Journal of Nuclear and Radiochemical Sciences, Vol. 2, No. 1-2, pp. R13-R21, 2001

Reviews
The Nature of Bonding of Hyperlithiated Molecules Beyond the Octet Rule
Hiroshi Kudo*
Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan
Received: November 2, 2001; In Final Form: November 16, 2001
Following an overview on the nature of bonding of such hypervalent molecules as LinA (Li6C, Li3O, Li4O, Li3S,
Li4S, Li4P) and M2CN (M = Li, Na, K), the present paper deals with the molecular and electronic structures of
newly found lithium-rich Li2F and Li2OH molecules as well as Li2Fn−1 (n = 3, 4) and Lin(OH)n−1 (n = 3−5) clusters
which have been detected in supersonic beams effusing from a laser ablation source. The ionization energies (IEs)
determined by photoionization were 3.78 ± 0.2 eV for Li2F, 4.32 ± 0.2 eV for Li3F2, and 4.30 ± 0.2 eV for Li4F3.
Agreements of these IEs with theoretical ones calculated by ab initio MO methods support that Li2F is in a hyperlithiated configuration (HLC) in which the excess electron delocalizes over the two lithiums, while Li3F2 and Li4F3
are in a segregated configuration (SC) comprising ionic and non-ionic lithiums resulting from localization of theexcess valence electron. Ionization efficiency curves (IECs) measured for Lin(OH)n−1 (n = 2−5) are well reproduced with a simulation involving Franck-Condon factors, and this enabled us to identify the global-minimum
structure of these species predicted by theoretical calculations with the DFT method. The IEs determined were
4.053 ± 0.003 eV for Li2OH in HLC, 3.687 ± 0.003 eV for Li3(OH)2 in HLC, 4.133 ± 0.003 eV for Li3(OH)2 in
SC, and 3.418 ± 0.009 eV for Li4(OH)3 in SC, and 3.60 ± 0.11 eV for Li5(OH)4 in SC. Also, IE of Li3O was determined as 3.59 ± 0.02 eV from reinvestigation with the photoionization technique. Furthermore, Li3O was found to
be a floppy molecule sharing both the D3h and C2v structures from a precise analysis of the observed IEC taking
account of the potential energy surface for both neutral and cationic Li3O. This is the first experimental evidence
for “electronomers” or electronic isomers of Li3O, which have nearly the same stability but are different in localization of the SOMO. It is eventually stressed that delocalization of the excess valence electron over all of thelithium atoms in a molecule is essential to afford hyperlithiated molecules and that the shape of SOMO or HOMO,
which accommodates the excess valence electron or electrons, plays a key role in determining the stability ofhyperlithiated molecules.

1. Introduction
Comprehensive understanding of the nature of hyperlvalentbonding is a subject of current interest since the discovery of
Li3O in the equilibrium vapor over Li2O crystals at elevatedtemperatures in 1978 by Kudo, Wu, and Ihle with Knudseneffusion mass spectrometry.1, 2 This molecule possessing ninevalence electrons, at least formally, was found to be stabletoward dissociation to the corresponding octet molecule Li2O.
For a molecular system with covalent bonds of light elements,
the octet rule states that the most stable molecule is formed
when eight electrons are shared in the valence shell.3, 4 All of
the hydrides of elements in the second- and third-row of theperiodic table obey the rule. However, replacement ofhydrogen atoms by lithium atoms in such hydrides as CH 4,
NH3, H2O, and H2S changes the nature of bonding. In fact,
further experiments by our group 7−14 as well as theoreticalwork by Schleyer et al.15−27 have confirmed the existence ofthermodynamically stable polylithiated molecules with nine ormore valence electrons; e.g., Li3S and Li4P with nine valence
electrons and Li6C, Li4O, and Li4S with 10 valence electrons.
These molecules possessing excess valence electrons andstability toward dissociation are called “hyperlithiated” orhypervalent molecules. Does the hyperlithiated moleculeviolate the octet rule?
Extended search for hyperlithiated molecule by Knudseneffusion mass spectrometry gave evidence for another type ofhyperlithiated or hypervalent molecules M2CN (M = Li, Na,K), in which the bonding situation was apparently different*E-mail: kudoh@mail.cc.tohoku.ac.jp. FAX: +81-22-217-6597.

from that of LinA ; i.e., Li6C, Li3O, Li4O, Li3S, Li4S, Li4P.28-32
Although Schleyer17 predicted the existence of other hyperlithiated molecules like Li4N, Li5N, Li2F, and Li3F from histheoretical calculations, it was hard to get fruitful experimental
results with Knudsen-effusion mass spectrometry for these
species. Recently, however, we have detected hyperlithiated
Li 2 F and Li 2 OH molecules as well as lithium-rich clusters
Li2Fn−1 (n = 3, 4) and Lin(OH)n−1 (n = 3−6) in supersonic beams
effusing from a laser ablation source.33−36
Investigation of molecular and electronic structures of the
LinFn−1 and Lin(OH)n−1 systems with excess valence electrons
are interesting from a viewpoint of the metal-insulator transition. Recently, experimental and theoretical studies haveextensively been carried out to understand the mechanism ofmetal-insulator transitions, much attention being paid to transitional electronic characters between metal and ionic crystals in
non-stoichiometric clusters.37 For non-stoichiometric clusters
with excessive metal atoms, segregation into metallic and ionicparts is envisaged. From the measurement of ionization energies (IEs) for LinHm (n = 2−11, m = 1−3), for instance, Vezin etal. reported structures segregated into metallic Lin−m and ionic(LiH)m.38 Bonacic-Koutecký et al. confirmed the segregation
by ab initio MO calculations.39 Lievens et al. measured IEs of
LinO (n = 2−70) as a function of the cluster size n, and founddistinct steps at n =10, 22, and 42.40 These steps are in agreement with a prediction of the shell model for metallic clusters,
assuming that two of the lithium valence electrons localize on
the oxygen atom. This indicates that the clusters are segregated into metallic Lin-2 and ionic Li2O. Other examples ofsegregation were reported for LinC (n = 2−70),41 LinHm+ [m =1−6, n ≤ 22, (n−m) > 3],42, 43 CsmOn (0 < m < n, n = 3−14)44,
and NanFn−1.45−47© 2001 The Japan Society of Nuclear and Radiochemical Sciences
Published on Web 12/28/2001

Kudo

R14 J. Nucl. Radiochem. Sci., Vol. 2, No. 1-2, 2001
Alkali halide clusters with one excess alkali atom, Mn Xn−1,
tend to leave the excess electron localize at a specific site.37, 46−50
The electron localization is one of the important aspects ofsegregation. The most part of Mn X n−1 clusters is ionicallybound (ionic part) in contrast to the metal excessive clusters
such as LinO (n ≥ 8), where the metallic part prevails.40 For
instance, Durand et al. revealed the electron-localization in
NanFn-1 (n = 2−29) clusters based on a one-electron pseudopotential calculation, and reported that the measured IEs reflectedfaithfully the localization character of the excess electron.49
In the present paper, I will first briefly summarize the natureof bonding of such hypervalent molecules as LinA (Li6C, Li3O,
Li4O, Li3S, Li4S, Li4P) and M2CN (M = Li, Na, K), which weredetected in equilibrium vapors over solid or liquid samples byKnudsen-effusion mass spectrometry combined with electron
impact ionization. This method has an advantage for determining the dissociation energy of the detected species,
although it has some disadvantages for obtaining precise
values of IE when we use the electron impact ionization. Next,
I will discuss on the molecular and electronic structures ofhyperlithiated Li2F and Li2OH molecules as well as lithiumrich clusters Li 2 F n−1 (n = 3, 4) and Li n (OH) n−1 (n = 3−5)detected in supersonic beams effusing from a laser ablation
source. The experiments were performed by a time-of-flightmass spectrometer in which species in the supersonic beam
were ionized with pulses from a dye laser pumped by an
Nd:YAG laser.36 This sophisticated method is advantageous indetermining IEs of these species more accurately. A detailed
analysis of ionization efficiency curves (IECs) measured by

Figure 1. Features of SOMO in Li3S (C2v) and HOMO in Li4S (C2v) as
well as molecular structures deduced from theoretical calculations at
UHF/STO-3G level; roman letters are the bond length in Å and italic
letters the natural charge.

photoionization enables us to identify the global-minimum
structure of the clusters existing in the supersonic beam.
Furthermore, I will interpret the molecular and electronic
structures of the Li 3 O molecule reinvestigated by an IEC
analysis combined with simulations.
2. LinA (Li6C, Li3O, Li4O, Li3S, Li4S, Li4P) and M2CN (M =Li, Na, K) Molecules
Despite their unusual stoichiometries, the LinA molecules(Li6C, Li3O, Li4O, Li3S, Li4S and Li4P) are stable toward dissociation to the corresponding octet molecules.1, 2, 7-14 The dissociation energies are summarized in Table 1. The results of abinitio MO calculations indicate that occupancy of the ninevalence electrons in Li3S, for instance, is (5a1)2(3e)4(6a1)2(7a1)1
and that of 10 valence electrons in Li4S is (6a1)2(3b1)2(7a1)2(3b2)2(8a1)2. The highest orbital (7a1) of Li3S is singly occupied orbital (SOMO) and the 8a 1 orbital of Li 4S is HOMO.
The excess valence electrons accommodate in SOMO or
HOMO. Either one and two excess valence electrons in thesemolecules delocarize over all of the lithium atoms andcontribute to the formation of a Linm+ cage with Li-Li bonds.
Figure 1 depicts the features of SOMO in Li3S and HOMO in
Li4S deduced from theoretical calculations at the UHF/STO3G level.14 The SOMO of Li3S seems to build the cage. The
widely spreading HOMO of Li 4S suggests more clearly thelithium cage formation in the molecule. The SOMO of Li3S
and HOMO of Li 4 S are antibonding between the Li and S
atoms, but are bonding between all pairs of lithium atoms inthese molecules. In spite of the antibonding character of
SOMO and HOMO, the central S atom is bound to lithiums
through an electrostatic interaction.
Charge populations calculated by the natural bond orbital(NBO) analysis51 on the central atoms in LinA were −0.93 for
C in Li6C, −0.87 for O in Li3O, −1.89 for S in Li3S, and −1.92
for S in Li4S. The calculated charges on C, O, and S do notincrease appreciably as more Li atoms are added; e.g., Li4C (C,−0.81), Li2O (O, −0.81), and Li2S (S, −1.84). The fact indicates that the excess valence electron is not associated with thecentral atom and that the central atom remains content with its
normal octet.5, 15 For hyperlithiated LinA molecules, therefore,
it is concluded that the electronegative central atom (Am−) isembedded in the Linm+ cage. Although the Li-A bond is antibonding in character, the electrostatic attraction between Linm+
and Am− would play a role in enhancing the overall stability ofneutral LinA molecules.
As listed in Table 1, M2CN (M = Li, Na, K) molecules with
one excess valence electron are all stable toward the dissociation to give M and MCN.28−32 Of these hypervalent molecules,

TABLE 1: Dissociation Energies (D0o) and Ionization Energies (IE) of Hyperlithiated and Hypervalent Molecules
D0o/kJ mol
MnA(g)→ Mn−1A(g) + M(g)Theor.
Expt.

Theor.aExpt.

Li3O (D3h)
Li3S (C3v)
Li4P (Td)
CLi6 (Oh)
Li4O (Td)
Li4S (C2v)

198.3b148.5
141.8(273)c120.9b123.2b212 ± 42138 ± 1486 ± 24(274 ± 11)c
197 ± 30212 ± 13

3.48b
4.11
3.40b
4.08b
4.71b
4.09

3.6 ± 0.1
4.4 ± 0.2-

Li2CN (Cs)
Na2CN (Cs)
K2CN (Cs)

103.8
72.8
74.5

137 ± 14104 ± 1482 ± 8

5.13
4.66
3.70

5.4 ± 0.2
4.9 ± 0.2
4.5 ± 0.5

Number ofexcessvalence electrons

Molecule(Point group)

1

2

1

a

Vertical ionization energy (vIE).
Schleyer et al.5, 6, 15cCLi6(g) → CLi4(g) + Li2(g) process.
b

IE/eV
MnA → MnA+

The Nature of Bonding of Hyperlithiated Molecules

J. Nucl. Radiochem. Sci., Vol. 2, No. 1-2, 2001 R15o

Li2CN 1 (D0 = 137 kJ/mol) is the most stable. Each of M2CN
molecules has several structural isomers with a global
minimum. Figure 2 illustrates molecular structures of all
isomers of Li2CN calculated at the MP2(FC)/6-31-G* level,
together with the SOMOs of the planar 1 and linear 4 isomers.
The optimized geometries calculated for Na2CN and K2CN at
the MP2(FU)/6-31-G* level also gave four structural isomers
to each molecule, similar to the case of Li2CN. For M2CN, themost stable isomer in the planar structure with Cs symmetry isa hypervalent molecule in which the excess valence electron
delocalizes over the two alkali-metal atoms forming a M 2 +cation. The IEs observed for these molecules, 5.4 ± 0.4 eV for
Li2CN, 4.9 ± 0.2 eV for Na2CN, 4.5 ± 0.5 eV for K2CN, areclose to those for Li2 → Li2+ (4.9 eV), Na2 → Na2+ (4.9 eV),and K2 → K2+ (4.1 eV). The fact suggests that the ionization
occurs from the SOMO. M2CN molecules possessing the M2+
unit in it can be described as M2+CN−. On the other hand, thelinear isomers of M2CN, that are less stable than the planar
isomers, would be complexes described as M+ CN − · M and
M · CN−M+; these are "electronomers" or electronic isomers inwhich the localization of the excess valence electron isdifferent each other.

In addition, new clusters LinFn−1 (n = 3, 4) with an excess electron were detected in the same supersonic beam. Table 2 lists
the IEs of Li2Fn−1 (n = 2−4) species determined by photoionization, together with the dissociation energy (D0o) of the isomers
calculated at the MP2(FULL)/6-311+G(d)//B3LYP/6311+G(d) level of theory. Figure 3 illustrates the theoreticallydeduced structures of LinFn−1 (n = 2−4) isomers.
The observed IE of Li2F (3.78 ± 0.3 eV) agrees well withthe theoretical adiabatic IE (aIE = 3.9 eV). This fact verifies a
result of theoretical calculations that the Li2F molecule (1a) is
one of the hyperlithiated molecules and the excess valence
electron delocalizes on the two Li atoms. Also, the fact that IE
of Li2F is significantly lower than that of the Li atom (5.39 eV)
is ascribed to the antibonding character of the SOMO between
the Li and F atoms, as described by Gutsev and Boldyrev for"superalkali" species.52 Although the presence of the isomer
1b is suggested theoretically, only the isomer 1a existed in the
supersonic beam because 1a (D 0 o = 147.4 kJ/mol) is more

3. Li2F Molecule and Li2Fn–1 (n = 3, 4) Clusters
Although theoretically predicted hyperlithiated Li2F was
hardly observed with Knudsen-effusion mass spectrometry, it
was eventually detected in a supersonic beam of vapors generated by laser ablation of a solid mixture of LiF and Li3N.33−34

Figure 2. Structural isomers of Li2CN and features of SOMO of theplanar isomers 1 [Li2+(CN)−] and the linear isomer 4 [Li · (CN)−Li+]
deduced from calculations at MP2(FC)/6-31-G*; roman letters are thebond length in Å and italic letters the natural charge.

Figure 3. Structural isomers of Li2Fn−1 (n = 2−4) obtained by calculations at B3LYP/6-311+G(d); roman letters are the bond length in Å
and italic letters the natural charge.

TABLE 2: Ionization Energies and Dissociation Energies of LinFn–1 (n = 2–4)
Experimental
IE/eV

Isomer

Li2F

3.78 ± 0.20

Li3F2

4.32 ± 0.20

Li4F3

4.30 ± 0.20

1a (C2v)
1b (C∞v)
2a (C2v)
2b (Cs)2c (D3h)
3a (C3v)
3b (Cs)3c (C2v)
3d (C2v)avIE/eV
4.43
6.84
5.26
4.51
3.78
4.26
4.53
5.58
3.46

a

Classificationc

TheoreticalaIE/eV a

D0 /kJ mol

3.86
−
3.78
4.15
3.78
3.61
4.06
3.87
−

147.4
26.7
97.8
94.9
33.0
87.4
74.8
66.2
52.8

o

−1 b

HLC
SC
SC (planar)
SC (Li-tail)HLCSC
SC (Li-tail)
SC (planar)
SC

Vertical and adiabatic ionization energies (vIE and aIE) at MP2(FULL)/6-311+G(d)// B3LYP/6-311+G(d).
At B3LYP/6-311+G(d).
cHLC, the hyperlithiated configuration; SC, the segregated configuration.
b

Kudo

R16 J. Nucl. Radiochem. Sci., Vol. 2, No. 1-2, 2001ostable than 1b (D 0 = 26.7 kJ/mol). The isomer 1b is in asegregated configuration (SC).
The observed IE of Li3F2 (4.32 eV) indicates the predominance of SC in this cluster. This IE value is close to aIE calculated for the isomer 2b, which is in SC with D0o = 94.9 kJ/mol.
Here, one can consider that the isomer 2a in another SC with asimilar stability (D0o = 94.9 kJ/mol) would be present because
the observed IE is in between the theoretical aIE and vertical
ionization energy (vIE) of 2a. However, the presence of 2a inthe supersonic beam is denied from a comparison of IECs
between the experiment and the simulation shown in Figure 4;
the theoretical IEC was obtained by taking account of theFranck-Condon factor for the ionization process, the detail ofwhich will be described elsewhere. The isomer 2c with ahyperlithiated configuration (HLC) is obviously minor,
because the observed IE (4.32 eV) is significantly higher inenergy than vIE calculated for 2c (3.7 eV). Furthermore, thedissociation energy of 2c is calculated to be quite small (D0o =33.0 kJ/mol) in comparison with the other isomers of Li3F2 aslisted in Table 2. The Li4F3 cluster would prefer SC. The IE
observed for Li4F3 (4.3 eV) is close to vIEs calculated for 3aand 3b, both of which are in SC. No big difference is seen in
dissociation energies between 87.4 kJ/mol for 3a and 74.8
kJ/mol for 3b, but the shape of IEC shown in Figure 4 indicates that the isomer detected in the supersonic beam is 3b.
In the LinFn−1 system, Li2F is a hypervalent molecule, but
Li3F2 prefers to be in SC despite a possibility to be in HLC.
Every isomer of Li4F3 is in SC. Thus, at n ≥ 3 the LinFn−1 clusters tends to take SC in which the excess valence electron is
localized at any of the Li atom.

source in which lithium metal pressed on a sample disk was
irradiated by 532 nm laser pulses. Figure 5 shows ionization
efficiency curves (IECs) of the Li2(OH) molecule as well as
Lin(OH)n−1 (n = 3−5) clusters.36 The experimental values of IE
determined here for each isomer of these species are summarized in Table 3, together with both the theoretical vertical
ionization energy (vIE) and adiabatic ionization energy (aIE)calculated at the MP2(FULL)/6-311+G(d)//B3LYP/6311+G(d) level as well as the dissociation energies calculated
at the B3LYP/6-311+G(d,p) level. The structural isomers andfeatures of SOMO of Li2(OH) and Li3(OH)2 deduced by theoretical calculations at the B3LYP/6-311+G(d,p) level are illustrated in Figure 6. The theoretically obtained molecular
structures and isosurfaces of SOMO of Li4(OH)3 and Li5(OH)4
are shown in Figures 7 and 8, respectively.
The results of our theoretical investigation reveal that IEs of
Li n (OH) n−1 (n = 2−5) species with an excess lithium atom
depend largely on their structure.35 Every cluster has several
stable structural isomers, the structure of which is closely
related to the charge population associated with the location of
the excess valence electron of the Li atom. In some isomers,
the excess electron delocalizes over all of the lithium atoms in
the cluster, forming a metallic network (Lin+) similar to hyperlithiated molecules like Li3O and Li6C. In other isomers, theexcess valence electron localizes at a specific site, making themetallic and ionic parts segregated. In the Lin (OH)n-1 (n = 2−5) system, the isomers 1a and 2a seem to have HLC withrespect to the charge population. All of the lithium atoms
possess almost the same atomic charge in these isomers as

4. Li2OH Molecule and Lin(OH)n–1 (n = 3–5) Clusters

Relative intensity (arb. units)

Relative intensity (arb. units)

To detect Lin(OH)n−1 (n = 2−5) species, we injected small
amounts of water vapor diluted with air into an laser ablation

Photon energy (eV)Figure 4. Ionization efficiency curves (IECs) observed for Li2Fn−1(n = 2−4) in comparison with simulations based on Franck-Condon
factors.

Photon energy (eV)Figure 5. Ionization efficiency curves (IECs) of Li 2 (OH) andLin (OH)n−1 (n = 3−5) clusters measured by photoionization.

The Nature of Bonding of Hyperlithiated Molecules

J. Nucl. Radiochem. Sci., Vol. 2, No. 1-2, 2001 R17

shown in Figures 6 and 7. To confirm whether or not theseisomers are in HLC, we examined their electronic structureand stability in terms of a character of SOMO which accommodates the excess electron. As described in the previous
section, hyperlithiated molecules Li3 O, Li 6 C, and Li 3 S arestabilized by an electrostatic attraction between the anionic
center and the cationic lithium network which is maintained bysharing the excess electron. The SOMO spatially covers alllithium atoms, making their structures highly symmetric; e.g.,
D3h for Li3O, Oh for Li6C, and C3v for Li3S. The SOMO shouldhave an antibonding character between, at least, one of thelithium atoms and the central atom. However, the equal posi-tive charge on all lithiums produces an equal electrostatic
attraction between each Li atom and the central atom. The
SOMO spreading over the whole lithium network plays a keyrole in the formation of molecules with HLC.

Figure 6. Structures and features of SOMO of Li2(OH) and Li3(OH)2
obtained by calculations at B3LPY/6-311+G(d,p); roman letters are
the bond length in Å and italic letters the natural charge.

Figure 7. Structural isomers of Li4(OH)3 and Li5(OH)4 obtained by
calculations at B3LPY/6-311+G(d,p); roman letters are the bondlength in Å and italic letters the natural charge.

TABLE 3: Ionization Energies and Dissociation Energies of Lin(OH)n–1 (n = 2–5)
Experimental
IE/eV

Isomer

Li2OH

4.35 ± 0.12

Li3(OH)2

3.66 ± 0.02
4.16 ± 0.04

Li4(OH)3

3.33 ± 0.11

Li5(OH)4

3.60 ± 0.11

1a (C2v)
1b (C∞v)
2a (D3h)2b (Cs)2c (C2v)
3a (C3v)
3b (C2v)
3c (Cs)3d (C2v)
3e (C2v)
4a (Cs)4b (C2v)
4c (C2)4d (Cs)4e (C2v)
4f (C2v)avIE/eV

4.45
6.58
3.57
4.13
5.10
3.40
3.31
4.21
3.29
5.46
3.71
3.55
3.05
4.18
3.19
5.62

a

D0 /kJ mol

4.03
5.55
3.57
4.13
4.17
3.38
3.31
2.96
3.29
4.28
3.18
3.23
3.01
3.82
2.86
4.41

146.7
19.4
92.5
92.0
82.6
120.1
88.7
81.7
81.6
46.5
80.9
79.6
76.4
71.9
47.1
12.5

Vertical and adiabatic ionization energies (vIE and aIE) at MP2/6-311+G(d,p).
At B3LYP/6-311+G(d,p).
c
HLC, the hyperlithiated configuration; SC, the segregated configuration.
b

Classificationc

TheoreticalaIE/eV a

o

−1 b

HLC
SC
HLC
SC (Li-tail)
SC (planar)SCSC
SC (Li-tail)(SC)
SC (planar)
SC
SC
(SC)
SC (Li-tail)SC
SC (planar)

R18 J. Nucl. Radiochem. Sci., Vol. 2, No. 1-2, 2001

Kudo

The result of theoretical calculations indicates further that
IEs of the isomers of Li n (OH) n−1 depend on the number ofterminal lithium atoms as shown in Figure 9, irrespective of
the stability toward dissociation (Table 3). For example, thedifference in IEs between the isomer 2a and 2c of Li3(OH)2 is
as large as 1.43 eV, although the difference in the dissociationenergies is only 0.1 eV (9.9 kJ/mol). The IEs of planar
isomers (1a, 2c, 3e, 4f) with two terminal lithiums (nTL = 2)
tend to increase from 4.5 to 5.6 eV with an increase of n. The
IE of Li-tail isomers (2b, 3c, 4d) with nTL = 1 is around 4.2 eV
independent of n. The isomers without terminal Li atoms have
IE lower than 3.7 eV. The vIE of the linear isomer 1b (6.58
eV) is quite higher than that of the Li atom (5.39 eV).
Based on the Koopmans theorem that the vertical ionizationenergy directly corresponds to the orbital energy of SOMO,
the present result is explained by considering the stability of
SOMO, from which the extra electron is removed in theionization process. In the Lin(OH)n−1 clusters, the OH− groups
with negative charge would deform the SOMO as a consequence of the electronic repulsion as suggested from the spatial
distribution of SOMO. When repulsion by OH − groups
becomes larger, the SOMO becomes less stable and then theionization energy becomes lower. This leads to the importanceof spatial arrangement of the OH− groups against the SOMO
within the cluster. We focus the discussion on the spatial
distribution of the SOMO to explain the correlation between
the ionization energy and the number of terminal lithium atoms
in the Lin(OH)n−1 clusters. The SOMO tends to localize aroundthe terminal lithium atom. In the planar isomers with thehighest IE, the SOMO distributes in a space between the twoterminal lithium atoms, independent of the cluster size. The
deformation of SOMO from a spherical symmetry is rather
small in these planar isomers, because the neighboring OH− isfairly distant from the SOMO. In the Li-tail isomers with thesecond highest ionization energy in each size of the cluster, theSOMO localizes around the terminal Li atom and is deformedby the nearest OH− group as seen in 2b (Figure 6). It is to be

noted that the Li-tail isomers in which the SOMO localizes
around only one Li atom have lower ionization energy than theplanar isomers in which the SOMO delocalizes between two Li
atoms. In the isomers without terminal lithium, the SOMO
delocalizes over the lithium network. In particular, the SOMO
is largely deformed and widely distributed over the whole
lithium network in the hyperlithiated isomers 2a (Figure 6).
The ionization energies of these isomers are significantly low
as seen in Table 3.
From comparison of IEs between the experiment and thetheory listed in Table 3 it is concluded that the isomers exitedin the supersonic beam of the present experiment were
Li2(OH) 1a, Li3(OH)2 2a, 2b, Li4(OH)3 3a, and Li5(OH)4 4a.
The global-minimum structure is in HLC at n = 2 and 3 and in
SC at n = 4, indicating the occurrence of the transition from
HLC to SC between n = 3 and 4. The second stable isomer 2bin SC was also observed for Li3(OH)2. This might be attributed to nearly the same stability of the two isomers; D0o = 92.5
kJ/mol for 1a and D0o = 92.0 kJ/mol for 2b. The conclusion
was also confirmed by comparing the shape of measured IECs
with that obtained by simulations involving the FranckCondon factor (FCF), the detail of which is reported elsewhere.35

Figure 8. Isosurfaces of SOMO in structural isomers of Li4(OH)3 andLi5(OH)4 obtained by calculations at B3LPY/6-311+G(d,p).

Figure 9. Relation between vertical ionization energy (vIE) and nTL

5. Reinvestigation of Molecular Structure and Ionizationof Li3O; Evidence for Electronomers
When we reported the first evidence for the existence ofhyperlithiated Li3O,1, 2 the ionization energy (IE) determinedby electron impact ionization was 4.5 ± 0.2 eV. The dissociation energy of Li3O to give Li2O was determined as 212 ± 42
kJ/mol. Although the dissociation energy agreed considerably
well with the theoretical value (198.3 kJ/mol) calculated by
Schleyer et al.,5 a rather large difference was seen in the IE
between the experiment and theory (3.48 eV). The question
remained to be solved for a long time. Recently, Lievens et al.
have reported an experimental value (3.54 ± 0.3 eV) for IE of
Li3O by photoionization measurements.40 This stimulated us
to reinvestigate the ionization process of Li3O present in thesame supersonic beam used for detecting the Li n (OH) n−1(the number of terminal lithium atoms) in each cluster size n.

The Nature of Bonding of Hyperlithiated Molecules

species described in the previous section. Figure 10(a) shows
the ionization efficiency curve (IEC) for Li3 O obtained bytime-of-flight mass spectrometry combined with photoionization. There are two prominent features in the profile of IEC,
i.e., two-stage rise and gradual linear rise between thethreshold (3.59 ± 0.02 eV) and the second onset (4.4 ± 0.1 eV).
The two-stage rise has already been reported by Lievens et al.40
and attributed to some ionization processes other than the firstionization of Li3O to give the ground state Li3O+ of current
interest. The threshold determined here is in excellent agreement with the theoretical IE. Both the theoretical vIE and aIE
are calculated as 3.59 eV at a sophisticated level of
CCSD(T)/6-311+G(d) assuming the D 3h structure for theneutral geometry.
Schleyer et al. reported in 1982 that the most stable structureof Li3O was in C2v symmetry from the calculation at the HF/321G level,5 and then reported in 1992 that their higher level ofcalculation at MP2(FULL)/6-31+G* revealed the D 3 hsymmetry.6 Figure 11 illustrates the result of our calculation
on molecular structures of neutral and ionic Li3O at the MP2/6311+G(d) level of ab initio MO theory.53 For the neutral, boththe D3h and C2v structures are local minima on the potential
energy surface. Single-point energy calculations at the
CCSD(T)/6-311+(d) level indicate that the D 3h structure isslightly favorable in energy (0.8 kJ/mol), but the energy difference between those structures is much smaller than the accuracy of the calculation. The true minimal energy structure is
still unpredictable. However, a simulation of the profile ofIEC for Li3O shown in Figure 10(b) provided a new clue to themolecular structure.
We can make simulations of IEC for small molecules by a"direct counting of vibrational states" method, using the sameprocedure as applied to the Lin(OH)n−1 system.36 An essential
idea of simulation is to calculate Franck-Condon factors (FCF)
within harmonic approximation. The calculation includes thedisplacement of molecular geometry, the frequency change,
and the normal mode rotation between the neutral and cationicstates. All of these parameters can be computed by density

J. Nucl. Radiochem. Sci., Vol. 2, No. 1-2, 2001 R19
functional theory (DFT) or ab initio MO theory calculations.
The simulated IECs for Li3O are superimposed on the experimentally observed IEC in Figure 10(b). The ionization of theD 3h structure of neutral Li 3 O does not reproduce well theobserved gradual linear rise. Even with parameters for the C2v
structure, the simulation is far from the observed linear rise ofIEC. The well-fitted curve in Figure 10(b) was obtained when
two in-plane bending frequencies were adjusted to 10 cm−1 andthe molecule is restricted to populate only on the zero-pointlevel in these modes; i.e., no vibrational excitation in these two
bending modes. We assumed a flat potential energy surface
for the neutral Li3O to reproduce the observed curve.53 In fact,
the ab initio MP2 calculation gives a very flat potential well inthe two Li-O-Li bending modes. Figure 12 shows a twodimensional potential energy surface spanned by the two
bending coordinates; the horizontal axis for scissoring and thevertical for rocking. We can see a three-fold flat bottom
consisting of one D3h minimum and three C2v minima in Figure12(a). A cross sectional view on the horizontal axis shows adouble well potential consisting of one of the three C2v minima
and the D 3h minimum [Figure 12 (b)]. The barrier height
between the D3h and C2v minima is negligibly small (0.3 kJ/mol
from the D3h well). Consequently, the vibrational zero-point(v = 0) level, which is indicated by the horizontal solid line,
lies above the barrier and thus spreads over these two minima.
This wide v = 0 level indicates that the wave function of thevibrational ground state is delocalized over the three C 2v

Figure 11. Molecular structures of neutral (D3h, C2v) and cationic(D3h) Li3O calculated at MP2/6-311-G(d) level.

Figure 12. Ab initio potential energy surfaces of Li 3 O. (a) The

Figure 10. Photoionization efficiency curve measured for Li3O (a)and the simulation for the threshold region (b). A good fit was
obtained with a flat potential energy surface shown in Figure 12.

potential well consists of three C 2v minima and one D 3h
minimum in the two bending motions. (b) The vibrational
ground-state wave function spreads over the saddle points
between D3h and C2v minima. (c) The vertical ionization fromthe flat-bottomed potential accesses a wide energy range of thecation.

Kudo

R20 J. Nucl. Radiochem. Sci., Vol. 2, No. 1-2, 2001
minima and the D 3h minima. With this large amplitude ofvibrational motion, a wide range of cationic potential energy
surface is accessible by the vertical ionization from the v = 0
level as shown in Figure 12(c). Thus the Li3O molecule isdescribed as a floppy molecule sharing both the D3h and C2v
structures which have nearly the same stability but are
different in the localization of the SOMO.
The most significant difference between the D3h and C2v
structures is the shape or spatial distribution of their SOMO.
The shape of SOMO is important characteristics in hyperlithiated molecules. The D 3h structure shows fully delocalized
SOMO (Figure 13), forming a lithium network comprising allof the three lithium atoms, similar to other hyperlithiated molecules. In contrast, the C2v structure has SOMO localized on
two lithium atoms to form one Li-Li bond and the remaining
lithium atom is completely cationic with an natural atomic
charge of +0.95. Therefore, the C2v structure can be regarded
as a salt of Li2+ and LiO−. In other words, the C2v structure has
an electronic structure segregated into a metallic-like Li2 +cation and a LiO− anion. Both the D3h and C2v structures havenearly the same stability. Theoretically, the existence of suchnearly degenerate isomers with different localization of SOMOin the same irreducible representation was predicted by
Schleyer's group for hyperlithiated Li2CN.54 They called theisomers "electronomers." From this point of view, D3h and C2v
structures of Li 3 O are electronomers, the experimental
evidence for which has been provided for the first time. It canbe concluded that the Li 3 O molecule is a floppy molecule
sharing both the hyperlithiated D3h and segregated C2v structures which possess nearly the same stability but are different
in the localization of the SOMO.
5. Conclusion
In hyperlithiated or hypervalent molecules such as Lin A(Li6C, Li3O, Li4O, Li3S, Li4S, Li4P), M2CN (M = Li, Na, K),
Li2Fn−1 (n = 2−4), and Lin(OH)n−1 (n = 2−5), the excess valence
electron is not associated with the electronegative C, O, F, S,
and P atoms as well as CN and OH groups, and the electronegative constituent remains content with its normal octet. The
excess valence electron delocalizes over lithium atoms
contributing to the formation of a lithium network or cage
(Linm+) with the Li-Li bond, and the hyperlithiated molecules
are stabilized by the electrostatic attraction between the
cationic Linm+ and the anionic species (e.g., C0.9−, O0.9−, F1.0−,
S1.9−, CN1.0−, OH1.0−), despite the antibonding character between
each of the lithium atom and the electronegative constituent.
Delocalization of the excess valence electron is essential toafford hyperlithiated molecules, and the spatial distribution or
shape of SOMO and HOMO, which accommodates the excess
valence electron, plays a crucial role in determining thestability of hyperlithiated molecules. In the Li2Fn−1 (n = 2−4)

Figure 13. Features of SOMO of Li3O. The excess valence

electron is fully delocalized and forms a lithium cage in the D3hstructure, while it is localized and forms a salt consisting of
Li2+ and LiO− in the C2v structure.

and Lin(OH)n−1 (n = 2−5) systems, SOMO widely spreads over
the whole molecule giving a hypelithiated configuration (HLC)at small n, but tends to localize around a specific site affording
a segregated configuration (SC) with an increase of n. Of
these Li-rich clusters, IE is relatively high in planar isomers
with two terminal lithium atoms (n TL = 2) reflecting thestability of SOMO.
From the reinvestigation of ionization processes of Li 3O,
this hyperlithiated molecule was found to be a floppy molecule
sharing both D3h (HLC) and C2v (SC) structures which havenearly the same stability but are different in the localization of
SOMO. This is the first experimental evidence for electronomers or electronic isomers.
References(1) H. Kudo, C. H. Wu, and H. R. Ihle, J. Nucl. Mater. 78,
380 (1978).
(2) C. H. Wu, H. Kudo, and H. R. Ihle, J. Chem. Phys. 70,
1815 (1979).
(3) G. N. Lewis, J. Am. Chem. Soc. 38, 762 (1916).
(4) W. Kossel, Ann. Phys. 49, 229 (1916).
(5) P. v. R. Schleyer, E.-U. Wüthwein, and J. A. Pople, J. Am.
Chem. Soc. 104, 5839 (1982).
(6) E. Rehm, A. I. Boldyrev, and P. v. R. Schleyer, Inorg.
Chem. 31, 4834 (1992).
(7) H. Kudo, Chem. Lett. 1986, 1611.
(8) C. H. Wu, Chem. Phys. Lett. 139, 357 (1987).
(9) H. Kudo and C. H. Wu, Chem. Express, 5, 633 (1990).
(10) H. Kudo and K. F. Zmbov, Chem. Phys. Lett. 187, 77(1991).
(11) H. Kudo, Nature 355, 432 (1992).
(12) H. Kudo and C. H. Wu, J. Nucl. Mater. 201, 261 (1993).
(13) H. Kudo, J. Mass Spectrom. Soc. Jpn. 41, 317 (1993).
(14) H. Kudo, K. Yokoyama, and C. H. Wu, J. Chem. Phys.
101, 4190 (1994).
(15) P. v. R. Schleyer, E.-U. Wüthwein, E. Kaufmann, T.
Clark, and J. A. Pople, J. Am. Chem. Soc. 105, 5930
(1983).
(16) E.-U. Wüthwein, P. v. R. Schleyer, and J. A. Pople, J. Am.
Chem. Soc. 106, 6973 (1984).
(17) P. v. R. Schleyer, in “New Horizons of Quantum
Chemistry,” ed. by P.-O. Löwdin and B. Pullman, Reidel
Publ., Dortrecht (1986), p. 95.
(18) A. E. Reed, R. B. Weinstock, and F. Weinhold, J. Chem.
Phys. 83, 735 (1985); J. Am. Chem. Soc. 108, 3586
(1986).
(19) A. E. Reed and F. Weinhold, J. Am. Chem. Soc. 107,
1919 (1985).
(20) J. P. Ritchie and S. M. Bacharach, J. Am. Chem. Soc. 109,
5909 (1987).
(21) C. J. Marsden, J. Chem. Soc., Chem. Commun. 1989,
1356.
(22) J. Ivanic and C. J. Marsden, J. Am. Chem. Soc. 115, 7503
(1993).
(23) J. Ivanic, C. J. Marsden, and D.M. Hassett, J. Chem. Soc.,
Chem. Commun. 1993, 822.
(24) G. L. Gutsev and A. I. Boldyrev, Chem. Phys. Lett. 92,
262 (1982).
(25) V. G. Zakrewski, W. von Niessen, A. I. Boldyrev, and P.
v. R. Schleyer, Chem. Phys. Lett. 197, 195 (1992).
(26) M. Gutovski and J. Simons, J. Phys. Chem. 98, 8326
(1994).
(27) Z. Shi, J. Wang, and R. J. Boyd, J. Phys. Chem. 99, 4941
(1995).
(28) H. Kudo, M. Hashimoto, K. Yokoyama, C. H. Wu, A. E.
Dorigo, F. M. Bickelhaupt, and P. v. R. Schleyer, J. Phys.
Chem. 99, 6477 (1995).
(29) M. Hashimoto, K. Yokoyama, H. Kudo, C. H. Wu, and P.

The Nature of Bonding of Hyperlithiated Moleculesv. R. Schleyer, J. Phys. Chem. 100, 15770 (1996).
(30) H. Kudo, M. Hashimoto, K. Yokoyama,C. H. Wu, and P.
v. R. Schleyer, Thermochim. Acta 299, 113 (1997).
(31) H. Kudo and K. Yokoyama, Bull. Chem. Soc. Jpn. 69,
1459 (1996).
(32) H. Kudo, M. Hashimoto, H. Tanaka, and K. Yokoyama, J.
Mass Spectrom. Soc. Jpn. 47, 2 (1999).
(33) K. Yokoyama, N. Haketa, M. Hashimoto, K. Furukawa,
H. Tanaka, and H. Kudo, Chem. Phys. Lett. 320, 645(2000).
(34) K. Yokoyama, N. Haketa, H. Tanaka, and H. Kudo,
Chem. Phys. Lett. 330, 339 (2000).
(35) H. Tanaka, K. Yokoyama, and H. Kudo, J. Chem. Phys.
113, 1821 (2000).
(36) H. Tanaka, K. Yokoyama, and H. Kudo, J. Chem. Phys.
114, 152 (2001).
(37) U. Landman, D. Sharf, and J. Jortner, Phys. Rev. Lett. 54,
1860 (1985).
(38) B. Vezin, Ph. Dugourd, D. Rayane, P. Labastie, J.
Chevaleyre, and M. Broyer, Chem. Phys. Lett. 206, 521(1993).
(39) V. Bonacic-Koutecký, J. Gaus, M. F. Guest, L. Češpiva,
and J. Koutecký, Chem. Phys. Lett. 206, 528 (1993).
(40) P. Lievens, P. Thoen, S. Bouckaert, W. Bouwen, F.
Vanhoutte, H. Weidele, R. E. Silverans, A. N.-Vázquez,and P. v. R. Schleyer, J. Chem. Phys. 110, 10316 (1999).
(41) P. Lievens, P. Thoen, S. Bouckaert, W. Bouwen, F.

J. Nucl. Radiochem. Sci., Vol. 2, No. 1-2, 2001 R21
Vanhoutte, H. Weidele, and R. E. Silverans, Chem. Phys.
Lett. 302, 571 (1999).
(42) R. Antoine, Ph. Dugourd, D. Rayane, E. Benichou, and M.
Broyer, J. Chem. Phys. 107, 2264 (1997).
(43) R. Antoine, Ph. Dugourd, D. Rayane, and M. Broyer, J.
Chem. Phys. 104, 110 (1996).
(44) H. G. Limberger and T. P. Martin, J. Chem. Phys. 90,
2979 (1989).
(45) P. Labasite, J.-M. L'Hermite, Ph. Poncharal, and M.
Sence, J. Chem. Phys. 103, 6362 (1995).
(46) E. C. Honea, M. L. Homer, and R. L. Whetten, Phys. Rev.
B 47, 7480 (1993).
(47) G. Rajagopal, R. N. Barnett, and U. Landman, Phys. Rev.
Lett. 67, 727 (1991).
(48) A. W. Castleman Jr. and K. H. Bowen Jr., J. Phys. Chem.
100, 12911 (1996).
(49) G. Durand, J. Giraud-Girard, D. Maynau, F. Spiegelmann,and F. Calvo, J. Chem. Phys. 110, 7871 (1999).
(50) R. L. Whetten, Acc. Chem. Res. 26, 49 (1993).
(51) A. E. Reed, L. A. Curtiss, and F. Weinhold, Chem. Rev.
88, 899 (1985).
(52) G. L. Gutsev and A. I. Boldyrev, Chem. Phys. Lett. 92,
262 (1982).
(53) K. Yokoyama, H. Tanaka, and H. Kudo, J. Phys. Chem. A
105, 4312 (2001).
(54) A. Dorigo and P. v. R. Schleyer, Chem. Phys. Lett. 186,
363 (1991).