atom have a small negative charge (except Li2Cl and Li4Cl3 where Li atoms are on the same
distance from Cl), while the inner Li atoms have positive charges. On the other hand, all Li
atoms in cationic and neutral clusters with ionic bonds have partial positive charges.
Figure 10. Charge distribution and the highest occupied NBOs for neutral LinClm clusters.
Considering HOMOs, we can see that for all ionic clusters, HOMOs are mutually very
similar, they are centered on the chlorine atoms, and are denoted as lone pairs (LPs). In
hyperlithiated clusters, the highest occupied NBO are located on the lithium cage, and
View Article Online
DOI: 10.1039/C7CP04181K
38
differences in electronic structures and stability are just the result of differences in these
NBOs. In the closed-shell clusters Li3Cl, Li4Cl2, and Li5Cl2+, HOMO is delocalized over three

lithium atoms in the cage (in Li4Cl2 and Li5Cl2+ one Li atom, between Cl atoms, does not
form a cage), and that is denoted as a 3c/2e NBO. In Li5Cl and Li6Cl+ there are two
degenerate HOMOs that are delocalized over three lithium atoms (two 3c/2e). This type of
NBOs (the 3c/2e bridge-bond, or τ-bond90) is the best known extension of the localized
Lewis-type concept. For cationic Li4Cl+, the HOMO is delocalized between three Li atoms
(3c/2e) (there is no symmetry reason for not being delocalized over all four lithium atoms,
however the used NBO software is limited to three-center bonds). For all open-shell clusters,
Li2Cl, Li4Cl, Li6Cl, Li3Cl2, Li5Cl2, Li3Cl+ and Li5Cl+, the highest energy orbitals are centered
between two lithium atoms, which is denoted as the 2c/1e spin-NBO. Clusters Li4Cl3 and
Li4Cl2+ stand out with three-center bonds with one electron (3c/1e).
In conclusion, the important reason for higher stability of closed-shell over the open-
shell hyperlithiated clusters is the delocalization of electrons over the lithium cage, which is
more energetically favored than the localization of electron between two lithium atoms.
V CONCLUSION
In this work, direct generation of cluster ions of the types LinCl+ (n = 2-6), LinCln–1+ (n
= 3-5), and LinCl2+ (n = 4-7) has been demonstrated by the evaporation of lithium chloride
salt from the Knudsen cell as a chemical reactor, in the temperature range between 1800-
2700 K. The Li4Cl3+, Li5Cl4+, Li4Cl2+, Li5Cl2+, Li6Cl2+, and Li7Cl2+ were detected for the first
time. In current experimental setup, the Li2Cl+ and Li3Cl2+ cluster ions appear to be highly
stable having the highest intensity and longest range of heater’s temperature; Li6Cl+, Li4Cl+,
Li4Cl3+, Li5Cl4+ belong to the group of medium-stable clusters, while clusters Li3Cl+ and
Li5Cl+ to unstable; clusters LinCl2+ have had the lowest intensities. The proposed
View Article Online
DOI: 10.1039/C7CP04181K
39
modification of Knudsen cell presents an effective and simple method for obtaining the non-
stoichiometric clusters.

Based on DFT, CC computations, and NBO analysis, we can make the following
conclusions: a) The number of low-energy isomers is large already at 0 K, and at higher

temperatures, the properties of clusters can be essentially derived from the most stable
isomers, despite of certain changes in chemical bonds. b) Contrary to neutral clusters, in
many cationic structures the chlorine atom(s) occupy internal position; also cationic species
have many 3D open structures. c) Except of Li2Cl2 and Li2Cl2+ that have similar structures
(but not identical), all other lowest-energy neutral and the corresponding cationic clusters do
not have similar geometries; therefore, following ionization, the geometries of the resulting
cationic clusters are significantly distorted as compared to those of their corresponding
neutral species. d) The best description of forming LinClm(0,+1) clusters is by adding one
lithium atom; e) Binding energies per atom for lithium-chlorine clusters are larger in
comparison with the pure lithium clusters; binding energies and chemical hardness decrease
with the addition of Li atoms for the fixed number of Cl atoms; however, due to the fact that
Li-Cl bond has higher bonding energy than Li-Li or Cl-Cl, the stability is maximized for
equal numbers of Li and Cl atoms in neutrals (the same pertains to Lin+1Clm+1 clusters). Still,
taking into account only this criterion for the stability of clusters, we cannot successfully
explain the experimentally obtained stability of ions; f) Intensities and stability of clusters in
our experiments can be described in the best way by analyzing dissociation energies; they can
serve as an indicator of cluster (chemical) stability at high temperatures; g) All LinClm
clusters have lower ionization energies than Li atom and can be classified as "superalkalis";
h) From IE and De values one can see a preference for the systems with an even number of
electrons (closed-shells), i) The chlorine atom is in anionic form (Cl−) both in neutral and
cationic clusters, therefore heterogeneous lithium-chlorine LinClm(0,+1) clusters can be viewed

View Article Online
DOI: 10.1039/C7CP04181K
40
as species consisted of the negative Cl− and positively charged Lin(+1,+2) motifs; j) Upon
ionization, electron is detached from the lithium cage; k) All species can be classified to ionic

and hyperlithiated clusters, the later have ‘excess’ electrons; Hyperlithiated clusters have
binding energies between the most and the last stable ionic species. l) The important reason
for higher stability of closed-shell hyperlithiated clusters is the delocalization of electrons
over the lithium cage.
AUTHOR INFORMATION
Corresponding author
Milan Milovanovic
e-mail: milan.milovanovic@ffh.bg.ac.rs
CONFLICTS OF INTEREST
There are no conflicts of interest to declare
ACKNOWLEDGMENT
This work was supported by the Ministry of Education, Science and Technological
Development of the Republic of Serbia (under projects ON-172040 and ON-172019).
REFERENCES
1 S. N. Khanna and P. Jena, Phys. Rev. B, 1995, 51, 13705–13716.
2 G. L. Gutsev and A. I. Boldyrev, Chem. Phys., 1981, 56, 277–283.
3 G. L. Gutsev, Chem. Phys. Lett., 1982, 92, 262–266.
4 P. v. R. Schleyer, E. U. Wurthwein and J. A. Pople, J. Am. Chem. Soc., 1982, 104,
5839–5841.
5 E. Rehm, A. I. Boldyrev and P. v R. Schleyer, Inorg. Chem., 1992, 31, 4834–4842.
6 V. G. Zakrzewski, W. von Niessen, A. I. Boldyrev and P. von R. Schleyer, Chem.
Phys., 1993, 174, 167–176.

View Article Online
DOI: 10.1039/C7CP04181K
41
7 X.-B. Wang, C.-F. Ding, L.-S. Wang, A. I. Boldyrev and J. Simons, J. Chem. Phys.,
1999, 110, 4763–4771.

8 C. Ashman, S. N. Khanna, M. R. Pederson and J. Kortus, Phys. Rev. B, 2000, 62,
16956–16961.
9 B. K. Rao, P. Jena, S. Burkart, G. Gantefor and G. Seifert, Phys. Rev. Lett., 2001, 86,
692–695.
10 W. Xu, G. Li, G. Yu, Y. Zhao, Q. Li, Y. Xie and H. F. Schaefer III, J. Phys. Chem. A,
2003, 107, 258–266.
11 A. N. Alexandrova and A. I. Boldyrev, J. Phys. Chem. A, 2003, 107, 554–560.
12 K. A. Nguyen and K. Lammertsma, J. Phys. Chem. A, 1998, 102, 1608–1614.
13 T. B. Tai and M. T. Nguyen, Chem. Phys. Lett., 2010, 489, 75–80.
14 T. B. Tai and M. T. Nguyen, Chem. Phys., 2010, 375, 35–45.
15 T. B. Tai, P. V. Nhat, M. T. Nguyen, S. Li and D. A. Dixon, J. Phys. Chem. A, 2011,
115, 7673–7686.
16 S. Bandaru, A. Chakraborty, S. Giri and P. K. Chattaraj, Int. J. Quantum Chem., 2012,
112, 695–702.
17 H. P. Cheng, R. N. Barnett and U. Landman, Phys. Rev. B, 1993, 48, 1820-1824.
18 B. T. Truong, V. N. Pham and M. T. Nguyen, Phys. Chem. Chem. Phys., 2010, 12,
11477–11486.
19 C. Sporea, F. Rabilloud, X. Cosson, A. R. Allouche and M. Aubert-Frécon, J. Phys.
Chem. A, 2006, 110, 6032–6038.
20 D. Hao, J. Liu and J. Yang, J. Phys. Chem. A, 2008, 112, 10113–10119.
21 G. Gopakumar, P. Lievens and M. T. Nguyen, J. Phys. Chem. A, 2007, 111, 4353–
4361.
22 V. T. Ngan, J. De Haeck, H. T. Le, G. Gopakumar, P. Lievens and M. T. Nguyen, J.

View Article Online
DOI: 10.1039/C7CP04181K
42
Phys. Chem. A, 2009, 113, 9080–9091.
23 R. O. Jones, A. I. Lichtenstein and J. Hutter, J. Chem. Phys., 1997, 106, 4566–4574.

24 Y. Yuan and L. Cheng, Int. J. Quantum Chem., 2013, 113, 1264–1271.
25 A. Aguado, A. Ayuela, J. López and J. Alonso, Phys. Rev. B, 1997, 56, 15353–15360.
26 K. Yokoyama, N. Haketa, H. Tanaka, K. Furukawa and H. Kudo, Chem. Phys. Lett.,
2000, 330, 339–346.
27 N. Haketa, K. Yokoyama, H. Tanaka and H. Kudo, J. Mol. Struct. Theochem, 2002,
577, 55–67.
28 J. Đustebek, M. Milovanović, S. Jerosimić, M. Veljković and S. Veličković, Chem.
Phys. Lett., 2013, 556, 380–385.
29 M. Z. Milovanović and S. V. Jerosimić, Int. J. Quantum Chem., 2014, 114, 192–208.
30 J. Tong, Y. Li, D. Wu and Z.-J. Wu, Inorg. Chem., 2012, 51, 6081–6088.
31 J. Tong, Z. Wu, Y. Li and D. Wu, Dalton Trans., 2013, 42, 577–584.
32 J. Tong, Y. Li, D. Wu, Z. R. Li and X. R. Huang, J. Chem. Phys., 2009, 131, 164307–
5.
33 J. Tong, Y. Li, D. Wu, Z. R. Li and X. R. Huang, J. Phys. Chem. A, 2010, 114, 5888–
5893.
34 M. Veljković, O. Nešković, M. Miletić and K. F. Zmbov, Rapid Commun. Mass
Spectrom., 1996, 10, 619–620.
35 O. M. Nesković, M. V Veljković, S. R. Velicković, L. T. Petkovska and A. A. Perić-
Grujić, Rapid Commun. Mass Spectrom., 2003, 17, 212–214.
36 S. Velicković, V. Djordjević, J. Cvetićanin, J. Djustebek, M. Veljković and O.
Nesković, Rapid Commun. Mass Spectrom., 2006, 20, 3151–3153.
37 S. R. Veličković, V. J. Koteski, J. N. Belošević Čavor, V. R. Djordjević, J. M.
Cvetićanin, J. B. Djustebek, M. V. Veljković and O. M. Nešković, Chem. Phys. Lett.,

View Article Online
DOI: 10.1039/C7CP04181K
43
2007, 448, 151–155.
38 J. Đustebek, S. Veličković, S. Jerosimić and M. Veljković, J. Anal. At. Spectrom.,

2011, 26, 1641–1647.
39 S. R. Veličković, J. B. Djustebek, F. M. Veljković, B. B. Radak and M. V Veljković,

Rapid Commun. Mass Spectrom., 2012, 26, 443–448.
40 S. R. Veličković, J. B. Đustebek, F. M. Veljković and M. V Veljković, J. Mass
Spectrom., 2012, 47, 627–631.
41 Ş. Şentürk, Zeitschrift fur Naturforsch. - Sect. A J. Phys. Sci., 2011, 66, 372–376.
42 A. K. Srivastava and N. Misra, Mol. Simul., 2016, 42, 981–985.
43 Y. Li, D. Wu and Z.-R. Li, Inorg. Chem., 2008, 47, 9773–9778.
44 A. K. Srivastava and N. Misra, New J. Chem., 2014, 38, 2890–2893.
45 A. K. Srivastava and N. Misra, Mol. Phys., 2014, 112, 2621–2626.
46 V. Stolyarova, in Materials Chemistry at High Temperatures: Characterization, ed. J.
W. Hastie, Humana Press, Totowa, NJ, 1990, pp. 405–414.
47 M. J. Stickney, M. S. Chandrasekharaiah and K. A. Gingerich, in Materials Chemistry
at High Temperatures: Characterization, ed. J. W. Hastie, Humana Press, Totowa, NJ,
1990, pp. 187–195.
48 L. N. Sidorov, Int. J. Mass Spectrom. Ion Process., 1992, 118–119, 739–754.
49 V. L. Stolyarova and G. A. Semenov, Mass Spectrometric Study of the Vaporization of
Oxide Systems, Wiley, New York, 1994.
50 K. N. Marushkin, G. D. Nipan and V. B. Lazarev, J. Chem. Thermodyn., 1995, 27,
465–474.
51 J. Kapala, D. Kath and K. Hilpert, Metall. Mater. Trans. A, 1996, 27, 2673–2677.
52 A. I. Zaitsev, A. D. Litvina and B. M. Mogutnov, Inorg. Mater., 1997, 33, 1265–1273.
53 O. V. Boltalina, D. B. Ponomarev and L. N. Sidorov, Mass Spectrom. Rev., 1997, 16,

View Article Online
DOI: 10.1039/C7CP04181K
44
333–351.
54 C. Bergman, F. Bennour, R. Chastel, J. Rogez and J. C. Mathieu, Rev. Metall. Cah.

D’Informations Tech., 1998, 95, 1101–1108.
55 A. Popovič, B. Malič and L. Bencze, Rapid Commun. Mass Spectrom., 1999, 13,
1129–1137.
56 J. W. Hastie, D. W. Bonnell and P. K. Schenck, J. Nucl. Mater., 2001, 294, 175–178.
57 M. Miller and K. Armatys, Open Thermodyn. J., 2013, 7, 2–9.
58 C. H. Wu, H. Kudo and H. R. Ihle, J. Chem. Phys., 1979, 70, 1815–1820.
59 H. Kudo, Nature, 1992, 355, 432–434.
60 H. Kudo, M. Hashimoto, K. Yokoyama, C. H. Wu, A. E. Dorigo, F. M. Bickelhaupt
and P. V. R. Schleyer, J. Phys. Chem., 1995, 99, 6477–6482.
61 H. Kudo and K. F. Zmbov, Chem. Phys. Lett., 1991, 187, 77–80.
62 H. Kudo, K. Yokoyama and C. H. Wu, J. Chem. Phys., 1994, 101, 4190–4197.
63 C. H. Wu, Chem. Phys. Lett., 1987, 139, 357–359.
64 M. Saunders, J. Am. Chem. Soc., 1987, 109, 3150–3152.
65 T. B. Tai and M. T. Nguyen, J. Chem. Theory Comput., 2011, 7, 1119–1130.
66 C. Lee, W. Yang and R. G. Parr, Phys. Rev. B, 1988, 37, 785–789.
67 A. D. Becke, J. Chem. Phys., 1993, 98, 5648–5652.
68 R. A. Kendall, T. H. Dunning and R. J. Harrison, J. Chem. Phys., 1992, 96, 6796–
6806.
69 D. E. Woon and T. H. Dunning, J. Chem. Phys., 1993, 98, 1358–1371.
70 P. J. Knowles, C. Hampel and H.-J. Werner, J. Chem. Phys., 1993, 99, 5219–5227.
71 P. Knowles, C. Hampel and H. Werner, J. Chem. Phys., 2000, 112, 3106–3107.
72 J. Watts, J. Gauss and R. Bartlett, J. Chem. Phys., 1993, 98, 8718–8733.
73 K. a. Peterson and T. H. Dunning, J. Chem. Phys., 2002, 117, 10548–10560.

View Article Online
DOI: 10.1039/C7CP04181K
45
74 D. R. Lide, P. Cahill and L. P. Gold, J. Chem. Phys., 1964, 40, 156–159.
75 E. F. Pearson and W. Gordy, Phys. Rev., 1969, 177, 52–58.

76 S. H. Bauer, T. Ino and R. F. Porter, J. Chem. Phys., 1960, 33, 685–691.
77 H. J. Werner, P. J. Knowles, G. Knizia, F. R. Manby, M. Schütz, P. Celani, T. Korona,

R. Lindh, A. Mitrushenkov, G. Rauhut, K. R. Shamasundar, T. B. Adler, R. D. Amos,
A. Bernhardsson, A. Berning, D. L. Cooper, M. J. O. Deegan, A. J. Dobbyn, F. Eckert,
E. Goll, C. Hampel, A. Hesselmann, G. Hetzer, T. Hrenar, G. Jansen, C. Köppl, Y.
Liu, A. W. Lloyd, R. A. Mata, A. J. May, S. J. McNicholas, W. Meyer, M. E. Mura, A.
Nicklass, D. P. O’Neill, P. Palmieri, D. Peng, K. Pflüger, R. Pitzer, M. Reiher, T.
Shiozaki, H. Stoll, A. J. Stone, R. Tarroni, T. Thorsteinsson and M. Wang, MOLPRO,
version 2012.1, a package of ab initio programs, see http://www.molopro.net.
78 R. Lindh, Theor. Chim. Acta, 1993, 85, 423–440.
79 F. Eckert, P. Pulay and H.-J. Werner, J. Comput. Chem., 1997, 18, 1473–1483.
80 G. Rauhut, A. El Azhary, F. Eckert, U. Schumann and H.-J. Werner, Spectrochim.
Acta Part A Mol. Biomol. Spectrosc., 1999, 55, 647–658.
81 A. E. Reed and F. Weinhold, J. Chem. Phys., 1983, 78, 4066–4073.
82 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R.
Cheeseman, J. J. A. Montgomery, T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam,
S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.
A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa,
M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H.
P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E.
Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y.
Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S.
Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K.

View Article Online
DOI: 10.1039/C7CP04181K
46
Raghavachari, J. B. Foresman, J. V Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J.
Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L.

Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M.
Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez and J.

A. Pople, GAUSSIAN 03 (Revision C.01), Gaussian Inc., Wallingford CT, 2004.
83 T. Suzuki, H. Iwabuchi, K. Takahashi, M. Nomura, M. Okamoto and Y. Fujii, Int. J.
Mass Spectrom. Ion Process., 1995, 145, 131–137.
84 R. Rousseau and D. Marx, J. Chem. Phys., 1999, 111, 5091–5101.
85 R. Rousseau and D. Marx, Phys. Rev. Lett., 1998, 80, 2574–2577.
86 K. P. Huber and G. Herzberg, Molecular Spectra and Molecular Structure Constants
of Diatomic Molecules, van Nostrand-Reinhold, New York, 1978.
87 J. Berkowitz, C. H. Batson and G. L. Goodman, J. Chim. Phys., 1980, 77, 631–645.
88 A. W. Potts and E. P. F. Lee, J. Chem. Soc. Faraday Trans. 2 Mol. Chem. Phys., 1979,
75, 941–951.
89 R. G. Pearson, J. Chem. Sci., 2005, 117, 369–377.
90 F. Weinhold and C. R. Landis, Valency and Bonding: A Natural Bond Orbital Donor-
Acceptor Perspective, Cambridge University Press, Cambridge, 2005.
91 P. V. R. Schleyer, New Horizon of Quantum Chemistry, Reidel, Dordrecht, 1983.

Milovanovic 2017

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Milovanovic 2017

Uploaded by

Copyright:

Available Formats

View Article Online

acceptance, before technical editing, formatting and proof reading.

You can find more information about Accepted Manuscripts in the

Please note that technical editing may introduce minor changes

Structure and Stability of Small Lithium-Chloride

Physical Chemistry Chemical Physics Accepted Manuscript

PAC 105305, 11158 Belgrade, Republic of Serbia

Belgrade, Republic of Serbia

KEYWORDS. lithium-chloride clusters; mass spectrometry; cluster stability; charge

distribution; electronic structure calculations; B3LYP; RCCSD(T).

stability, although there is a typical closed-shell – open-shell alternation in stability.

detected clusters. Heterogeneous lithium-chloride clusters can be viewed as species consisted

Physical Chemistry Chemical Physics Accepted Manuscript

the titled clusters can be classified as “superalkalis”.

blocks for new materials, with tailored properties.1

lithium clusters,12–16 aluminium doped lithium clusters,17,18 mixed silicon-lithium clusters,19,20

measurements.28,34–40 Neutral LinCl (n = 1-7) species were also theoretically investigated.41

Physical Chemistry Chemical Physics Accepted Manuscript

M2X would be the smallest clusters possessing such exceptional properties.

An important use of superalkalis and superhalogens, as building blocks for novel

superatom fragments, (superalkalis and superhalogens), which distinguish them from

superalkalis (Li2X) and superhalogens (LiX2).

Formation of charged clusters was investigated in series of experiments by Knudsen

small heterogeneous lithium clusters of different types LinX and LinXn–1 (X –

Physical Chemistry Chemical Physics Accepted Manuscript

clusters, LinClm(0,+1) (n ≥ m, n = 1-6, m = 1-3). Although some information about these

(DFT) optimizations; further, stability of these clusters will be discussed by investigating

our present conclusions.

Physical Chemistry Chemical Physics Accepted Manuscript

pressures in the ion sources region were approximately 10–7 mbar.

In the standard experimental conditions, the temperature of cell is uniform throughout

The maximum temperature of heater was 2700 K.

Physical Chemistry Chemical Physics Accepted Manuscript

III COMPUTATIONAL METHODS

The structures of low-lying isomers of clusters were obtained by using a random-kick

using B3LYP functional66,67 in the cc-pVDZ68,69 basis set.

correlation-consistent polarized valence quadruple-zeta basis set cc-pVQZ.68,69 Zero-point

vibrational energy (ZPVE) corrections were found by computing harmonic vibrational

frequencies at the same level of theory.

quadruple-zeta [(aug-)cc-pVQZ] basis sets68,69 at the B3LYP, RCCSD, and RCCSD(T)levels.

restricted Hartree-Fock wave function as a reference.70,71 RCCSD(T) abbreviates the same

Physical Chemistry Chemical Physics Accepted Manuscript

In Supporting Information (Table S1), we show equilibrium bond distances of LiCl

compared with time-consuming ab initio RCCSD(T)/aug-cc-pwCVQZ method, the

(Ref75) is quite good predicted with B3LYP/cc-pVQZ (641 cm–1).

Additionally, also in Supporting Information, in Tables S2 and S3, we present

Physical Chemistry Chemical Physics Accepted Manuscript

species, single-point RCCSD(T)/cc-pwCVTZ calculations were performed at the B3LYP-

software81 implemented in Gaussian03.82

IV RESULTS AND DISCUSSION

Physical Chemistry Chemical Physics Accepted Manuscript

a very difficult task.

Physical Chemistry Chemical Physics Accepted Manuscript

Figure 1. The mass spectrum of positive LinCln–1+ (n = 3, 4 and 5) and LinCl2+ (n = 4, 5, 6,

Physical Chemistry Chemical Physics Accepted Manuscript

obtained in previous study,39 it is not presented. However, in Supporting Information (Table

temperature of the heater.

Physical Chemistry Chemical Physics Accepted Manuscript

According to the presented results, the proposed modification of Knudsen cell

predominant ion emission mechanism cannot be experimentally determined by apparatus

strategy for the preparation of lithium chloride clusters.

The structures of clusters determine many of their measurable properties, so finding

geometrical structures. However, the impact of thermal fluctuations on properties of small