Research: Science and Education

edited by
Advanced Chemistry Classroom and Laboratory Joseph J. BelBruno
Dartmouth College
Hanover, NH 03755

Electronic Structure Principles and Aromaticity

P. K. Chattaraj,* U. Sarkar, and D. R. Roy
Department of Chemistry, Indian Institute of Technology, Kharagpur 721302, India; *[email protected]

The purpose of this article is to familiarize the reader The inverse relationship between the hardness (η) and
with the relationship between aromaticity and stability in the polarizability (α) (soft molecules are more polarizable)
molecules on the basis of quantities such as hardness and elec- along with the maximum hardness principle (MHP) led to
trophilicity, which are based on density functional theory and the minimum polarizability principle (MPP) (15) that states,
polarizability. It is shown that the aromaticity and antiaro- “The natural direction of evolution of any system is towards
maticity may be analyzed using the principles of maximum a state of minimum polarizability.” Various physicochemical
hardness, minimum energy, minimum polarizability, and processes as well as stability and reactivity of different sys-
minimum electrophilicity. tems have been analyzed (4) in the light of the MHP and
Density functional theory (1) offers theoretical founda- MPP. It has been observed that the maximum hardness and
tions of qualitative chemical concepts such as electronega- minimum polarizability conditions are complementary to the
tivity (χ) (2), hardness (η) (3, 4), polarizability (α) (5), and minimum energy criterion for stability (16): “In general, a
electrophilicity (ω) (6). Pauling (7) introduced the concept stable state (minimum energy configuration) or a favorable
of electronegativity as the power of an atom in a molecule to process is associated with the maximum hardness and mini-
attract electrons to itself. Pearson’s hard–soft acid–base mum polarizability and a transition state with the minimum
(HSAB) principle (8, 9), that is, “hard likes hard and soft hardness and maximum polarizability.”
likes soft”, introduced the concept of hardness. For an N- To analyze the possible connection between the extremal
electron system, χ (10), η (11), and ω (6) are defined as values of electrophilicity (ω) and stability it has been shown
(17) that the extremum on the ω occurs during chemical re-
∂E I + A actions, molecular vibrations, and internal rotations at the
χ = −µ = − ≈ (1) points for which the following condition is satisfied
∂N v (r ) 2
∂µ µ ∂η
= (4)
∂λ 2 η ∂λ
1 ∂2E 1 ∂µ I − A
η = = ≈
2 ∂N 2 2 ∂N 2 (2) where λ can be a reaction coordinate (reaction), bond length
v (r ) v (r )
(stretching), bond angle (bending), or dihedral angle (inter-
nal rotation). Since µ is negative and η is positive owing to
χ2 the convexity in energy, the extremum of ω occurs when the
ω = (3) slopes of the variations of µ and η are of opposite signs.
2η
Therefore, the extrema in chemical potential and hardness
where µ and v(r) are the chemical and external potentials, will ensure extremum in ω. In general µ and η are maxima
respectively; I and A are the ionization potential and elec- for the equilibrium geometry implying the minimum value
tron affinity, respectively, and E is the energy. In eqs 2 and for ω. In those cases the stability would be related to the mini-
3, half factors are arbitrary. mum value of ω.

Electronic Structure Principles Aromaticity

Aromaticity (18, 19) is a molecular property generally
There exist several important electronic structure prin-
manifested through low reactivity, high stability compared
ciples associated with these reactivity descriptors. Sanderson’s
to the similar nonaromatic molecule, low magnetic suscepti-
electronegativity equalization principle (12) states,
bility (diatropic), and preference of substitution over addi-
During an electron transfer process in a chemical reac- tion arising in planar, conjugated, cyclic molecules with (4n
tion, electrons flow from a species of lower electronega- + 2) π electrons, for example, in benzene with 6 π electrons.
tivity (higher chemical potential) to one with higher On the other hand molecules such as cyclobutadiene with 4
electronegativity (lower chemical potential) until the elec- π electrons are termed as antiaromatic (18, 19) and are gen-
tronegativities get equalized to a value approximately erally more reactive, less stable, and exhibit a paratropic shift
equal to the geometric mean of the electronegativities of in magnetic susceptibility. These molecules are generally pla-
the isolated species. nar or near planar cyclic, conjugated π-electron systems with
In addition to the HSAB principle there exists another hard- 4n instead of (4n + 2) π electrons. They undergo rapid addi-
ness-related principle, that is, the maximum hardness principle tion reactions to the double bonds.
(13, 14), that states, “There seems to be a rule of nature that The concepts of aromaticity and antiaromaticity recently
molecules arrange themselves so as to be as hard as possible.” have been extended to the all-metal inorganic systems (20) such

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 Research: Science and Education

A B
Table 1. Quantities Describing the Delocalized C6H6
and Localized Hypothetical Cyclohexatriene Molecules
Quantity Delocalized Localized
E/Eh ᎑232.3085 ᎑232.2846
NICS (ppm) ᎑8.8884 ᎑7.4926
µ/eV ᎑3.6775 ᎑3.7058
η/eV 5.5561 5.5033
ω/eV 1.2170 1.2477
Figure 1. Optimized geometries for the (A) C6H6 and (B) hypotheti- α/(e2a02/Eh) 59.1787 60.2523
cal cyclohexatriene (geometry is constrained as reported in ref 23)
molecules.

A B Table 2. Quantities Describing the Delocalized

and Localized C4H4 Molecules
Quantity Delocalized Localized
E/Eh ᎑154.7089 ᎑154.7185
NICS (ppm) ᎑3.1033 25.3625
µ/eV ᎑3.5899 ᎑3.5593
η/eV 4.1113 4.3495
Figure 2. Optimized geometries for the C4H4 (A) delocalized (trip- ω/eV 1.5673 1.4563
let) and (B) localized (singlet) molecules. α/(e a0 /Eh)
2 2
38.7050 36.5053

as Al42− and Al44−. These systems are being studied in our labo- The polarizability α is calculated as the mean value as given
ratory. These characteristics of aromaticity–antiaromaticity are in the following equation
mainly based on energetic, geometric, and magnetic criteria.
1
A connection between hardness and aromaticity has been es-
tablished (21). This article highlights the chemical reactivity
α =
3
(α xx + α yy + α zz ) (6)
criteria of aromaticity mainly through an analysis of global
chemical reactivity descriptors such as hardness, electrophi- For comparison, the nucleus-independent chemical shift
licity, and polarizability in addition to energy vis-à-vis various (NICS) values at the center of the ring (24) are also calcu-
associated electronic structure principles. To do this we choose lated. The NICS, or precisely the NICS (0), is defined (24)
the prototypical examples of benzene and cyclobutadiene to as the negative of the magnetic shielding calculated at the
analyze aromaticity and antiaromaticity, respectively. center of the ring in a molecule. A large negative NICS value
Benzene, cyclohexatriene, and cyclobutadiene (localized inside the ring implies aromaticity (24) through the induced
and delocalized) are optimized at the B3LYP/6-311G** level diatropic ring currents.
of theory. For the delocalized cyclobutadiene a triplet state
is considered as in ref 22. The bond lengths of cyclohexatriene Results and Discussion
are taken from ref 23, which are used to have a constrained
geometry optimization. Zero NIMAG (number of imaginary The optimized structures of benzene, cyclohexatriene,
frequencies) values in all cases ensure the true minimum en- and cyclobutadiene (delocalized and localized) are shown in
ergy configurations for the molecules. Equations 1–3 are used Figures 1 and 2. Table 1 reports the energy, NICS value,
for evaluating µ, η, and ω. Necessary I and A values are cal- chemical potential, hardness, electrophilicity, and polarizabil-
culated from the energies of the neutral molecules along with ity of benzene and cyclohexatriene. As expected benzene is
those of the corresponding cations and anions computed energetically more stable, harder, with a lower (more nega-
through single-point calculations with the geometry of the tive) NICS value, less electronegative (with higher chemical
neutral molecule. potential), less electrophilic and less polarizable than cyclo-
The electric dipole polarizability is a measure of the lin- hexatriene. These results prove that aromatic molecules are
ear response of the electron density in the presence of an in- more stable than their nonaromatic counterpart and this fact
finitesimal electric field of magnitude F and it represents a is corroborated by the principles of maximum hardness, mini-
second-order variation in energy as mum energy, minimum polarizability, and minimum electro-
philicity (where the conditions of maxima of chemical
potential and hardness are valid).
α a ,b = − ∂ 2 E Table 2 reports the E, NICS, µ, η, ω, and α values of
∂ Fa ∂ Fb a, b = x , y , z (5)
cyclobutadiene (both localized and delocalized). All these val-

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 Research: Science and Education

A B Table 3. Quantities Describing the Al42–

and Al44– Molecules
Al42– Al44–
Quantitiy
Delocalized Localized Delocalized Localized
E/Eh ᎑969.7405 ᎑969.7238 ᎑969.2592 ᎑969.2617
NICS (ppm) ᎑34.4166 15.6569 ᎑25.1793 ᎑5.7114
µ/eV 3.6248 3.5386 8.7190 8.7030
Figure 3. Optimized geometries for the Al4 2− (A) delocalized (sin- η/eV 1.9647 1.6010 1.2059 1.1942
glet) and (B) localized (triplet) molecules. ω/eV 3.3438 3.9105 31.5209 31.7136
α/(e2a02/Eh) 525.7897 594.1903 2276.3937 1910.6437

A B
Table 4. The Λaromaticity Values for C6H6, C4H4, Al42–,
and Al44– Molecules
Λaromaticity C 6H 6 C4H4 Al42– Al44–
E/Eh ᎑0.0239 0.0096 ᎑0.0167 0.0025
α/(e2a02/Eh) ᎑1.0736 2.1997 ᎑68.4006 365.7500
ω/eV ᎑0.0307 0.1110 ᎑0.5667 ᎑0.1927
Figure 4. Optimized geometries for the Al4 4− (A) delocalized (trip- η/eV 0.0528 ᎑0.2382 0.3637 0.0117
let) and (B) localized (singlet) molecules.

ues, except for the NICS, signify that the C4H4 molecule gets may be the corresponding hypothetical localized structure as
destabilized owing to delocalization, a hallmark of shown above or a related open-chain system (30). It is obvi-
antiaromatic molecules. Similar studies on cyclobutadiene have ous that a positive value of Λaromaticity (Λ ≡ η) implies aroma-
pointed out the NICS values of the delocalized C4H4 as ᎑5.30 ticity and a corresponding negative value implies
(25) and localized C4H4 as +23.55 (22) with other levels of antiaromaticity. On the other hand a positive value of
calculations. Of course the large positive NICS value charac- Λaromaticity (Λ ≡ E, α, ω) implies antiaromaticity and corre-
terizes the antiaromaticity of C4H4, which prefers to have a sponding negative value implies aromaticity. Table 4 presents
singlet rectangular shape over a triplet square one owing to various Λaromaticity values for benzene, cyclobutadiene, Al42−,
Jahn–Teller distortion arising out of σ–π interactions (26). and Al44− systems. While benzene and Al42− are aromatic sys-
Figures 3 and 4 present the structures of Al42− (localized tems according to these criteria, cyclobutadiene is shown to
and delocalized) and Al44− (localized and delocalized), respec- be antiaromatic. Exact nature of Al44− is yet to be ascertained.
tively, optimized at the B3LYP/6-311+G* level of theory. Aromaticity in other inorganic systems, such as polyacene
Table 3 reports their E, NICS, µ, η, ω, and α values. All analogues of Na6 (31), C3N3H3 (32), B3N3H6 (32), B3O3H3
these values dictate that Al42− is aromatic in nature. Although (32) and so forth, is also analyzed.
E and α values signify the antiaromatic nature of Al44−, its In summary, aromatic molecules are less energetic,
η, ω, and NICS values reveal its aromatic characteristics. This harder, less polarizable, and less electrophilic whereas
highlights the inadequacy in the aromaticity–antiaromatic- antiaromatic molecules are more energetic, softer, more po-
ity definition when applied to Al44−. It may be noted that larizable, and more electrophilic than a suitable reference
although there is no confusion in the aromatic behavior (20a) molecule, as expected from the principles of minimum en-
of Al42− the exact nature of Al44− is not yet established (20b). ergy, minimum polarizability, and minimum electrophilicity
Synthesis of Al44− by laser vaporization followed by photo- as well as the principle of maximum hardness.
electron spectroscopic and ab initio studies (20c) as well as
its electron localization function analysis (27) show that Al44− Acknowledgments
is antiaromatic. However, it has been argued through the
NICS (28) and magnetic field induced current density (29) We are thankful to CSIR, New Delhi, and BRNS,
analyses that the σ-aromaticity of Al44− dominates over its Mumbai, for financial assistance and V. Subramanian for
π-antiaromaticity to display its overall aromatic behavior. helpful discussion.

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