Journal of Molecular Structure: THEOCHEM 861 (2008) 18–26

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Journal of Molecular Structure: THEOCHEM

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

Electronic structure of Li3

Fabio E. Penotti *
Consiglio Nazionale delle Ricerche, Istituto di Scienze e Tecnologie Molecolari, Via Golgi 19, I-20133 Milano, MI, Italy

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

Article history: Non-orthogonal single- and multi-configuration ab initio calculations have been carried out on ground-
Received 26 February 2008 state Li3 in its minimum-energy C2v geometry. Their results have been compared with published work
Received in revised form 1 April 2008 and with those of SCF, frozen-core SDCI and full-valence CI calculations.
Accepted 2 April 2008
The calculations confirm the feasibility of explicit basis-set optimisation, by second-order analytical
Available online 10 April 2008
methods, for correlated wavefunctions in non-linear molecules, and compare use of optimised STO basis
sets with standard, high-accuracy, GTO basis sets.
Keywords:
The results are used as basis for a discussion of the molecule’s electronic structure.
Electron density
Electron density difference
The molecule’s electron density is shown to exhibit a non-nuclear maximum, both at the SCF and frozen-
Non-nuclear attractors core full-CI levels, and with core-correlated non-orthogonal wavefunctions.
Non-orthogonal multiconfiguration An ‘Atoms-in-Molecules’ topological analysis of the electron density shows features that may be viewed
methods as related to the occurrence of Interstitial Orbitals in non-orthogonal electronic wavefunctions for this
Basis-set optimization system.
The electron density difference map (molecule minus atoms) exhibits a non-nuclear maximum at roughly
the same location as the molecule’s total electron density, plus three 3p-type enrichment-depletion pat-
terns, one centred on each nucleus. Corresponding patterns are found in Li2.
Li3’s electric dipole and electric field gradient at the nuclei are also computed. Unexpectedly, the electric
dipole value is found to exhibit significant dependence on the inclusion of inner-shell out-of-plane cor-
relation in the wavefunction.
Ó 2008 Elsevier B.V. All rights reserved.

1. Introduction
In its equilateral-triangle (D3h) nuclear geometry, the Li3 mole-
cule has a degenerate electronic ground state (X 2E0 ). This is a point
of conical intersection, and as the symmetry is lowered to C2v, the
degenerate state’s two components split in energy, giving rise to
what are usually described as the two sheets of the X 2E0 adiabatic
potential energy surface. A descent-in-symmetry table immedi-
ately shows that the two sheets must correspond to 2B2 and 2A1
electronic states. The B2 sheet turns out to be the one that goes
down in energy as one moves away from D3h geometry, while
the A1 sheet goes up. The two sheets extend of course to cover Cs
geometries as well, where the two states are both A0 , but obviously
cannot split any further as there is no residual electronic degener-
acy, other than that from the non-zero value of the spin.
The adiabatic potential surfaces for the X 2E0 state and the A2E00
state, which also exhibits a conical intersection, have been
accurately characterized in relatively recent work which joined
high-resolution spectroscopy with high-accuracy theoretical calcu-
lations [1–3]. This has shown that, for both the X 2E0 and the A2E00
states, the lower sheet exhibits three equivalent C2v minima, in
* Tel.: +39 2 50314294; fax: +39 2 700507208.
E-mail address: f.penotti@istm.cnr.it
which the three nuclei are at the corners of ‘obtuse’ isosceles trian-
gles, separated by interconversion barriers culminating in saddle
points that correspond to ‘acute’ isosceles triangles [1,2]. (In this
context, an isosceles triangle is usually said to be ‘obtuse’ if its un-
ique angle exceeds the equilateral value of 60°, ‘acute’ otherwise).
The X state interconversion barriers are low enough to give rise
to the dynamic Jahn–Teller effect, making Li3 a ‘floppy’ molecule.
Its rovibrational motion cannot be properly characterized in terms
of a C2v asymmetric rotor and its normal modes of vibration [2]. In
fact, by numerical solution, in hyperspherical coordinates, of the
Schrödinger equation for nuclear motion with the exact rotation–
vibration Hamiltonian, it has been shown that the height of the
interconversion barriers above the minima is less than twice the
zero-point rovibrational energy [2].
On the other hand, the X state’s lowest conical intersection, i.e. the
D3h geometry of lowest energy, lies at a height, above the state’s low-
er sheet’s C2v minima, equal to more than twelve times the zero-
point rovibrational energy, while the vertical excitation energy in
the region of the minima is more than 40 times that same zero-point
energy [2]. This implies that, in the system’s lowest few rovibrational
states, the D3h geometry, and the upper sheet, are essentially inac-
cessible. Therefore, the adiabatic approximation can be safely ap-
plied to obtain low-lying rovibrational states, provided only the
‘geometric phase’ (Berry phase) factor [4] is properly dealt with [1,2].

0166-1280/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.theochem.2008.04.003
 F.E. Penotti / Journal of Molecular Structure: THEOCHEM 861 (2008) 18–26
All this leads to a simple conclusion that is of direct significance
to the present work: the relative inaccessibility of the D3h geome-
try, and of the whole 2A1 sheet, imply that, with a few caveats that
will be raised in this paper’s final section, it makes sense to study
Li3’s electronic structure and density at (any) one of its three equiv-
alent C2v 2B2 minimum-energy geometries, as representative of the
molecule’s actual properties, despite the presence of a conical
intersection right in their midst.
To this end, the present work will take as its starting point a study
[5] of the orbital structure of the single-configuration Spin-Coupled
[6–10] electronic wavefunction for this system (among other Li clus-
ters), and build on its results by considering a series of electronic
wavefunctions that include an increasing number of variationally-
optimised non-orthogonal orbital configurations, in the process
bringing to the forefront Interstitial Orbitals that enter the single-
configuration SC wavefunction, in part, in a somewhat disguised
manner [6–10]. Although this will be a series of nine-electron calcu-
lations, leading up to core-correlated wavefunctions, an effort to as-
sess the accuracy of numerical results will be made by comparing
those of a shorter series of corresponding frozen-core non-orthogo-
nal wavefunctions with those of a frozen-core full-CI calculation.
The molecule’s electron density will be shown to exhibit a non-
nuclear maximum, located rather close to the centre of mass. This
is in agreement with previous RHF results [11], and is of course
hardly a surprise, given that such non-nuclear maxima, though ab-
sent from most molecules [12], appear in higher lithium clusters
[13], while Li2 has long been known to exhibit one at the SCF level
[14], even though its persistence at correlated levels of approxima-
tion has only been proved in more recent times [13,12,15–18].
Moreover, an ‘Atoms-in-Molecules’ [19] topological analysis
will be used to characterize the molecule’s bonding structure,
highlighting Bond Path features that may be viewed as related to
the occurrence of Interstitial Orbitals in the electronic
wavefunction.
Finally, Li3’s electron density difference map (molecule minus
atoms) will be shown to exhibit 3p-type enrichment-depletion pat-
terns, one centred at each nucleus, on top of the expected non-nu-
clear maximum located at about the same position as in the total
density. Corresponding patterns will be shown to exist for Li2.
2. Method
Calculations were carried out in the framework of the Generalized
Multiconfiguration Spin-Coupled (GMCSC) approach [20,21]. The
method is essentially a multiconfiguration generalization of the
Spin-Coupled (SC) approach ([6–8]; see e.g. [9] or [10] for a review),
though it can also be viewed as a non-orthogonal generalization of
the Multiconfiguration Self-Consistent Field (MCSCF) approach.
More specifically, in the GMCSC method the wavefunction is ex-
pressed as a linear combination of configurations, each the anti-
symmetrized product of an orbital ‘string’ and a spin function.
Each orbital ‘string’ is just the product of as many orbitals as there
are electrons, while its associated spin function is a linear combi-
nation of all possible modes of spin coupling, embodied by the
Yamanouchi-Kotani (YK) spin functions [22], with adjustable coef-
ficients termed spin-coupling coefficients. The theory was initially
formulated under the assumption of a single set of spin-coupling
coefficients, common to all configurations, as the MCSC approach
[20], and later generalized to allow for a separate set of spin-cou-
pling coefficients for each configuration [21].
Just as in SCF, SC or MCSCF theory, each orbital is in turn ex-
pressed as a linear combination, with adjustable coefficients (orbi-
tal coefficients), of basis functions, usually of Gaussian or Slater
type. And, just as in the single-configuration SC method, the orbi-
tals are not restricted by double-occupancy or orthogonality
19
requirements, though selective such constraints may be imposed
on arbitrarily chosen configurations [21,23].
In the ‘‘Optimised Basis Set” variant of the GMCSC approach
(OBS–GMCSC) [20,21], basis function exponential parameters are
also treated as adjustable parameters, to be determined by energy
minimization simultaneously with all other variational parameters
in the wavefunction, i.e. configuration, spin-coupling, and orbital
coefficients. Aside from often significant variational improvement,
this ensures rigorous compliance with the virial theorem; of
course, optimisation of a single scale factor, common to all expo-
nential parameters, would suffice for the latter purpose.
Energy minimization is carried out by use of the so-called Sta-
bilized Newton–Raphson method, originally introduced in eco-
nomic theory as ‘‘quadratic hill climbing” [24], a maximization
method, and long used as the workhorse of the single-configura-
tion SC approach [7]. This second-order iterative minimization
method requires the availability of the first and second derivatives
of the energy with respect to all variational parameters, cross
terms included. These are computed analytically at each iteration.
Convergence on an energy minimum, as appropriate for electronic
ground states, is assumed when the second-derivative matrix is
positive definite, and the gradient is essentially zero. In GMCSC cal-
culations, the convergence threshold for gradient components is
usually set at 108 atomic units.
2.1. Geometry, basis sets, integrals
Except when otherwise indicated, calculations were carried out
at the equilibrium C2v geometry, with the two equal Li–Li distances
R set to 5.225 a0 and the intervening angle a set equal to 71.6° [1],
so the third Li–Li distance was 6.113 a0 (here a0 denotes the atomic
unit of distance, or Bohr: 1 a0 = 0.5291772  1010 m [25]).
This minimum-energy geometry, determined in a high-accu-
racy theoretical–experimental study [1–3], is quite close to that
found in high-quality CCSD(T) calculations [26], i.e. R = 5.218 a0
and a = 71.8°.
In the present work, the two symmetry-equivalent nuclei were
placed at (x = 0.0, y = ±3.056404 a0, z = +4.237808 a0), with the
third nucleus at the origin.
Most calculations were carried out with even-tempered
[8s,4p,1d,1f] or [8s,4p,1d] Slater-type basis sets, even-tempered
meaning that the exponential parameters of the 1s STOs were
assumed to be given by
fi ¼ a1s bi1
1s
for i = 1, 2,. . ., 8, and similarly for the four 2p STOs.
STO-based energy integrals were computed using M2CNEW
[27,28], a program that in its newer version, SMILES [29], is being
included in the MOLPRO package [30]. The use of M2CNEW in con-
nection with basis-set optimisation has been discussed elsewhere
[31]. STO-based integrals of the electric field gradient at the nuclei
were computed with the highly accurate and efficient INTEGARM-
IRREG program [32].
Exponential parameters for the larger [8s,4p,1d,1f] basis set
were as optimised for an eight-configuration CASSCF wavefunction
for Li2 [23]. Those for the smaller [8s,4p,1d] basis set were either
equal to the corresponding ones in the larger set, or as directly
optimised for the smaller set, either for the same Li2 CASSCF wave-
function, or specifically for Li3 at various correlation levels. In all
these optimisations, the parameters (a and b) of each of the two
geometric progressions were determined by effectively treating
them as variational parameters (details available, on request, from
the present author), together with the exponential parameters of
the 3d and, when present, 4f STOs, and all other variational param-
eters in the wavefunction. Optimised values are given in Table 1:
20 F.E. Penotti / Journal of Molecular Structure: THEOCHEM 861 (2008) 18–26
no simple trend with increasing correlation can be easily
discerned.
RHF calculations were carried out to establish the zero of corre-
lation energy, both with these STO basis sets and, for comparison,
using the freely available GAMESS-US package [33], with standard
high-accuracy CGTO basis sets. These consisted of (11s,5p,2d,1f)
and (12s,6p,3d,2f,1g) cartesian Gaussian primitives contracted to
[4s,3p,2d,1f] and [5s,4p,3d,2f,1g] CGTOs, respectively, (cc-pVTZ
and cc-pVQZ [34,35]). Numerical results are given in Table 2. As
can be seen, at the RHF level specific optimisation of the basis-
set parameters more than makes up for omission of the 4f STO,
and leads to an energy that is even lower than that given by the
much larger cc-pVQZ Gaussian basis set, albeit not by much
(0.001 eV).
The same two Gaussian basis sets were also used for the single-
configuration Spin-Coupled wavefunction, to provide a correlated-
level comparison with the STO results. In this case, all three STO
basis sets explored (Table 2) led to lower energies than even the
larger Gaussian basis set, by 0.031, 0.034 and 0.040 eV.
3. Results
3.1. The SC description of Li3
For the single-configuration SC wavefunction, variational opti-
misation at the equilibrium C2v geometry spontaneously yields a
‘clean-symmetry’ 2B2 solution, with no need for any symmetry con-
straints. The SC orbitals are all even under reflection in the plane of
the nuclei, and stable with respect to mixing-in of basis functions
that are odd under such reflection. They consist of three pairs of
‘inner’ orbitals (in-pair overlap 93%), and three ‘valence’ orbitals.
Unsurprisingly, one of the inner pairs consists of a1 orbitals that
are essentially atomic 1s orbitals centred on the ‘apical’ nucleus,
a second pair also consists of essentially 1s orbitals, but centred
on one of the two C2-related nuclei, and the third pair can be ob-
tained by applying C2 to the second pair. The ‘valence’ orbitals con-
sist of two a1 orbitals, with a 62% mutual overlap and a 5–14%
overlap with inner orbitals, and a b2 orbital with ±7% and ±12%
overlap with the inner orbitals in the two symmetry-related pairs.
The valence orbitals, as obtained with a specifically optimised
[8s,4p,1d] STO basis set, are depicted in Fig. 1, and are qualitatively
much the same as those obtained in previous work by Tornaghi et
al. [5]. This despite their use of a (9s 5p) ? [3s 2p] Gaussian basis
set, and of a geometry chosen as appropriate for a cut through a bcc
lattice, rather than the isolated molecule, and thus somewhat dif-
ferent from that adopted here. And despite the fact that those cal-
culations adopted a ‘frozen core’ consisting of the lowest three RHF
orbitals (doubly-occupied), to which the valence orbitals could be
taken orthogonal, with the presumable introduction of extra nodal
surfaces close to the nuclei.
In that work [5], one of the valence a1 orbitals was described as
an Interstitial Orbital (IO) associated with the unique side of the
isosceles triangle, and the other two were viewed as the in-phase
(a1) and out-of-phase (b2) combinations of IOs associated with
Table 1
Optimised parameters for even-tempered [8s,4p,1d,1f] and [8s,4p,1d] STO basis sets
Molecule Method Number of configurations
Total Indep.
Li2 CASSCF 8 7
Li2 CASSCF 8 7
Li3 SCF 1 1
Li3 SC 1 1
Li3 GMCSC 6 4
Li3 GMCSC 15 9 (0.520651,
the two equal sides (the occurrence of IOs was a recurrent theme
for higher Li clusters as well [5]).
The valence SC orbitals are reproduced here mostly for compar-
ison with those from multiconfiguration wavefunctions to be dis-
cussed later.
As for the spin part of the SC wavefunction, it is mostly deter-
mined by the observation that there are 42 possible YK spin func-
tions for nine electrons coupled to a doublet, but only two for three
electrons thus coupled. Thus, if the inner orbitals are taken as the
first six orbitals, and ordered pair after pair, only the 28th and
the 42nd (perfect pairing) standard-order YK functions correspond
to singlet coupling of each of the three inner pairs, and not surpris-
ingly the coefficients of the other 40 spin functions turn out to be
of order 103 or less. If furthermore the a1 valence orbitals are ta-
ken as orbitals 7 and 8, the coefficients of YK functions 28 and 42
turn out to be 0.44 and 0.90, respectively, so that perfect pairing
alone accounts for 81% of the wavefunction.
Correspondingly, omission of the 40 ‘secondary’ spin functions
leads to a small energy penalty, of the order of microhartrees, both
for the SC wavefunction and for the multiconfiguration wavefunc-
tions to be described later. Nevertheless, the results given in this
paper always refer to calculations including all 42 spin functions,
subject only to those constraints that are required by symmetry
[38,31] and/or the presence of any doubly-occupied orbitals (the
spin part of the SC wavefunction spontaneously satisfies the
requirements for overall 2B2 symmetry, as expected, in the sin-
gle-configuration case, when orbital symmetry allows [6,38]).
At the SC level specific optimisation of the basis-set parameters
does not quite make up for omission of the 4f STO (see Table 2).
Still, it does lead to an energy which is 0.03 eV lower than that
yielded by the cc-pVQZ CGTO basis set, even though the latter in-
cludes almost three times as many basis functions (249 cartesian
Gaussian primitives contracted to 210 CGTOs, vs. 75 STOs).
3.2. The GMCSC description
It is also possible to obtain, at the same equilibrium C2v geom-
etry, a solution consisting of a pair of configurations that are con-
strained to be connected by a C2 rotation, have equal and opposite
configuration coefficients, and share the same set of spin-coupling
coefficients (so this is, strictly speaking, a MCSC rather than a
GMCSC wavefunction). All orbitals turn out to be even under
reflection in the plane of the nuclei, and the solution thus has clean
2
B2 symmetry, even though each individual configuration does not,
and in fact the two configurations’ 44% overlap implies their sym-
metry distortion is significant. The wavefunction can of course be
seen as a single symmetry-adapted linear combination (SALC) of
two configurations. The six ‘inner’ orbitals in either of the two ‘res-
onating’ configurations are quite similar to their SC counterparts.
On the other hand, two of the valence orbitals appear to be essen-
tially IOs associated with the two equal sides of the triangle. Their
overlap is only about 5%. The third valence orbital looks like a rota-
tion and distortion of SC orbital 9, i.e. the essentially unpaired b2
orbital. The common spin part can be made to be heavily domi-
1s (a/a01, b) 2p (a/a01, b) 3d f 4f f
(0.573899, 1.455226) (0.636270, 1.424770) 0.788438 0.948885
(0.578254, 1.451966) (0.720272, 1.390743) 0.863570 ––
(0.565501, 1.454940) (0.523926, 1.648522) 0.789639 ––
(0.602985, 1.499617) (0.583532, 1.498391) 0.800953 ––
(0.517043, 1.420801) (0.708769, 1.703738) 0.858543 ––
1.420011) (0.704527, 1.745813) 0.866966 ––
 F.E. Penotti / Journal of Molecular Structure: THEOCHEM 861 (2008) 18–26 21

Table 2
Main numerical results at MR–CI equilibrium geometry (R = 5.225 a0, h = 71.6° [1])

Method Configurations E/Eha Ecorrb/eV lc/D Electric field gradient d/(103 e a03)
Total Indep. Nucleus 1 Nuclei 2 and 3
|| || || ||
RHFe 1 1 22.308131 0.67 9.9 +1.4 +8.5 4.7 2.9 +7.6
RHFf 1 1 22.308196 0.65 10.1 +1.5 +8.6 4.7 2.8 +7.5
RHFg 1 1 22.308229 0.65 10.4 +1.8 +8.6 4.9 2.7 +7.6
RHFh 1 1 22.308277 0.68 10.3 +1.9 +8.4 4.9 2.7 +7.6
OBS–RHFi 1 1 22.308325 0.00 0.68 10.4 +1.8 +8.6 4.9 2.9 +7.8
SCh 1 1 22.372502 1.75 1.48
SCi 1 1 22.373652 1.79 1.46 14.1 6.2 +20.3 9.6 3.5 +13.1
OBS–SCj 1 1 22.373739 1.79 1.44 13.9 6.3 +20.3 9.5 3.6 +13.0
SCg 1 1 22.373976 1.79 1.46 14.3 5.9 +20.2 9.8 3.1 +12.9
MCSCg 2 1 22.380238 1.96 0.12 8.1 0.2 +8.3 13.9 3.3 +17.2
VB–CIg 3 2 22.380994 1.98 0.51 13.9 3.8 +17.7 8.3 0.8 +9.1
GMCSCg 3 2 22.399022 2.47 0.36 17.5 +5.6 +11.9 11.8 +0.2 +11.6
GMCSCg 4 3 22.403465 2.59 0.53 16.2 +5.7 +10.5 10.7 1.2 +11.9
GMCSCg 6 4 22.407860 2.71 0.49 15.2 +5.3 +10.0 8.9 1.6 +10.5
GMCSCg 8 5 22.408013 2.72 0.49 15.1 +5.4 -9.8 8.9 1.7 +10.6
GMCSCf 6 4 22.406898 2.68 0.48 14.4 +4.0 +10.4 8.1 1.4 +9.5
GMCSCk 6 4 22.408555 2.73 0.42 15.3 +5.9 +9.4 9.0 2.0 +11.0
OBS–GMCSCl 6 4 22.412503 2.84 0.34 19.5 +5.2 +14.3 13.1 2.9 +16.0
GMCSCl 9 6 22.418797 3.36 0.37 4.0 2.4 +6.5 13.3 2.5 +15.8
GMCSCl 15 9 22.444839 3.72 1.01 10.8 3.8 +14.6 5.2 3.5 +8.7
OBS-GMCSCm 15 9 22.444953 3.72 1.00 10.8 3.9 +14.7 5.2 3.5 +8.7
CCSD(T)n 22.48830 4.90
D–QMCo 22.4900 ± 0.0023 4.94 ± 0.06
Experiment 22.502 ± 0.006p 5.3 ± 0.2
a
Eh denotes the atomic unit of energy, or Hartree: 1 Eh = 4.35975  1018 J [25].
b
Correlation energy, in electron-volts: 1 eV = 1.602177  1019 J [25].
c
Electric dipole moment, in Debye: 1 D = 3.335641  1030 C m [25].
d
Eigenvalues of the electronic distribution’s electric field gradient at the nuclei (traceless part only), in atomic units: 1 ea03 = 1.081203 1022 C m3 [25]. Symbols label
the direction of the corresponding eigenvectors (perpendicular to the plane of the nuclei: ; in the plane of the nuclei: ||).
e
(11s,5p,2d,1f) ? [4s,3p,2d,1f] cartesian GTO basis (cc-pVTZ [34]).
f
[8s,4p,1d] even-tempered STO basis, exp. parameters as optimised for Li2 [8s,4p,1d,1f] basis (CASSCF).
g
[8s,4p,1d,1f] even-tempered STO basis, exponential parameters as optimised for Li2 (CASSCF).
h
(12s,6p,3d,2f,1g) ? [5s,4p,3d,2f,1g] cartesian GTO basis (cc-pVQZ [34]).
i
[8s,4p,1d] even-tempered STO basis, exp. parameters as optimised for SCF wavefunction.
j
[8s,4p,1d] even-tempered STO basis, exp. parameters as optimised for SC wavefunction.
k
[8s,4p,1d] even-tempered STO basis, exp. parameters as optimised for Li2 (CASSCF).
l
[8s,4p,1d] even-tempered STO basis, exponential parameters optimised for six-configuration GMCSC wavefunction.
m
[8s,4p,1d] even-tempered STO basis, exponential parameters optimised for 15-configuration GMCSC wavefunction.
n
CCSD(T) calculation [26], with (15s,9p,5d,3f,1g) ? [8s,7p,5d,3f,1g] dunning cc-pwCVQZ GTO basis.
o
Diffusion Quantum Monte Carlo calculation, with a geometry optimised at CASSCF level (R = 5.31 a0, h = 71.2°) [11].
p
Three times the total energy of Li [36], plus the experimental dissociation energy of Li3 [37], plus its zero-point energy [1,2], assuming errors to be dominated by that on
the dissociation energy [37].

nated by perfect pairing, with a 0.9998 coefficient, provided this
latter orbital is taken as # 7, i.e. spin-paired with one of the two
IOs, with which it has a 66% overlap, while the other IO, which
has a 31% overlap with orbital 7, is made orbital 9, i.e. the un-
paired orbital.
As can be seen from Table 2, the two-configuration solution’s
correlation energy is 1.96 eV, to be compared with the SC solution’s
1.79 eV.
The relative importance of the two descriptions can be better
assessed by putting these two equivalent configurations together
with the SC configuration, in a three-configuration wavefunction.
If this is done simply in a non-orthogonal CI calculation (VBCI),
equivalent to varying only configuration and spin-coupling coeffi-
cients while keeping all orbitals fixed, the correlation energy in-
creases a paltry 0.02 eV to 1.98 eV. However, if all orbitals are
simultaneously re-optimised, in a three-configuration GMCSC cal-
culation that includes an SC-like configuration, identified as such
by appropriate orbital and spin symmetry constraints [38,30],
and a pair of configurations that are constrained to be related by
C2 and to have identical spin-coupling coefficients, with all orbitals
constrained to be invariant under reflection in the plane of the nu-
clei, the correlation energy increases to 2.47 eV.
In such a calculation, the re-optimised SC-like configuration
ends up having a limited overlap (±33%) with each of the other
two configurations, whose mutual overlap rises to 72%.
Perfect pairing remains dominant for all three configurations.
The SC-like configuration assumes a weight (Chirgwin-Coulson
occupation number [39]) equal to 0.36, with the two symmetry-
equivalent configurations making up the balance to 1.0. This sug-
gests all three configurations are equally important, and should
be taken as reference functions for the introduction of double exci-
tations, to provide ‘‘out-of-plane” correlation.
The re-optimised orbitals in the SC-like configuration are rea-
sonably similar to their counterparts in the SC wavefunction itself,
but the three ‘valence’ ones display extra nodal surfaces, a struc-
ture that they will retain when doubly-excited configurations are
added. In fact, they are quite similar to their counterparts in a
15-configuration GMCSC wavefunction to be described later (see
Fig. 2), though in the latter the a1 orbital that was viewed as an
IO associated with the triangle’s unique side moves towards the
molecule’s central region, its amplitude showing a maximum at
y = 0.0 a0, z = 2.48 a0, and could be described as the in-phase com-
bination of either all three IOs, or of three distorted sp2-type hy-
brids, each centred on one of the nuclei. The two descriptions
22 F.E. Penotti / Journal of Molecular Structure: THEOCHEM 861 (2008) 18–26

Fig. 2. Contour plots of the amplitudes, in the plane of the nuclei, of the SC-like
Fig. 1. Contour plots of the amplitudes, in the plane of the nuclei, of the single- configuration’s ‘valence’ orbitals in the 15-configuration GMCSC wavefunction.
configuration SC ‘valence’ orbitals. Contours have been drawn every 0.02 a03. Contours have been drawn every 0.02 a03. Dashed lines mark negative contours.
Dashed lines mark negative contours.

can perhaps be reconciled, if the IOs themselves are assumed to

arise from the superposition of the sp2-type hybrids.
The appearance of the orbitals in the two C2-related configura-
tions also remains more or less the same as in the two-configura-
tion MCSC wavefunction. And while the two that are essentially
IOs associated with either of the equal sides of the triangle will re-
tain their essence in the final 15-configuration wavefunction (see
Fig. 3), the one that in the three-configuration wavefunction still
looks like a distortion of the b2 SC orbital will there take on its ex-
pected role as the third IO, the one associated with the triangle’s
unique side, undergoing substantial changes that will make it look
like a very recognizable distortion of its a1 counterpart in the SC
wavefunction (Fig. 3). It thus appears that it takes the inclusion
of three reference configurations and of ‘out-of-plane’ double exci-
tations out of them to see all three IOs make their direct appear-
ance in the wavefunction.
To gain some sense of the convergence behaviour, double exci-
tations out of the three reference configurations were added in
stages. First, one consisting in the replacement of the ‘valence’ pair
of a1 orbitals in the SC-like configuration with a doubly-occupied
b1 orbital, recovering an extra 0.12 eV of correlation energy. Then,
a pair of C2-related configurations obtained by replacing the first
two of the a0 valence orbitals in either of the other two reference
configurations with one of a pair of C2-related doubly-occupied
a00 orbitals (a0 and a00 are used here to denote orbitals that are only
constrained to be even or odd, respectively, under reflection in the Fig. 3. Contour plots of the amplitudes, in the plane of the nuclei, of the ‘valence’
plane of the nuclei, using Cs-group notation). This GMCSC calcula- orbitals in one of the pair of C2-related reference configurations, as they appear in
tion, whose configurations are the first six listed in Table 3, recov- the 15-configuration GMCSC wavefunction. Contours have been drawn every
0.02 a03. Dashed lines mark negative contours.
ered a further 0.12 eV of correlation energy. Adding a pair of C2-
related configurations obtained by replacing the first and third of
the a0 valence orbitals in either of the two C2-related reference con- two configurations, not listed in Table 3, were omitted in subse-
figurations (orbitals 7 and 9) with one of another pair of C2-related quent calculations.
doubly-occupied a00 orbitals, in an eight-configuration GMCSC cal- As can be seen from Table 2, at the six-configuration level spe-
culation, yielded only an extra 0.01 eV of energy (Table 2). These cific optimisation of the basis-set parameters more than made up
 F.E. Penotti / Journal of Molecular Structure: THEOCHEM 861 (2008) 18–26 23

for omission of the 4f STO, as had been the case at the RHF level In an effort to assess the accuracy of the present results, at least
(but not at the SC level). with respect to the treatment of valence correlation, frozen-core
Subsequent calculations added inner-shell ‘out-of-plane’ corre- calculations, using SCF core orbitals, were carried out at various
lation, first for the SC-like configuration: one excitation consisted correlation levels, all the way up to full-valence CI (FVCI). To make
in the replacement of the pair of ‘inner’ a1 orbitals with a dou- the latter calculation possible, with the freely-available GAMESS
bly-occupied b1 orbital, while two other symmetry-related excita- [33] program, on the present author’s PC, the cc-pVTZ CGTO basis
tions were obtained by replacing either of the two C2-related set was used. The results, given in Table 4, show that the frozen-
‘inner’ orbital pairs with one of two doubly-occupied (and C2-re- core six-configuration GMCSC wavefunction recovers 86% of the
lated) a00 orbitals. This nine-configuration GMCSC calculation full-valence correlation energy, and provides a value of the dipole
yielded an extra 0.52 eV of correlation energy (Table 2). moment that is in reasonably good agreement with the FVCI value.
Finally, six more configurations were added, similarly providing In fact, the six-configuration GMCSC dipole value is better than
inner-shell ‘out-of-plane’ correlation for the pair of C2-related ref- that obtained in a CI calculation supplementing the SCF configura-
erence configurations, yielding an extra 0.36 eV of correlation en- tion with all (valence) single and double excitations out of it (SDCI),
ergy. As can be seen from Table 2, this final GMCSC wavefunction even though the latter, with its 5713 configurations, recovers 95%
recovers about 70% of the total correlation energy. The list of all of the full-valence correlation energy. On the other hand, the six-
15 configurations can be found in Table 3. configuration GMCSC dipole moment is still little more than half
The final wavefunction remained dominated by the first three that yielded, upon inclusion of core correlation, by the 15-configu-
configurations (weights: 0.28, 0.35, 0.35), the other 12 configura- ration GMCSC wavefunction. Since ‘in-plane’ core correlation does
tions having weights that, while positive, were all below 0.01. Per- not increase dipole moment values, as can be seen in a comparison
fect pairing still dominated all configurations. The re-optimised SC- of Table 4 results with their Table 2 counterparts, the accuracy of
like configuration ended up having a ±88% overlap with each of the the 15-configuration GMCSC value hinges on its last nine configu-
other two reference configurations, whose mutual overlap became rations providing an adequate description of ‘out-of-plane’ core
large and negative (95%). correlation.
As can be seen from Table 2, inclusion of inner-shell ‘out-of-
plane’ correlation, aside from lowering the total energy, unexpect- 3.3. Electron density
edly almost tripled the molecule’s electric dipole moment, to 1.0 D,
a value that falls roughly halfway between the RHF and SC values. At the C2v minimum-energy geometry, the molecule’s electron
One might suspect that this may be due to the fact that some core density was searched for any maxima or minima. Density values
correlation was allowed in, already at the single-configuration SC were first computed on a three-dimensional grid covering the
level, by lifting the double-occupancy constraint on inner orbitals. range 0.0 a0 6 x 6 +4.0 a0, 6.0 a0 6 y 6 +6.0 a0, 2.0 a0 6 z 6
However, when the SC calculation was repeated, using the even- +6.0 a0. Then, each grid point at which the density was higher
tempered STO [8s,4p,1d,1f] basis set, with the six inner orbitals (lower) than at all nearest neighbours and next-nearest neighbours
constrained to be identical in pairs, thus restoring the double-occu- was taken as a starting point for a stabilized Newton–Raphson
pancy constraint on inner orbitals, the overestimated dipole mo- search, using analytical values of the density’s first and second
ment fell by less than 0.01 D (while the energy rose by as much derivatives with respect to the three cartesian coordinates. As
as 1.21 eV). mentioned above, one of the nuclei was placed at the origin, the
The electric field gradient at the nuclei also appears to be signif- other two at (x = 0.0, y = ±3.056404 a0, z = +4.237808 a0).
icantly affected by inner-shell ‘out-of-plane’ correlation (Table 2), The molecule’s electron density was found to exhibit a non-nu-
but this is perhaps to be expected. More generally, both quantities clear maximum; no minima were found. The contour plot in Fig. 4
appear to be quite sensitive to the level of correlation included. Of has been obtained from the 15-configuration OBS–GMCSC
course, the best values should be those obtained with the 15-con- wavefunction.
figurations OBS–GMCSC wavefunction. Here the non-nuclear maximum has about the same value as
that exhibited by Li2: 0.0121 a03 compared with 0.0132 a03 for
the diatomic (see e.g. Ref. 40). In Fig. 4 the triatomic’s maximum
Table 3
Orbital configurationsa used in GMCSC calculations on Li3 lies at z = 3.095 a0, just 0.27 a0 from the molecular centre of mass,
which is at z = 2.825 a0.
1 1a1 2a1 1a0 2a0 C21a0 C22a0 3a1 4a1 1b2
As originally shown by R.K. Owen at a similar geometry
2 3a0 4a0 5a0 6a0 7a0 8a0 9a0 10a0 11a0
3 C23a0 C24a0 C25a0 C26a0 C27a0 C28a0 C29a0 C210a0 C211a0 (R = 5.31 a0, h = 71.2°) [11], a corresponding non-nuclear maximum
4 1a1 2a1 1a0 2a0 C21a0 C22a0 1b1 1b1 1b2 is found at the RHF level. In the present work, its existence has also
5 3a0 4a0 5a0 6a0 7a0 8a0 1a00 1a00 11a0
6 C23a0 C24a0 C25a0 C26a0 C27a0 C28a0 C21a00 C21a00 C211a0
7 2b1 2b1 1a0 2a0 C21a0 C22a0 3a1 4a1 1b2 Table 4
8 1a1 2a1 2a00 2a00 C21a0 C22a0 3a1 4a1 1b2 Main frozen-core results (cc-pVTZ basis set) at MR–CI equilibrium geometry
9 1a1 2a1 1a0 2a0 C22a00 C22a00 3a1 4a1 1b2 (R = 5.225 a0, h = 71.6° [1])
10 3a00 3a00 5a0 6a0 7a0 8a0 9a0 10a0 11a0
11 3a0 4a0 4a00 4a00 7a0 8a0 9a0 10a0 11a’ Method Configurations E/Eha Ecorrb/eV lc/D
12 3a0 4a0 5a0 6a0 5a00 5a00 9a0 10a0 11a0
Total Indep.
13 C23a00 C23a00 C25a0 C26a0 C27a0 C28a0 C29a0 C210a0 C211a0
14 C23a0 C24a0 C24a00 C24a00 C27a0 C28a0 C29a0 C210a0 C211a0 RHF 1 1 22.308131 0.00 0.670
15 C23a0 C24a0 C25a0 C26a0 C25a00 C25a00 C29a0 C210a0 C211a0 SC 1 1 22.329182 0.573 (42%) 1.449
a
MCSC 2 1 22.335155 0.735 (54%) 0.288
Orbitals are identified by a symmetry label preceded by a number, which is only GMCSC 3 2 22.342923 0.947 (70%) 0.379
meant to distinguish different orbitals of the same symmetry. Thus, 1a1 is the first GMCSC 6 4 22.351403 1.177 (86%) 0.508
orbital of a1 symmetry, in the full C2v group, appearing in the Table, while 2a1 is the SDCI 5713 5713 22.355417 1.287 (95%) 0.437
second orbital of the same symmetry. The a’/a00 labels are used to denote orbitals FVCI 92,167 92,167 22.358161 1.361 (100%) 0.587
which are even/odd under reflection in the plane of the nuclei, but are neither even
a
nor odd under the other operations of the C2v group. Note different orbitals are not Eh denotes the atomic unit of energy, or Hartree: 1 Eh = 4.35975  1018 J [25].
b
orthogonal, unless this is implied by symmetry. In fact, the first three pairs of every Correlation energy, in eV, and as a percentage of the full-valence correlation
configuration are essentially ‘inner’ orbitals, and the two orbitals of each such pair, energy.
c
even when different, overlap strongly (and are almost exactly singlet-coupled). Electric dipole moment, in Debye: 1 D = 3.335641  1030 C  m [25].
24 F.E. Penotti / Journal of Molecular Structure: THEOCHEM 861 (2008) 18–26
been verified at the FVCI level (cc-pVTZ basis set) and, at the RHF
level, both with CGTO (cc-pVTZ and cc-pVQZ [34,35]) and STO ba-
sis sets (the [8s,4p,1d,1f] optimised for Li2, and with the specifically
optimised [8s,4p,1d]). Of course, quantitative details do depend on
basis set and correlation level (see Table 5).
Fig. 4 also shows, superimposed on the contour plot, so-called
Bond Critical points (BCPs) and Bond Paths, defined in accordance
with Baden’s ‘‘Atoms-in-Molecules” theory [19]. The Bond Paths’
trajectories support the contention that the three nuclei are indi-
rectly bound together, through the electron density’s non-nuclear
maximum, in accordance with similar observations for Li2, Li4
and Li5 [13]. It is interesting to note that two of the three Bond
Paths, as they lead away from the non-nuclear maximum, initially
bend in the general direction of the midpoints of the two equiva-
lent sides of the ‘nuclear triangle’, before turning towards the
two equivalent nuclei. This feature, which is even more obvious
in the shape of one of the two 0.011 a.u. contours, may be con-
nected with the appearance of Interstitial Orbitals in the electronic
wavefunction. In any case, this ‘bending’ is barely discernible in a
similar plot based on the SCF wavefunction, but well developed
for the full-valence CI density. It thus appears to be mostly a prod-
uct of electron correlation, whether or not one wishes to ascribe it
to Interstitial Orbitals.
Values of the laplacian of the electron density at the three BCPs
are approximately +0.01 a.u. They are therefore of comparable
magnitude to those found in Li2, Li4 and Li5 [13], and much smaller
than typical molecular values [19], implying a low value of kinetic
energy per electron, a trait that has been associated with good con-
duction properties [12].
In general, positive values of the laplacian imply the electron
density is locally depleted and, when found at BCPs, are usually
associated with non-covalent interactions dominated by kinetic-
energy contributions [19]. However, the significance, in this re-
spect, of laplacian values at BCPs has been downplayed for Li2,
Li4 and Li5 [13], in favour of the dominant negative sign of the
laplacian in the internuclear regions, taken to imply covalent inter-
actions dominated by potential-energy contributions [19,13]. This
behaviour of the laplacian can be seen in Li3 as well (Fig. 5).
At intermediate correlation levels, the non-nuclear maximum
can actually split into two or three maxima. Notably, at the sin-
gle-configuration Spin-Coupled level, with STO basis sets (both
the [8s,4p,1d,1f] optimised for Li2, and the specifically optimised
[8s,4p,1d]), and with the CGTO cc-pVTZ [34,35] basis, there are
three non-nuclear maxima. For these basis sets, the highest of
the three non-nuclear maxima lies on the z axis, at z = +3.7 bohr.
The other two, symmetry-equivalent, non-nuclear maxima are at
Fig. 4. Contour plot of Li3’s electron density, in the plane of the nuclei, as computed
from the 15-configuration GMCSC wavefunction. Contours have been drawn every
0.001 a03, up to 0.012 a03 (the nuclear cusps rise to 13.862, 13.862 and 13.819 a03).
Crosses mark the positions of the nuclei, black dots those of the three Bond Critical
Points. Bond Paths have also been marked.
y = ±1.8 bohr, z = +2.1 bohr. However, the cc-pVQZ single-configu-
ration SC electron density exhibits a single maximum at
z = +3.69 bohr, and two equivalent saddle points at y = ±1.87 bohr,
z = +2.05 bohr. These two saddle points are characterized by a sin-
gle positive (and rather small) eigenvalue of the second-derivative
matrix. Because of this, and of their positions, they are obviously
closely related to the two symmetry-equivalent non-nuclear max-
ima observed, also at the SC level, with the cc-pVTZ and STO basis
sets.
For the six-configuration GMCSC wavefunction, an admittedly
minor splitting of the electron density non-nuclear maximum, into
a pair of closely-spaced and symmetrically placed maxima with
barely a dip between them, also appears to be basis-set dependent
(see Table 5).
Though at this minimum-energy geometry such ‘splittings’ are
probably an artefact of specific correlation levels and basis sets,
similar behaviour would actually not be unexpected over some
range of geometries, in analogy with what has been well docu-
mented for Li2 (see e.g. Ref. [40], and references therein).
At the D3h geometry of lowest energy (R = 5.428 a0 [1,2]), the
electron density also appears to show a single non-nuclear maxi-
mum which, for the 2E0 component correlating with 2B2, lies at
4.1, 2.8 and 2.8 a0 from the three nuclei (1.0 a0 from the molecular
centre of mass), and has a value of 0.0131 a03. For the orthogonal
component, it lies on the opposite side of the molecular centre of
mass, at 0.6 a0 from it and at 2.5, 3.5 and 3.5 a0 from the three nu-
clei, and has a value of 0.0128 a03.
At the C2v interconversion saddle points (R = 5.715 a0, a = 52.2°
[1,2]), an electron density maximum is found close to the midpoint
between the two equivalent nuclei, whose separation is only
5.029 a0, close to the experimental equilibrium internuclear dis-
tance in Li2 (5.051 a0 [41]).
3.4. Electron density difference
If the electron density difference (molecule minus atoms) is
plotted in the nuclear plane, one also observes a non-nuclear max-
imum not far from its location in the total molecular density, plus
three 3p-type enrichment-depletion patterns, with their own posi-
tive-lobe maxima and negative lobe minima, one such pattern cen-
tred at each nucleus. The contour plot in Fig. 6 was obtained using
the 15-configuration OBS–MCSC wavefunction for the molecule,
and, for each Li atom, a nine-configuration OBS–GMCSC wavefunc-
tion that can be described as
X
3 X
5
2
ðsI sII sIII Þ þ k ðp2a sIV Þ þ l ðdb sV Þ;
a¼1 b¼1
with both spin functions included for the first configuration. The
atomic wavefunction used a specifically-optimised even-tempered
[8s,4p,1d] STO basis set.
In this contour plot, the axes of the 3p-type patterns appear to
meet at approximately z = 1.0 a0. On the other hand, the non-nu-
clear maximum closest to the one in the total density lies at
z = 3.40 a0, and has a value of 0.006 a03. Qualitatively similar pat-
terns have been observed at all correlation levels and with all basis
sets (Gaussian and Slater) explored. They also occur at the D3h
geometry of lowest energy (R = 5.428 a0 [1,2]), with details
depending on which of the two spatial components of the 2E0 state
is being considered.
Such patterns have been previously published for higher lith-
ium clusters [42], and in the present case their orientation does
not appear incompatible with the contention that this molecule’s
electron density binds the three nuclei indirectly, through its
non-nuclear maximum. They also occur in the diatomic:
Fig. 7 shows a plot, at the diatomic’s experimental equilibrium
 F.E. Penotti / Journal of Molecular Structure: THEOCHEM 861 (2008) 18–26 25

Table 5
Electron-density non-nuclear maxima at MR–CI equilibrium geometry (R = 5.225 a0, h = 71.6°; all values in a.u.) [1]

Method Configurations Position Electron density Hessian eigenvaluesa/103

Total Indep. y z xb yb zb
c
SCF 1 1 0.00 +2.73 0.01339 4.57 0.53 3.31
SCFd 1 1 0.00 +2.69 0.01336 4.62 0.31 3.19
OBS–SCFe 1 1 0.00 +2.70 0.01321 4.37 0.32 3.14
FVCIc 92,167 92,167 0.00 +2.79 0.01280 4.24 0.43 2.77
GMCSCf 3 2 0.00 +2.76 0.01279 4.88 0.45 2.38
GMCSCf 6 4 0.00 +2.74 0.01239 3.92 0.32 2.53
OBS-GMCSCg 6 4 ±0.15 +2.68 0.01206 3.80 0.02h 2.32i
OBS-GMCSCj 15 9 0.00 +3.10 0.01208 3.78 0.56 1.87
a
Eigenvalues of the matrix of the electronic density’s second derivatives wrt cartesian coordinates.
b
Direction of the corresponding eigenvectors. The nuclei are in the yz plane; the C2 axis lies along z (see text).
c
(11s,5p,2d,1f) ? [4s,3p,2d,1f] cartesian GTO basis (cc-pVTZ [34]).
d
(12s,6p,3d,2f,1g) ? [5s,4p,3d,2f,1g] cartesian GTO basis (cc-pVQZ [34]).
e
[8s,4p,1d] even-tempered STO basis, exponential parameters as optimised for SCF wavefunction.
f
[8s,4p,1d,1f] even-tempered STO basis, exponential parameters as optimised for Li2 (eight-configuration CASSCF).
g
[8s,4p,1d] even-tempered STO basis, exponential parameters as optimised for six-configuration GMCSC wavefunction.
h
The corresponding eigenvectors actually lie at ±3.75° from the y axis.
i
The corresponding eigenvectors actually lie at ±3.75° from the z axis.
j
[8s,4p,1d] even-tempered STO basis, exponential parameters optimised for 15-configuration GMCSC wavefunction.

4. Conclusions

A compact non-orthogonal multiconfiguration wavefunction

Fig. 5. Contour plot of Li3’s electron density laplacian, in the plane of the nuclei, as
computed from the 15-configuration GMCSC wavefunction. Contours have been
drawn at ±2  10n a05, ±410n a05, ±810n a05, for n = 3, 2, 1, and 0, as in [13].
Dashed lines mark negative contours. The laplacian reaches arbitrarily large nega-
tive values sufficiently close to the nuclear cusps, at which it is of course undefined.
has been obtained for Li3 in its ground-state C2v minimum-energy
geometry. This wavefunction is based on just three reference con-
figurations, two of which symmetry-equivalent, and 12 ‘excita-
tions’ out of them, for a grand total of 15 configurations, which
can be grouped in just nine SALCs. Yet it is able to recover, for this
nine-electron open-shell system, about 70% of the total correlation
energy.
The description of the electronic structure that emerges can be
viewed as a relatively straightforward generalization and refine-
ment of that provided by the single-configuration SC wavefunction,
and in fact brings to the forefront the Interstitial Orbitals invoked
in the interpretation of the latter [5]. Given that, at the SC level,
descriptions in terms of Interstitial Orbitals apply to higher Li clus-
ters as well [5], broad aspects of its GMCSC generalization, as ob-
tained for Li3, can be reasonably expected to also extend to
higher clusters.
Li3’s electron density has been found to exhibit, in agreement
with previous RHF results [11], a non-nuclear attractor, coupled
with features that may be viewed as connected with the appear-
ance of Interstitial Orbitals in the electronic wavefunction. A topo-
logical ‘‘Atoms-in-Molecules” analysis of the electron density
supports the contention that the three nuclei are indirectly bound
to one another through the non-nuclear attractor, in agreement
with findings for higher clusters [13].

Fig. 6. Contour plot of Li3’s electron density difference (molecule minus atoms, see
text), in the plane of the nuclei. Contours have been drawn every 0.001 a03. Dashed
lines mark negative contours.

Fig. 7. Contour plot of Li2’s electron density difference (molecule minus atoms, see
internuclear distance of 5.051 a0 [41], as obtained from a nine-con- text), in a plane containing the internuclear axis. The nuclei are at z = ±2.5255 a0.
figuration GMCSC molecular wavefunction [23] and single-config- Contours have been drawn every 0.002 a03 (note this is twice the interval of Fig. 5).
uration SC atomic wavefunctions. Dashed lines mark negative contours.
26 F.E. Penotti / Journal of Molecular Structure: THEOCHEM 861 (2008) 18–26

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