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DOI: 10.1039/D0CP02750B.
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 Page 1 of 22 Physical Chemistry Chemical Physics

Structural effects of alkali-metals on the B12

View Article Online
DOI: 10.1039/D0CP02750B

Physical Chemistry Chemical Physics Accepted Manuscript

skeleton
Gerardo Hernández-Juárez,1 Estefanía Ravell,1 Jessica Arcudia,1 Ximena Zarate,2 Zhong-hua Cui,3

Gabriel Merino,1,* Jorge Barroso.1,*

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1Departamento de Física Aplicada, Centro de Investigación y de Estudios Avanzados,

Unidad Mérida, km 6 Antigua carretera a Progreso, Apdo. Postal 73, Cordemex, 97310

Mérida, Yucatán, México

2Instituto de Ciencias Químicas Aplicadas, Facultad de Ingeniería, Universidad Autónoma

de Chile, Av. Pedro de Valdivia 425, Santiago, Chile

3Institute of Atomic and Molecular Physics, Jilin Provincial Key, Laboratory of Applied

Atomic and Molecular Spectroscopy, Jilin University

Changchun, China

E-mail: gmerino@cinvestav.mx

jorge.barroso@cinvestav.mx
 Physical Chemistry Chemical Physics Page 2 of 22

Abstract View Article Online

DOI: 10.1039/D0CP02750B

After an exhaustive exploration of the potential energy surface of B12E- and B12E2 (E=Li-Cs)

Physical Chemistry Chemical Physics Accepted Manuscript

systems, it was found that for the anionic series, a cage-type and a quasi-planar structure (very

similar to the naked B12 cluster) compete to be the putative global minimum. For neutral

systems, competition arises between the quasi-planar cluster and a double-ring with the alkali-

metals on the highest-symmetry axis. The chemical bonding analyses show that for the entire
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series, the interaction, predominantly electrostatic, is essentially indistinguishable regardless

of the alkali-metal and insufficient for determining the isomeric preference. The isomerization

energy decomposition analysis (IEDA) reveals that in the anions, the structural change in the

lighter complexes is possible because of the relatively low energy required for the boron

skeleton deformation, as opposed to the case of heavy metals. In the case of the neutral systems,

the factor determining one isomer over the other corresponds to that of the energy deformation

of the alkali-metal dimer.

 Page 3 of 22 Physical Chemistry Chemical Physics

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DOI: 10.1039/D0CP02750B

Introduction

Physical Chemistry Chemical Physics Accepted Manuscript

The electronic deficiency of boron is its blessing and curse. On the one hand, the plethora of

unusual geometries adopted by these systems makes it a promising candidate for a wide range

of applications with exciting properties, such as superhard,1 semiconducting,2 and magnetic

materials,3 but on the other hand, the bonding pattern, though extensively studied, remains
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unpredictable and sometimes disconcerting.4–7

In small clusters, the story is no different. Progress in determining the structure of boron

clusters is recent. For pure boron anionic clusters with as many as 40 atoms, it has been possible

to identify, by photoelectronic spectroscopy and theoretical computations, a planar or quasi-

planar geometry.5–10 In contrast, for neutral clusters, it is suggested that the 2D to 3D transition

occurs at B20,11 and for cationic systems at B16+.12 Therefore, not only does the increase in the

number of boron atoms lead to tubular- and cage-shaped clusters, among other three-

dimensional forms, but that the charge of the system also has a decisive role.

In some cases, the doping of some boron clusters creates completely different forms.

For example, if B10 is doped with Nb or Tb, it is transformed into a flat boron wheel with the

metal at the center,13 Similarly, in B6Ta2, B8Ln2, and BxLa2 (x = 7-9), the lanthanide or

transition metal atoms induce the formation of monocyclic boron rings, which are not found in

bare boron clusters.14–16 In B18Co and B18Rh, a drum and a metallo-borophene are the two most

stable structures lying very close to each other in energy.17,18 For the instance of B11-, two

completely different but energetically favorable structures arise from doping it with Be6.19 In

some boron clusters, doping enables dynamic properties to the system, such as the nano-

compasses B8Mg2,20 B7M2- and B8M2 (M = Zn, Cd, Hg),21 or some Wankel-type rotors

described by some of us.22–25 Among the various topologies, motifs of two or three boron rings

with the doping atoms on the axis of highest symmetry are regularly found as the putative
 Physical Chemistry Chemical Physics Page 4 of 22

global minimum, such as the double-rings B16Co,26 B18Na2 and B18Na2-,27 B18Mg,DOI:
28 the three-
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10.1039/D0CP02750B

ring tubular structure in Li2B24,29 or the cage-shape for the case of B24Mo.30

Physical Chemistry Chemical Physics Accepted Manuscript

A particularly exciting example is the B12 icosahedron, which is a ubiquitous building

block in the bulk phases of boron.31–33 The naked B12 is a quasi-planar cluster that is only

slightly modified by the interaction with one lithium, but two lithium atoms interacting

electrostatically give rise to a double boron ring as the lowest-lying structure.34 Similarly, B24
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requires two lithium atoms to turn into a triple-ring boron tube, the smallest so far.29 More

recently, some of us found that the putative global minimum for the B10M2 (M = Rh, Ir) clusters

also adopt a double boron ring with the transition metal atoms interacting covalently with the

boron skeleton.35 Thus, an inevitable question comes to mind: which factors, and to what

extent, lead to such a radical structural rearrangement as that of the double boron ring? To

answer these questions and have a better understanding of the boron bonding nature, herein,

we perform a series of computations. After a systematic exploration of the potential energy

surfaces (PESs) of B12E- and B12E2 (E = Li-Cs), we established that the quasi-planar Cs (A)

structure, similar to the bare B12, stands as the global minimum except with lithium, for which

it competes with a cage-shaped C2v structure (B) for anionic systems or with a double D6d ring

(C) for the neutral cases. We rationalized the structural preference in terms of the Natural Bond

Orbital (NBO), and through the Isomerization Energy Decomposition Analysis (IEDA) and

ultimately found that the structural preference is given by the distortion energy. In the case of

the anions with lighter alkali-metals, less energy is required to deform the boron skeleton into

a cage-shape than into the quasi-planar form. In neutral instances, the substantial deformation

that favors one isomer over the other corresponds to the E-E dimer.

Computational details
 Page 5 of 22 Physical Chemistry Chemical Physics

Extensive explorations of the PESs for both series of clusters, B12E- and B12 E210.1039/D0CP02750B
DOI: (E =ViewLi-
Article Online

Cs), in the singlet and triplet state were carried out through a modified genetic algorithm as

Physical Chemistry Chemical Physics Accepted Manuscript

implemented in the GLOMOS code.36 Details about GLOMOS are described elsewhere.37,38

The lowest-lying energy isomers (< 30 kcal/mol) were further re-minimized and characterized

at the TPSS-D3/def2-TZVP39,40 level. Relative energies were computed at the

CCSD(T)41/def2-TZVP//TPSS-D3/def2-TZVP level, so the energetic analysis is based on this

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last stage. The diagnostic of the T1 coupled-cluster operator was performed to verify whether

the energy evaluation scheme, based on a single-reference method, is appropriate to

characterize these systems. A method is considered adequate if the T1 value is less than or

equal to 0.02.42 Figures S1-S2 summarize the T1 result for the lowest energy structures of the

entire series. There are only two cases in which the T1 value is slightly higher (0.03) than the

recommended threshold, but it occurs in the most distant complexes from the global minimum

and not included in the structural discussion of this work. So, the systems are appropriately

characterized. Moreover, for preliminary insight into the bonding, the Wiberg Bonding Indices

(WBIs)43 and the Natural Population Analysis (NPA)44 were carried out following the NBO6.0

partitioning scheme.45 To take into account the relativistic effects for Rb and Cs atoms, the

effective core potentials ECP-28 and ECP-48,46 respectively, were employed. All these

computations were performed using Gaussian16.47

The reason why the most energetically stable structure is a double-ring for B12Li2 or a

cage-shape for B12Li- is explained in terms of the Isomerization Energy Decomposition

Analysis (IEDA) at the TPSS-D3(BJ)/ZORA/TZ2P level.48 So, the relativistic effects were

considered by the zeroth-order regular approximation (ZORA), without spin-orbit coupling,

and including all electrons. Under this approach, the energy difference between the two isomers

(∆Eiso) is separated in terms of the distortion energy of the boron framework (∆Edist) and the

change in the interaction energies of each isomer (∆∆Eint). Also, ∆∆Eint can be divided into the
 Physical Chemistry Chemical Physics Page 6 of 22

sum of the changes of Pauli repulsions (∆∆EPauli), and the attractive terms such as dispersion
DOI:
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energy (∆∆Edisp), electrostatics (∆∆Velstat), and orbital interactions (∆∆Eorb). The IEDA was

Physical Chemistry Chemical Physics Accepted Manuscript

performed at the TPSS-D3(BJ)/ZORA/TZ2P49-52 level using the ADF2017 software.53

Results

Figure 1 shows the lowest-lying arrangements for B12. Interestingly, this boron cluster
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has an extraordinary structural consistency as the motif remains virtually unchanged in its

neutral, anionic, and dianionic form.54 The symmetry reduction from C3v to Cs is because the

addition of one electron increases the bond lengths by 0.109 Å (from 1.815 to 1.924 Å) of the

boron atoms at the bottom, assuming the orientation in Figure 1. This is more notorious in the

dianion, where this B-B distance increases to 2.143 Å. In contrast, the B-B distances of the

inner ring are reduced to 1.684 Å and 1.660 Å (and 1.675 to 1.672 Å) by adding one and two

electrons, respectively. So, the charge of the boron skeleton modifies the structure, but its shape

remains the same. Dong et al. claimed that in order to form the double-ring, a high charge

transfer from two Li+ to the B12 fragment takes place, i.e., the interaction is mostly ionic, and

the system can be considered as Li+B12-. So, the doped fragment is B122- and our series of

explorations should focus on the stoichiometries B12E- and B12E2 (E = Li-Cs). With that in

mind, let us start by exploring those cases in which it is doped with one atom of the remaining

alkali-metals.
 Page 7 of 22 Physical Chemistry Chemical Physics

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DOI: 10.1039/D0CP02750B

Physical Chemistry Chemical Physics Accepted Manuscript

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Figure 1. TPSS-D3/def2-TZVP structures of B12, B12-, and B122-.

An exhaustive exploration of the PESs revealed that the most energetically favored

systems correspond to the singlet state. The only triplet around the lower energy structures

occurs in the anions and is the one that resembles the naked B12. The difference between this

triplet and its corresponding singlet is 5.3, 4.5, 2.3, 2.1, 0.9 kcal/mol as it goes from lithium to

cesium. The putative global minima of B12 with the heavier cations (Na, K, Rb, and Cs) are

structures with the boron fragment similar to the bare boron cluster and interacting with the

alkali metal on the concave face, A (Figure 2). In contrast, the putative global minimum for

lithium (B) adopts a C2v arrangement, which has not been reported as a viable boron skeleton,

with four boron atoms forming the inner ring and higher concavity. Note that both structures

correspond to the two most favorable ones for the entire series. The energy difference between

A and B is 0.3, -0.8, -0.2, -1.1, and -1.8 kcal/mol as moving from lithium to cesium. Although

these values indicate that the cage-shaped structure (B) is energetically stable only in the case

of lithium, the difference between A and B for the entire series is minimal, suggesting that both

structures may coexist in the gas phase. The HOMO-LUMO energy difference is larger in B

by 0.42 - 1.24 eV. Interestingly, other structures have larger gaps (Figure S1), so these systems
 Physical Chemistry Chemical Physics Page 8 of 22

do not comply with the principle of maximum hardness.55 The only shown tendency
DOI:is thatViewthe
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HOMO-LUMO energy difference grows from lithium to cesium in both arrangements. Other

Physical Chemistry Chemical Physics Accepted Manuscript

isomers closer in energy are included in Figure S1.

The dynamic behavior of the naked B12 cluster was already thoroughly analyzed.56 That

is, it has a transition state with an imaginary frequency mode associated with the rotation of the

inner B3 ring with respect to the peripheral B9 ring (Table 1). For the naked B12, the rotational
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barrier is 17.5 kcal/mol (19.0 kcal/mol for B122-). The doped systems B12Co-, B12Rh-, and B12Ir-

also result in the A structure, but with a slight distancing of the B3 ring from the frame, so the

rotational barrier is lowered. These anionic clusters have rotational barriers of 7.6, 7.3, and 5.0

kcal/mol, respectively.25 In the case of the B12E- (E = Li - Cs) series, the rotational barrier is

approximately 10.9 - 12.9 kcal/mol (Table 1). Also, the B12M- (M = Co, Rh, and Ir) clusters

have a C3v point group, while in B12E- (E = Li - Cs), such point group is a saddle point up to

3.1 kcal/mol above the quasi-planar Cs structure (A). A possible reason for the point group

reduction, from C3v to Cs is a pseudo Jahn-Teller effect since, in A, the degenerate orbital is

HOMO-1 and not the HOMO required for Jahn-Teller distortion.

Figure 2. TPSS-D3/def2-TZVP structures of B12E- (E = Li-Cs).

The natural population analysis (NPA) charges indicate that in both, A and B, there is

a high charge transfer from the alkali metal to the boron fragment (0.94 - 1.00 |e|), and also the
 Page 9 of 22 Physical Chemistry Chemical Physics

WBI of any cation with the boron skeleton is less than 0.02, suggesting a highly
DOI:ionic B-E
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10.1039/D0CP02750B

interaction. There are two different WBI values of B-B, one with a bond order of approximately

Physical Chemistry Chemical Physics Accepted Manuscript

twice the other. In the case of the quasi-planar structure (A), the WBI values between the boron

atoms forming the peripheral ring, WBI(B-Binner), is 1.15 - 1.16, while the WBI between the

boron atoms for the inner B3 fragment, WBI(B-Binner) is 0.56 - 0.59, somehow in line with the

corresponding average bond lengths (r(B-Binner) = 1.587 - 1.596 Å and (r(B-Binner) = 1.670 -
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1.674 Å). Similarly, the WBI value in the cage-shaped isomer (B) for the boron atoms forming

the external ring is 1.13 - 1.14 with an average bond distance of 1.605 Å, while for the internal

B4 ring is 0.65 - 0.66 with a B-B length of 1.768 Å. Figure 3 shows the dependence of the WBI

against the B-B length for three different types of bonds, the outer ring bond, the inner ring

bond and those between rings. In terms of the bond index, there are also three boron bonding

groups. A group with a WBI of 1.0 - 1.5 corresponding to the outer ring B-B bonds. A second

group with values ranging from 0.5 to 0.9, involving the inner ring bonds and some inter-ring

bonds, and the more distant B-B bonds form the third group with a WBI value less than 0.4.

These values indicate that the bonds of the inner ring of both structures comprise multicentric

bonds, while the external rings are constituted by multiple (single and double) bonds.
 Physical Chemistry Chemical Physics Page 10 of 22

Figure 3. WBI vs. distance between the boron atoms forming the external rings,DOI:
the10.1039/D0CP02750B
internal
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rings, and between rings for all global minima at the TPSS-D3/def2-TZVP level.

Physical Chemistry Chemical Physics Accepted Manuscript

Table 1. The relative energies, ∆EA-B, and rotational energy barrier, ∆Erot, in kcal/mol. The

harmonic vibrational frequency associated with the rotation, νmin, WBI and B-B distances for

the external ring (B-Bext), the internal fragment (B-Binner), within the ring (B-Binter), between
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rings, (B-Bintra), natural charge (q, |e|), and energy gap (∆H-L, eV) at the TPSS-

D3/def2-TZVP level.

A B
B-Bext B-Binner B-Bext B-Binner
E ∆EA- ∆Erot[a νmin WBI r WBI B-B qM ∆H-L WBI r WBI r qM ∆H-L
[a] ]
B
Li 0.3 10.9 257i 1.16 1.587 0.59 1.674 0.94 0.87 1.14 1.605 0.66 1.767 0.94 2.00
Na -0.8 12.2 280i 1.16 1.587 0.58 1.672 0.97 0.82 1.14 1.605 0.66 1.768 0.97 2.07
K -0.2 12.8 254i 1.16 1.592 0.57 1.670 0.98 0.66 1.13 1.605 0.65 1.769 0.99 1.79
Rb -1.1 12.9 262i 1.16 1.593 0.57 1.670 0.99 0.64 1.13 1.605 0.65 1.768 1.00 1.06
Cs -1.8 12.8 235i 1.15 1.596 0.56 1.673 0.99 0.56 1.13 1.605 0.65 1.768 1.00 1.58
[a]Computed at the CCSD(T)/def2-TZVP//TPSS-D3/def2-TZVP level.

Let us examine the cases in which a second alkali-metal is added, i.e., the B12E2 (E =

Li-Cs) series. As in the previous systems, the A-type structure resembling the B12 naked

skeleton is found as the global minimum for almost the entire set. The exception, once again,

is lithium, whose C form is the global minimum. This D6d structure, composed of two stacked

boron rings with the two lithium atoms capping them along the main axis, was reported by

Dong et al. (Figure 4). Note the larger separation between metals in C in comparison with A.

However, for the cluster with lithium, this distance is the one that grows the least (0.696 Å) of

the entire group, suggesting that the double-ring configuration is energetically less favorable

for the larger cations as it limits its approximation. For this stoichiometry, the energy difference
 Page 11 of 22 Physical Chemistry Chemical Physics

between the two lowest-lying forms, A and C, is 4.2, -14.0, -15.3, -17.8, and -18.3DOI:
kcal/mol as
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moving down Group 1. The corresponding lower-lying isomers are depicted in Figure S2.

Physical Chemistry Chemical Physics Accepted Manuscript

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Figure 4. TPSS-D3/def2-TZVP structures of B12E2 (E = Li-Cs). Bond lengths are shown in Å.

Concerning the NPA charges for neutral systems, in both scenarios, the trend is the

same, the larger the cation, the more charge it transfers. The charge transfer in A is 0.92 - 0.99

|e|, and 0.89 - 0.93 |e| in the double-ring (C). As in the anionic systems, the WBI value between

the boron fragment and the cation is only 0.01 - 0.02 in A, and 0.02 - 0.03 in C. This low WBI

value, as well as the significant charge transfer, indicate a predominant electrostatic interaction.

In A, the WBI values between the boron atoms of the external ring, B-Bext, is 1.24 - 1.25, and

0.62 - 0.65 between the boron atoms forming the inner B3 fragment, B-Binner, quite similar to

the values of anionic A. For these cases, the average distance for the B-Bs forming the outer

ring is 1.584 - 1.590 Å, and 1.677 - 1.688 Å for those forming the internal ring of the boron

skeleton. Structure C shows a bond order for the B-B in the same boron monocyclic, B-Bintra,

of 1.09 - 1.10 and 0.56 - 0.57 for the B-B bonds between rings, B-Binter. Once again, the WBI

values reveal that multicentric bonds comprise the inner moiety of A and the monocycles of C.

The double-ring structure exhibits average bonding lengths of r(B-Bintra) = 1.605 - 1.608 Å and

r(B-Binter) = 1.746 - 1.760 Å. For the gap, ∆H-L, the neutral clusters also do not follow the
 Physical Chemistry Chemical Physics Page 12 of 22

principle of maximum hardness,55 but the pattern is inverted with respect to B12EDOI:
- (E=Li-Cs),
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in both geometries, the lighter metals have largest gap (Table 2).

Physical Chemistry Chemical Physics Accepted Manuscript

Table 2. WBI for the external ring (B-Bext), B3 fragment (B-Binner), inter-ring (B-Binter), intra-

ring (B-Bintra), natural charge (q, |e|) and energy gap (∆H-L, eV) at the TPSS-D3/def2-TZVP

level.
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A C
B-Bext B-Binner B-Bintra B-Binter
E2 ∆EA- WBI r WBI r qM ∆H-L WBI r WBI r qM ∆H-L
[a]
C

Li 4.2 1.24 1.585 0.65 1.688 0.96 1.38 1.09 1.608 0.57 1.746 0.89 1.70
(0.92)
Na -14.0 1.25 1.584 0.65 1.684 0.97 1.25 1.10 1.606 0.56 1.754 0.91 1.57
(0.94)
K -15.3 1.25 1.587 0.63 1.679 0.99 1.00 1.10 1.605 0.56 1.758 0.92 1.53
(0.96)
Rb -17.8 1.25 1.588 0.63 1.677 0.99 0.96 1.10 1.605 0.56 1.760 0.92 1.51
(0.96)
Cs -18.3 1.24 1.590 0.62 1.677 0.99 0.87 1.10 1.605 0.56 1.759 0.93 1.46
(0.96)
[a]Computed at the CCSD(T)/def2-TZVP//TPSS-D3/def2-TZVP level.

Although the above data is relevant, it does not yet provide further information about

the underlying causes of the structural preference in both the neutral and anionic series. For a

better understanding of how a structure is energetically favored, we use the IEDA by taking

the boron skeleton and the alkali-metal as fragments. The preference of one isomer over the

other is addressed through the analysis of a set of energy partitions. The isomerization energy,

∆Eiso, is defined as the sum of the distortion energy, ∆Edist, and the interaction energy

difference, ∆∆Eint. In other words, to establish the factors that determine the preferred

geometry, the relationship between distortion and interaction energies for the two systems
 Page 13 of 22 Physical Chemistry Chemical Physics

should be considered. In our case, negative value implies that the term predominates in
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DOI: 10.1039/D0CP02750B

structure A and a positive one in B. In the anionic series, the interaction energy difference,

Physical Chemistry Chemical Physics Accepted Manuscript

∆∆Eint, is similar in all cases and higher for the cage-shaped structure (B) by 4.9 - 5.9 kcal/mol

(see Table 3), but that does not explain the energy preference between isomers. In general, the

differences in dispersion energies, ∆∆Edisp, are very close to zero, which means that the

contribution from van der Waals forces is also similar in both geometries. The electrostatic
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component remains relatively constant for the entire set, and noticeably higher for the cage-

shaped isomer, B, indicating that such form facilitates the ionic interaction between the

fragments. At the same time, the orbitalic contribution is only advantageous for A in LiB12-,

but raises its contribution in B for heavier metals. On the other hand, the isomerization energy,

∆Eiso, indicates a preference for the cage-type structure in Li and Na and more favorable toward

the quasi-planar form in the remaining alkali-metals. It was mentioned that isomerization

energy includes the terms ∆∆Eint and ∆Edist and that the former remains practically constant

for the entire anionic series. In contrast, the absolute values of ∆Edist for systems with K, Rb,

and Cs promote the quasi-planar isomer and are almost twice as large in comparison to lighter

metals. In summary, the prevailing factor in determining between structure A and B is the

distortion of the boron skeleton, which is less energetically expensive in LiB12- and NaB12-.

Table 3. IEDA at the TPSS-D3(BJ)/ZORA/TZ2P level (all-electron) for the A-E1-, and B-E1-

isomers using E+ and B12-2 as fragments. ∆∆Edist stands for the distortion energy of the cluster.

Energy values are in kcal/mol.

LiB12- NaB12- KB12- RbB12- CsB12-

∆Eiso 9.2 10.1 -2.8 -3.6 -3.7
∆∆Eorb -3.1 0.5 1.0 1.2 1.6
∆∆Velstat 8.0 8.5 8.2 7.1 5.9
 Physical Chemistry Chemical Physics Page 14 of 22

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∆∆EPauli 0.7 -3.1 -4.2 -3.6 -2.9
DOI: 10.1039/D0CP02750B

∆∆Edisp -0.2 0.0 0.1 0.1 0.3

∆Edist 3.8 4.2 -8.0 -8.5 -8.6

Physical Chemistry Chemical Physics Accepted Manuscript

∆∆Eint 5.4 5.9 5.2 4.9 4.9

Table 4 corresponds to the IEDA results of structures A and C, that is, the two

competing structures for B12E2 (E = Li - Cs). Similarly, a negative value implies the
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predominance of that term in A. For the case of the neutral systems, all the ∆∆Eint values are

positive, implying stronger interaction energy in the double-ring structure (C), especially in the

case of lithium (42.5 kcal/mol), almost twice as much as for any of the other cases (20.7 - 24.0

kcal/mol). The values corresponding to ∆∆Edisp are relatively small (1.7 - 2.8 kcal/mol) and

favor the double-ring isomer, but undermined by ∆∆EPauli (Pauli’s repulsion values are

positive). The orbitalic energy difference, ∆∆Eorb, is only advantageous for C in Cs2B12. The

term that stands out because of its larger values is the electrostatic one, ∆∆Velstat, which

predominates predominates in the double-ring but decreases when going from lithium to

cesium. But more importantly, it is the relationship between isomerization and distortion

energy. According to the first, and as expected, only Li2B12 suits the double-ring. The only

instance in which the interaction energy (42.5 kcal/mol) exceeds the absolute value of the

distortion energy, ∆Edist, (34.3 kcal/mol). This value includes the distortion of the boron

framework, ∆EdistB12, and that of the metallic dimer, ∆EdistE2. Interestingly, the distortion of the

boron skeleton demands roughly the same energy in every case (45.8 - 47.6 kcal/mol). Thus,

the factor that tips the balance is the distortion of the E-E fragment, which decreases from 11.2

to 0.9 kcal/mol as it goes down the group 1 of the periodic table. Therefore, the distortion of

the metallic dimer compensated with the interaction energy establishes the structurally

preferred isomer in the neutral clusters.

 Page 15 of 22 Physical Chemistry Chemical Physics

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DOI: 10.1039/D0CP02750B

Table 4. IEDA at the TPSS-D3(BJ)/ZORA/TZ2P level (all-electron) for the A-E2, and C-E2

Physical Chemistry Chemical Physics Accepted Manuscript

isomers using E2+ and B12-2 as fragments. ∆∆EdistB12 stands for the distortion energy of the boron

skeleton, and ∆∆EdistE2 for the distortion of the E2 fragment. Energy values are in kcal/mol.

Li2B12 Na2B12 K2B12 Rb2B12 Cs2B12

∆Eiso 8.2 -13.1 -17.8 -19.9 -26.0
∆∆Eorb -11.0 -13.6 -3.9 -1.9 3.0
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∆∆Velstat 67.8 43.5 32.9 28.7 24.8

∆∆EPauli -17.1 -7.7 -7.8 -6.5 -9.7
∆∆Edisp 2.8 1.9 2.3 1.7 2.7
∆Edist -34.3 -37.1 -41.3 -41.9 -46.7
∆∆Eint 42.5 24.0 23.5 22.0 20.7
∆EdistB12 -45.8 -45.9 -47.0 -47.2 -47.6
∆EdistE2 11.5 8.7 5.7 5.3 0.9

Conclusions

The exhaustive and systematic exploration of the PES of the systems B12E- and B12E2

(E = Li-Cs) identifies the most favorable isomer, for the anionic complexes, as either a cage-

type structure, or as a quasi-planar one whose boron skeleton is identical to the naked B12

cluster. In other words, only with certain alkali-metals the boron skeleton is radically deformed.

Analogously, in neutral systems, the global minimum in the form of a double-ring is only found

in B12Li2. In all other combinations, the lowet-lying energy structure remains, as in the anionic

case, similar to the B12 cluster. The NPA is not sufficient to determine the factors that promote

one isomer over the other. Both series, regardless of the alkali-metal involved, do not comply

with the principle of maximum hardness and show a predominantly electrostatic nature due to

their very high charge transfer and low WBI values. The determining factors for the isomeric

preference were obtained from the isomerization energy decomposition analysis (IEDA). In

the lighter anionic complexes, the IEDA results indicate that the structural transformation is
 Physical Chemistry Chemical Physics Page 16 of 22

viable because of the deformation energy of the boron skeleton is relatively low, DOI:
which isViewnot
Article Online
10.1039/D0CP02750B

the case for complexes with heavier alkali-metals. Interestingly, in neutral systems, the energy

Physical Chemistry Chemical Physics Accepted Manuscript

required to transform the boron skeleton is similar in both the double-ring and the quasi-planar

clusters. In other words, the distortion energy from the boron skeleton is not decisive in the

structural preference. The determining factor in these cases is the distortion energy

corresponding to the metal dimer.

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Acknowledgments

This work was funded by Cinvestav (Grant SEP-Cinvestav-2018-57). The CGSTIC

(Xiuhcoatl) is acknowledged for allocation of computational resources. J. A. and J. B. thank

Conacyt for their Ph.D. fellowship. X.Z. thanks FONDECYT 1180565. Z. C. acknowledges

the financial support from National Natural Science Foundation of China (No.11874178,

11922405, 91961204).

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