Journal of Molecular Structure: THEOCHEM 910 (2009) 50–55

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Journal of Molecular Structure: THEOCHEM

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

Theoretical study on the structures and properties of LiCn, LiCn þ ,

and LiCn  (n = 1–10) clusters
Guoliang Li a,*, Xiaohong Li b, Chaoyang Wang a, Guozheng Ma a
a
Center for Computational Quantum Chemistry, School of Chemistry and Environment, South China Normal University, Guangzhou, Guangdong 510006, China
b
Shandong Shengda Technology Co., LTD. Tai’an, Shandong 271000, China

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

Article history: The lithium-doped carbon clusters LiCn, LiCn þ , and LiCn  (n = 1–10) have been investigated systemically
Received 10 May 2009 with density functional theory (DFT) method at the B3LYP/6-311+G level. According to the total energies
Received in revised form 12 June 2009 of different kinds of isomers, the LiCn, LiCn þ , and LiCn  (n = 1–10) clusters have Li-terminated linear
Accepted 12 June 2009
ground states structures, except for LiC2, LiC3, LiC2  , and LiCn  (n = 4–6). The incremental binding ener-
Available online 21 June 2009
gies are evaluated to elucidate the stabilities of the clusters with different numbers of carbon atoms for
neutral molecules, cations, and anions, respectively. Clear even–odd alternation effects are observed for
Keywords:
the stability of the cationic LiCn þ clusters and anionic LiCn  clusters, while for neutral LiCn clusters the
Density functional theory
Lithium-doped carbon cluster
alternation effect is less pronounced. Similarly, the ionization potentials and electron affinities of LiCn
Structure also express an obvious parity alternation. In addition, the most favorable dissociation channels are
Stability acquired according to the fragmentation energies accompanying various pathways.
Ó 2009 Elsevier B.V. All rights reserved.

1. Introduction
Since the binary compounds corresponding to the formula
XCn were detected in interstellar medium in last decades [1–
7], heteroatom-doped carbon clusters containing a first- [8–
11], second- [12–25], third-row [19,26–43], or other heavy ele-
ment [19,44–47] of the periodic table have been extensively
studied to reveal their structures, spectra and other properties.
Studies on heteroatom-doped carbon clusters can also help us
to understand their stabilities, reveal their formation mecha-
nism, guide their application and synthesize new clusters. For
most of the heteroatom-doped small carbon clusters, the ground
states were reported to be in heteroatom-terminated linear or
quasi-linear forms, with the heteroatom-containing monocyclic
structures being competitive. For the carbon clusters doped by
a same heteroatom, the increased number of carbon atoms usu-
ally resulted in an even–odd (or odd–even) alternation effect in
their stability.
Lithium is the lightest metallic element. How can the lithium
atom affect the stability of small carbon clusters? Researches on
the LiCn clusters are very limited [48] except numerous work
on the smaller members LiC [48–53] and LiC2 [48,54–56]. In the
present work, we systematically study the LiCn, LiCn þ , and LiCn 
(n = 1–10) clusters in their energetically low-lying structures,
i.e., the Li-terminated linear configurations and the Li-containing
* Corresponding author. Tel.: +86 20 39310255; fax: +86 20 39310187.
E-mail address: glli@scnu.edu.cn (G. Li).
monocyclic ones. For each structure, two electronic states with
different multiplicities, i.e. the doublet and quartet states for neu-
tral LiCn and the singlet and triplet states for ionic LiCn  /LiCn þ , are
considered. Based on the total energies of different kinds of iso-
mers, the ground states were determined. Their stabilities, ioniza-
tion potentials, electron affinities and dissociation channels are
discussed.
2. Theoretical methods
All calculations were carried out with Gaussian 03 program
suites [57]. The theoretical approach employed herein was the
same as that in our previous works [12,19,38,46,47]. Briefly, the
LiCn /LiCn þ /LiCn  (n = 1–10) clusters were examined using density
functional theory (DFT) method at the B3LYP/6-311+G level of
theory, where B3LYP was formed from Becke’s three-parameter ex-
change functional [58] along with the Lee, Yang, and Parr correla-
tion functional [59]. As is known, the DFT-B3LYP method has been
successfully applied to many medium-sized heteroatom-doped
carbon clusters. The 6-311G specifies the standard split-valence
triple-f basis sets for C and Li atoms [60]. Since the inclusion of
both cations and anions in this study, the 6-311G basis sets were
augmented with d-polarization functions and diffuse sp-functions.
Harmonic vibrational frequencies were computed with the analytic
gradient techniques to estimate the nature of the stationary points.
The default integration grid (75, 302) of Gaussian 03 was mainly
applied, but the finer grid (99, 590) was also used to check some
suspicious results when necessary.

0166-1280/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.theochem.2009.06.014
 G. Li et al. / Journal of Molecular Structure: THEOCHEM 910 (2009) 50–55 51

3. Results and discussion linear LiCn clusters are all 2P states except for LiC and LiC2. For all
the linear neutral isomers, the electronic states can be deduced as
3.1. Structures and electronic states the following. When the core 1s2 electrons for lithium and carbon
atoms are excluded, linear LiCn have 4n + 1 valence electrons. The
All the optimized bond lengths and the electronic states for the electronic configurations are
ground states of LiCn /LiCn þ /LiCn  (n = 1–10) clusters are given in ( nþ1
ðcoreÞ1r2 1p4 ðn þ 1Þr2 p1 n-odd members
Fig. 1. The electronic states, the total energies and the numbers LiCn :  2
2 4 2 n 3
of imaginary vibrational frequencies for all the lowest-lying linear ðcoreÞ1r 1p ðn þ 1Þrp n-even members 2
and cyclic states are listed in Table 1. As shown in Fig. 1 and Table ðexcept for LiC : ðcoreÞ1r 2r 1p and LiC2 : ðcoreÞ1r2 2r2 3r1 1p4 Þ
2 1 2

1, the optimized neutral LiC has a 4R ground state with an equi-
librium Li–C bond length of 1.881 Å. For the rest neutral clusters
with the number of the carbon atoms from 2 to 10, the ground
states were predicted to be in cyclic form for LiCn (n = 2–3) and
in linear form for n = 4–10. For LiC2, the lowest-lying linear struc-
ture is a saddle point with two degenerate imaginary vibrational
frequencies (184i cm1). Following the normal mode of the imagi-
nary vibrational frequencies leads to the corresponding cyclic
state. On the contrary, the lowest-lying cyclic structure of LiC6 is
a saddle point, and the normal mode of its imaginary vibrational
frequency leads to a linear form. With 6-311+G basis sets, LiC10
in its lowest-energy state has two imaginary vibrational
frequencies. It has been noted that the 6-311+G basis sets become
over-complete for some carbon chain systems because of the large
overlap between the diffuse function [10,12,19,38,46,47]. With 6-
311G basis sets, in which diffuse sp-functions are excluded, the
lowest-energy state of LiC10 has no imaginary vibrational fre-
quency, indicating a genuine minimum. This is also the case for
cationic LiC9 þ , LiC10 þ and anionic LiC10  . In the lowest-energy lin-
ear structures, the Li–C bond distance is rather similar for all LiCn
clusters, in the range of 1.881–1.912 Å, with that in LiC being the
shortest and in LiC10 the longest. The C–C bond distances are with-
in the range of 1.243–1.335 Å, being typical of cumulene structures
with moderately strong double bonds. On the other hand, the clear
alternation in C–C distances suggests that there is a substantial
contribution of polyacetylenic valence-bond structures with alter-
nating triple and single C–C bonds. The electronic ground states of
There are 2n + 2 valence r-electrons and 2n  1 valence p-elec-
trons. After the 2n + 2 valence r-electrons fully occupy n + 1 r-
orbitals, one (for n-odd species) or three (for n-even species) of
the 2n  1 p-electrons are distributed over a pair of p-orbitals, cor-
responding to p1 or p3 distributions. Both of them will result in the
2
P electronic states.
In a recent article, Patrick et al. reported their theoretical stud-
ies of lithiated carbon clusters CxLiy (x = 1–3, y = 1–5) at the
B3PW91/6-311G level [48]. Therefore, the LiCn (n = 1–3) species
are also reported in that paper. To make a comparison between
our results and those given by Patrick et al., the electronic states,
equilibrium bond lengths (Re), vibrational frequencies (xe), disso-
ciation energies (De), ionization potentials (IP), electron affinities
(EA) and dipole moments (D) for the ground states of LiCn (n = 1–
3) are listed in Table 2. Obviously, the agreement is excellent. For
linear LiC2, Patrick et al. [48] predicted a 2P ground state. Although
our calculations found the 2R state has lowest energy for linear
LiC2, this state is a saddle point. Above the 2R state at +4.8 kcal/
mol we found the 2P state. This is in agreement with the result
of Patrick et al. that the 2P state lies 0.69 eV above the ground
2
A1 state.
Our results for the predicted ground states of LiCn are basically
in agreement with those of Redondo et al. for the NaCn clusters
[13], except for NaC3, in which a linear 2P ground state was found,
with the monocyclic 2B2 state being almost isoenergetic at the
B3LYP/6-311+G level. According to our calculations, LiC3 has a

1.881 2.300 2.113 1.288 1.998 171.6 1.309

LiC (C∞v, 4Σ−)
1.940 1.294
LiC+ (C∞v, 3Π) LiC2+ (C∞v, 3Π) LiC- (C∞v, 3Σ −) LiC3- (Cs , 3Α")
2.024 1.968 1.352
1.261 2.097 1.315 1.393
1.516 1.253
1.263 1.931
LiC2 (C2v, 2Α1) LiC3 (C2v, 2Α1) LiC3+ (C∞v, 1Σ +) 1.266
2.265 1.975
1.907 1.327 2.055 1.289
LiC2- (C2v, 1Α1) LiC4- (C2v, 1Α1)
1.255 1.281 1.284 1.325
LiC4 (C∞v, 2Π) LiC4+ (C∞v, 3Σ −)
1.373

1.240
1.255

1.352

1.378
1.255

1.907 1.311 1.297 2.039 1.303 1.306

1.266
1.256 1.279 1.254 1.263
LiC5 (C∞v, 2Π) LiC5+ (C∞v, 1Σ +) 2.272 2.159 2.537
1.910 1.328 1.314 2.020 1.295 1.281
2.055 2.441 1.949 2.099
1.248 1.247 1.281 1.269 1.273 1.314
LiC6 (C∞v, 2Π) LiC6+ (C∞v, 3Σ −) LiC5- (C2v, 1Α1) LiC6- (Cs, 1Α')
1.910 1.323 1.290 1.290 2.010 1.310 1.289 1.302 1.843 1.317 1.278 1.275
1.249 1.257 1.287 1.251 1.252 1.269 1.267 1.281 1.318
LiC7 (C∞v, 2Π) LiC7+ (C∞v, 1Σ +) LiC7- (C∞v, 3Σ −)
1.911 1.332 1.313 1.310 2.001 1.303 1.281 1.280 1.854 1.350 1.337 1.340
1.245 1.242 1.252 1.280 1.261 1.265 1.275 1.309 1.244 1.235 1.239 1.258
LiC8 (C∞v, 2Π) LiC8+ (C∞v, 3Σ −) LiC8- (C∞v, 1Σ +)
1.911 1.329 1.303 1.282 1.287 1.993 1.315 1.296 1.285 1.300 1.853 1.327 1.293 1.268 1.272
1.245 1.247 1.265 1.290 1.249 1.249 1.258 1.273 1.257 1.265 1.291 1.320
LiC9 (C∞v, 2Π) LiC9+ (C∞v, 1Σ +) LiC9- (C∞v, 3Σ −)
1.912 1.335 1.317 1.307 1.308 1.987 1.308 1.286 1.277 1.280 1.861 1.349 1.357 1.330 1.335
1.243 1.239 1.248 1.254 1.280 1.257 1.260 1.271 1.276 1.305 1.243 1.234 1.238 1.241 1.260
LiC10 (C∞v, 2Π) LiC10+ (C∞v, 3Σ−) LiC10- (C∞v, 1Σ +)

Fig. 1. Optimized geometries (in Å and degrees) for the ground states of the LiCn/LiCn þ /LiCn  clusters.
52 G. Li et al. / Journal of Molecular Structure: THEOCHEM 910 (2009) 50–55

Table 1
Total energies (Etot, in Hartrees), numbers of imaginary vibrational frequencies (Nimag, given in parentheses) and relative energies (Erel, in kcal/mol) for the lowest-lying linear
(structure na) and cyclic (structure nb) states of the LiCn ðÞ clusters at the B3LYP level with the 6-311+G basis sets. The relative energies do not include the zero-point vibrational
energies.

Cluster structure Neutral Cation Anion

State Etot (Nimag) Erel State Etot (Nimag) Erel State Etot (Nimag) Erel
LiC(±) 1a 4
R (C1v) 45.44285 (0) 0.0 3
P (C1v) 45.15996 (0) 0.0 3
R (C1v) 45.46648 (0) 0.0
2 
LiC2 ðÞ 2a R (C1v) 83.58121 (2)a 8.9 3
P (C1v) 83.25481 (0) 0.0 1 +
R (C1v) 83.64208 (0) 11.6
2 3
2b A1 (C2v) 83.59532 (0) 0.0 B1 (C2v) 83.24820 (1)b 4.1 1
A1 (C2v) 83.66052 (0) 0.0
2 1
LiC3 ðÞ 3a P (C1v) 121.66893 (0) 0.6 R+ (C1v) 121.40528 (0) 0.0 3
A00 (Cs) 121.70935 (0) 0.0
2 1
3b A1 (C2v) 121.66984 (0) 0.0 A1 (C2v) 121.37548 (1)b 18.7 3
B1 (C2v) 121.70823 (0) 0.7
2 3  1 +
LiC4 ðÞ 4a P (C1v) 159.77225 (0) 0.0 R (C1v) 159.47056 (0) 0.0 R (C1v) 159.85551 (0) 11.5
2 3
4b A2 (C2v) 159.76116 (0) 7.0 B1 (C2v) 159.42082 (1)b 31.2 1
A1 (C2v) 159.87384 (0) 0.0
2 1 + 3
LiC5 ðÞ 5a P (C1v) 197.85914 (0) 0.0 R (C1v) 197.59947 (0) 0.0 A (C1) 197.91754 (0) 8.4
2 1
5b A1 (C2v) 197.84026 (0) 11.8 A1 (C2v) 197.53653 (1)b 39.5 1
A1 (C2v) 197.93092 (0) 0.0
2 3  1 +
LiC6 ðÞ 6a P (C1v) 235.95659 (0) 0.0 R (C1v) 235.66971 (0) 0.0 R (C1v) 236.05559 (0) 1.6
2
6b B1 (C2v) 235.92221 (1)b 21.6 3
B1 (C2v) 235.59385 (1)b 47.6 1 0
A (Cs) 236.05806 (0) 0.0
2 1 + 3 
LiC7 ðÞ 7a P (C1v) 274.04321 (0) 0.0 R (C1v) 273.78759 (0) 0.0 R (C1v) 274.11947 (0) 0.0
2 1 1
7b A2 (C2v) 274.00385 (0) 24.7 A1 (C2v) 273.72999 (0) 36.1 A1 (C2v) 274.11585 (0) 2.3
2 3  1 +
LiC8 ðÞ 8a P (C1v) 312.13850 (0) 0.0 R (C1v) 311.86183 (0) 0.0 R (C1v) 312.24927 (0) 0.0
2 0 3 00 1
8b A (Cs) 312.09242 (0) 28.9 A (Cs) 311.79059 (0) 45.3 A1 (C2v) 312.22473 (0) 15.4
2 1 +
LiC9 ðÞ 9a P (C1v) 350.22532 (0) 0.0 R (C1v) 349.97326 (2)c 0.0 3 
R (C1v) 350.31645 (0) 0.0
2 1 1
9b B1 (C2v) 350.19158 (0) 21.2 A1 (C2v) 349.91522 (0) 36.4 A1 (C2v) 350.30462 (0) 7.4
2
LiC10 ðÞ 10a P (C1v) 388.31937 (2)c 0.0 3 
R (C1v) 388.05023 (2)c 0.0 1 +
R (C1v) 388.43928 (2)c 0.0
2 0 3 00 1
10b A (Cs) 388.28488 (0) 21.6 A (Cs) 387.99091 (0) 37.2 A1 (C2v) 388.41825 (0) 13.2
a
Further calculations following the normal mode of the imaginary vibrational frequency lead to the corresponding cyclic structure.
b
Further calculations following the normal mode of the imaginary vibrational frequency lead to the corresponding linear structure.
c
It has been noted that the 6-311+G* basis sets become over-complete for some carbon chain systems because of the large overlap between the diffuse functions. When we
re-investigate these systems using 6-311G* basis sets (in which diffuse sp-functions are excluded) for carbon atoms, they all have no imaginary vibrational frequency,
indicating that they should be minima.

Table 2
Comparison between our results (first line) and those given by Patrick et al. [48] (second line) for the ground states of LiC, LiC2 and LiC3 clusters.

Cluster State Re (Å) xe (cm1) De (eV) IP (eV) EA (eV) D (Debye)

4 
LiC R (C1v) 1.881 689 2.56 7.70 0.64 6.22
4
R (C1v) 1.884 693 2.67 7.77 0.52 6.12
2
LiC2 A1 (C2v) 2.024; 1.261 284; 613; 1850 9.27 1.77 6.10
2
A1 (C2v) 2.02; 1.26 288; 617; 1853 9.19 1.63 6.05
2
LiC3 A1 (C2v) 1.968; 1.516; 1.352 261; 371; 624; 859; 1185; 1624 7.20 1.08 5.81
2
A1 (C2v) 1.97; 1.51; 1.35 262; 377; 626; 887; 1209; 1631 9.06 0.44 5.71

bicyclic 2A1 ground state with the linear 2P state and the monocy-
clic 2B2 state being energetically 0.6 and 1.4 kcal/mol higher,
respectively.
Removing an electron from neutral LiCn gives the cationic LiCn þ
clusters, all of which are most stable in their linear configurations,
as shown in Fig. 1. Similarly, Redondo et al. also predicted linear
ground states for all cationic NaCn þ (n = 1–8) clusters [13]. All
the lowest-lying states of cyclic LiCn þ (n = 2–6) collapse to the cor-
responding linear structure by following the normal mode of their
imaginary vibrational frequencies. Alternate electronic states of
1 +
R (for n-odd clusters) and 3R (for n-even clusters) are gained
for linear LiCn þ (n = 3–10) as indicated by their electronic
distributions
( lowest-energy structures with the lithium atom side-bonded to en-
ðcoreÞ1r2 1p4 ðn1
2
Þp4 ðn þ 1Þr2 n-odd members
LiCn þ :
ðcoreÞ1r2 1p4 ðn þ 1Þr2 ðn2Þp2 n-even members
þ þ
ðexcept for LiC : ðcoreÞ1r2 2r1 1p1 and LiC2 : ðcoreÞ1r2 2r2 1p3 3r1 Þ
There are 2n + 2 valence r-electrons and 2n  2 valence p-elec-
trons. The 2n + 2 valence r-electrons fully occupy n + 1 r-orbitals.
For the species with odd n, the 2n  2 p-electrons constitute a
closed shell and result in a 1R+ electronic state. For the clusters with
even n, however, two of the 2n  2 p-electrons are distributed over
a pair of degenerate p-orbitals, corresponding to a half-filled p-
orbital open-shell and a 3R lowest-energy state. Our results that
LiC+, LiC2 þ and LiC3 þ have 3P, 3P and 1R+ ground electronic states,
respective, are in agreement with those of Patrick et al. [48] by
B3PW91/6-311G method.
Attaching an electron to neutral LiCn gives anionic LiCn  clus-
ters. As exhibited in Fig. 1, LiC has an optimized predicted bond
length of 1.998 Å, which is 0.117 Å longer than that of neutral
LiC. LiC2  has a Li-contained triangle ground state structure in
C2v symmetry. For LiC3  , the Li-terminated quasi-linear structure
and the Li-contained four- membered ring structure have similar
energies, with the former being only 0.7 kcal/mol more stable. In
the quasi-linear structure, the Li–C–C bond angle is 171.6°. Our
predicted ground states for LiC, LiC2  and LiC3  are in good agree-
ment with those of Redondo et al. for NaC, NaC2  and NaC3  [13].
When the carbon atom number n = 4–6, LiCn  all have the fan-like
tire (for LiC4  and LiC5  ) or half (for LiC6  ) carbon chain. This is
somewhat different from the NaCn  clusters, in which monocyclic
structures are predicted to the ground state structures for the
NaC4  , NaC5  and NaC6  clusters, just as shown by Redondo
et al. [13]. As seen in Table 1, the linear LiC2  , LiC4  , LiC5  , and
LiC6  are energetically higher than the corresponding fan-like iso-
mers by 11.6, 11.6, 8.4, and 1.6 kcal/mol, respectively. The
LiCn  clusters containing 7–10 carbon atoms have their energeti-
cally lowest-lying states in Li-terminated linear conformations.
This is in good agreement with the statement of Redondo et al. that
for larger NaCn  clusters open-chain isomers could be the pre-
ferred ones [13]. Like those in other linear clusters, the imaginary
 G. Li et al. / Journal of Molecular Structure: THEOCHEM 910 (2009) 50–55 53

vibrational frequencies for linear LiC10  also disappear as the 6- 220

Linear LiCn
311G basis sets instead of the 6-311+G basis sets are employed.
+
Opposite to cationic LiCn þ , the electronic states of the lowest-lying LiCn
200
linear anionic LiCn  are 3R for n-odd clusters and 1R+ for n-even -
LiCn
clusters, which are also consistent with the deduction of their elec-
tronic arrangement as followed 180

ΔΕ (kcal/mol)
(  
2 4 2 nþ1 2
ðcoreÞ1r    1p    ðn þ 1Þr 2
p n-odd members
LiCn  :  
ðcoreÞ1r2    1p4    ðn þ 1Þr 2 n
2
4
p n-even members 160

Ι
Anionic LiCn  clusters have 2n + 2 valence r-electrons and 2n va-
140
lence p-electrons. After the 2n + 2 valence r-electrons fully occupy
n + 1 r-orbitals, two (for n-odd species) or four (for n-even species)
of the 2n valence p-electrons are distributed over a pair of p-orbi- 120
tals, corresponding to 3R or 1R+ states for n-odd or n-even LiCn  ,
220
respectively. Cyclic LiCn
Our predicted ground states are in agreement with those of Pat- +
LiCn
rick et al. [48] for LiC and LiC2  , but not for LiC3  , since these 200 -
authors report a 3R+ ground state for LiC3  . According to our calcu- LiCn
lations, the ground state structure of LiC3  is in quasi-linear form
180
and the electronic state is 3A00 (as shown in Fig. 1), which is ener-

ΔΕ (kcal/mol)
getically 5.5 kcal/mol more stable the 3R state in linear form.
160
3.2. Stabilities
Ι

For the clusters with different sizes, the concept of incremental 140
binding energy [18,20–22,61], labeled as DEI, is introduced to com-
pare their relative stabilities. As suggested by Pascoli and Lavendy,
120
DEI is defined as the consecutive binding energy difference be-
tween adjacent LiCn /LiCn þ /LiCn  and LiCn1/LiCn1 þ /LiCn1  clus- 220
Ground States LiCn
ters, and can be determined by the reaction energies of +
LiCn
200
LiCn ! LiCn1 þ C ðDN1Þ -
LiCn
LiCn þ ! LiCn1 þ þ C ðDC1Þ
LiCn  ! LiCn1  þ C ðDA1Þ 180
ΔΕ (kcal/mol)

The incremental binding energies against the carbon atom numbers

160
of LiCn/LiCn þ /LiCn  are displayed in Fig. 2 for the lowest-lying linear
Ι

states, the lowest-lying cyclic states, and the ground states. For
linear isomers, we can observe a strong odd–even (even–odd) alter- 140
nation in their stabilities for ionic LiCn þ and LiCn  clusters, with the
n-odd members being more stable than the adjacent n-even ones
for cationic LiCn þ and oppositely the n-even members being more 120
stable than the adjacent n-odd ones for anionic LiCn  . This can be
n
explained by the ‘‘valence p-electrons number” rule [12]. As already 2 4 6 8 10

ascertained above, linear LiCn þ cluster contains 2n  2 valence LiCn/LiC+n/LiC-n

p-electrons. For odd n, these 2n  2 p-electrons fully populate
(n  1)/2 doubly degenerate p-orbitals, resulting in a   p4 elec-
tronic configuration and a 1R+ state, while for even n, the highest
occupied molecular orbital (HOMO) with p-symmetry is half-filled
with two electrons, resulting in a   p2 electronic configuration
and a 3R state. Clearly, the former situation (fully filled p-orbitals)
is energetically much more stable than the latter one (half-filled
p-orbital). For linear LiCn  clusters, the situation is just the opposite.
Two more p-electrons result in fully filled p-orbitals in n-even LiCn 
clusters and a half-filled p-orbital in n-odd LiCn  clusters, making
the former being more stable than the latter. For linear neutral LiCn
isomers, the even–odd alternation in their stabilities is less pro-
nounced because they all have 2P electronic states. The cyclic LiCn
/LiCn þ /LiCn  clusters essentially follow the same parity alternation
pattern as their linear isomers, only the amplitude of the alternation
being somewhat different. Additionally, since most ground states of
the LiCn /LiCn þ /LiCn  clusters have linear structures or have their
energies closer to the lowest-lying linear states, the even–odd alter-
nations in stability for the ground states of the Li-doped clusters are
also very similar to those for the lowest-lying linear states.
Fig. 2. Incremental binding energies for LiCn/LiCn þ /LiCn  in linear, cyclic, and
ground state structures vs the number of carbon atoms, respectively.
3.3. Ionization potentials and electron affinities
The ionization potentials (IP) and electron affinities (EA) of the
LiCn clusters are calculated in adiabatic form according to the total
energies for the ground states of LiCn, LiCn þ , and LiCn  . The adia-
batic IP and EA are determined by,
IP ¼ Eðoptimized cationÞ  Eðoptimized neutralÞ;
EA ¼ Eðoptimized neutralÞ  Eðoptimized anionÞ:
As shown in Fig. 3, both IPs and EAs have an obvious even–odd
alternation with n-even members having higher IP/EA values. This
is consistent with the stabilities of LiCn/LiCn þ /LiCn  as indicated in
Fig. 2. In detail, neutral LiCn express a smooth even–odd alternation
in their ground states, while n-odd cationic LiCn þ have much higher
stabilities than adjacent n-even LiCn þ , both of them result in higher
54 G. Li et al. / Journal of Molecular Structure: THEOCHEM 910 (2009) 50–55

220 200
DN1
IP DN2
200 EA 180 DN3
DN4
DN5
180 160 DN6

Fragmentation energy (kcal/mol)

DN7
DN8
160 140
IP/EA (kcal/mol)

140 120
80
100
60
80
40
60
20
40
0
0 2 4 6 8 10 n 20
LiCn
0
DC1
Fig. 3. Ionization potentials (IP) and electron affinities (EA) of LiCn vs the number of DC2
DC3
carbon atoms. 180 DC4
DC5
DC6
160 DC7

Fragmentation energy (kcal/mol)

DC8
DC9
IPs of n-even LiCn. The higher stabilities of n-even anionic LiCn  140 DC10
DC11
compared with n-odd LiCn  make the EAs of n-even LiCn higher. It
can also be easily seen in Fig. 3 that there is a tendency to lower 120

IPs and higher EAs as n increases.

100

3.4. Fragmentation energies 80

60
In above paragraphs, the fragmentation energies accompanying
channel DN1, DC1, and DA1, i.e. DEI, have been discussed. In addi-
40
tion, the fragmentation energies for many other dissociation reac-
tions are calculated and exhibited in Fig. 4, including the following 20
seven channels for neutral LiCn clusters:
0
LiCn ? LiCn2 + C2 (DN2) LiCn ? LiCn3 + C3 (DN3) DA1
DA2
LiCn ? Cn + Li (DN4) LiCn ? Cn1 + LiC (DN5) 180 DA3
DA4
LiCn ? Cn2 + LiC2 (DN6) LiCn ? Cn3 + LiC3 (DN7) DA5
DA6
LiCn ! Cn  + Li+ (DN8) 160 DA7
Fragmentation energy (kcal/mol)

DA8
DA9
140 DA10
the following ten channels for cationic LiCn þ clusters: DA11
DA12
LiCn þ ! LiCn2 þ + C2 (DC2) LiCn þ ! LiCn3 þ + C3 (DC3) 120 DA13
DA14
LiCn þ ! Cn þ + Li (DC4) LiCn þ ! Cn1 þ + LiC (DC5)
100
LiCn þ ! Cn2 þ + LiC2 (DC6) LiCn þ ! Cn3 þ + LiC3 (DC7)
LiCn þ Cn + Li+ (DC8) LiCn þ ? Cn1 + LiC+ (DC9) 80
LiCn þ ! Cn2 þ LiC2 þ (DC10) LiCn þ ! Cn3 þ LiC3 þ (DC11)
60
and the following thirteen channels for anionic LiCn  clusters:
40
LiCn  ! LiCn2  + C2 (DA2) LiCn  ! LiCn3  + C3 (DA3)
LiCn  ? LiCn1 + C (DA4) LiCn  ! LiCn2 þ C2  (DA5) 20
LiCn  ! LiCn3 þ C3  (DA6) LiCn  ! Cn  + Li (DA7)
LiCn  ! Cn1  + LiC (DA8) LiCn  ! Cn2  + LiC2 (DA9) 0
0 2 4 6 8 10 n
LiCn  ! Cn3  + LiC3 (DA10) LiCn  ? Cn + Li (DA11)
LiC/LiC+n/LiC-n
LiCn  ? Cn-1 + LiC (DA12) LiCn  ! Cn2 þ LiC2  (DA13)
LiCn  ! Cn3 þ LiC3  (DA14) Fig. 4. Fragmentation energies of the LiCn/LiCn þ /LiCn  clusters. DNx, DAx and DCx
corresponds to different dissociation channels, as shown in the text.

These channels can be divided into four groups: (1) losing small car-
bon particles such as C, C2, or C3; (2) losing lithium-contained small
fragments such as Li, LiC, LiC2, or LiC3; (3) losing ionic Li+/Li, LiC+/
LiC, LiC2 þ /LiC2  , or LiC3 þ /LiC3  fragments (for LiCn þ /LiCn  ); and (4)
losing anionic C, C2  , or C3  fragments (only for LiCn  ).
Comparing the fragmentation energies can help us to find some
dominant channels for the clusters investigated. In Fig. 4, the frag-
mentation energies of channel DN1, DC1, and DA1 are also in-
cluded, and some channels with very high energies (P200 kcal/
mol) are excluded. It is clear that losing a Li atom is the dominant
channel for neutral LiCn (channel DN4) and anionic LiCn  (channel
DA7), while the most favorable dissociation pathway is the loss of
Li+ ion (channel DC8) for cationic LiCn þ .
 G. Li et al. / Journal of Molecular Structure: THEOCHEM 910 (2009) 50–55 55

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