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Comment on The electron density vs. NICS scan: a new approach

to assess aromaticity in molecules with dierent ring sizes by
C. Foroutan-Nejad, S. Shahbazian and P. Rashidi-Ranjbar,
Phys. Chem. Chem. Phys., 2010, 12, 12630: is there a connection
between electron densities at the ring critical points and NICS?
Amnon Stanger
Received 4th November 2010, Accepted 2nd March 2011
DOI: 10.1039/c0cp02407d
Aromaticity is one of the fundamental concepts of organic
chemistry. It has many aspects, for example structural, energy
and magnetic. Never-the-less, there is no generally accepted
qualitative denition of aromaticity, certainly not a quantitative
one.1 It has been suggested that aromaticity is a multidimensional phenomenon, but here again, there are pro
and against this suggestion.2 It is self evident that a multidimensional method must rely on at least two measures that
are sensitive to aromaticity (and antiaromaticity).
In a recent paper,3 Foroutan-Nejad, Shahbazian and
Rashidi-Ranjbar (FSR) claim the development of a new
approach for assessing aromaticity, which is described in the
title of their paper. Though not explicitly stated, the method
that is suggested by FSR is a two-dimensional method for
assessing aromaticity and antiaromaticity. FSR chose a
magnetic criterion for one of the dimensions, and the second
dimension is an electron density parameter. FSR claim that
(as cited from the abstract of the paper) this study sheds new
light on the role of electron density on the magnitude of
NICS. Furthermore, it is claimed that the method that is
described in the paper yields a measure to compare the
strength of diatropic/paratropic currents in molecules with
dierent ring sizes or dierent numbers of p electrons.
There are three principle types of magnetic criteria for
aromaticity: magnetic exaltation, current density and NICS.
Out of the many versions of NICS approaches,4 FSR chose to
scan the NICSzz values as a function of distance from the
center of the plane of the ring,5 using the NICS-scan version.5c
As the electron density (r) parameter FSR chose the r at the
ring critical point (RCP) and above it, at the same distances
from the molecular plane at which the respective NICSzz is
calculated.
r at the RCP was used together with HOMA (a structural-based
aromaticity criterion) and NICS(0) by Howard and Krygowski.6

Schulich Faculty of Chemistry and The Lise-Meitner-Minerva Center

for Computational Quantum Chemistry, Technion Israel Institute of
Technology, Haifa 32000, Israel. E-mail: stanger@tx.technion.ac.il;
Fax: +972 4-829-3944

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Phys. Chem. Chem. Phys., 2011, 13, 1265212654

The correlation between the three was found to exist but it was
not so good. A later work by Palusiak and Krygowski7 found
a somewhat better correlation between the r at the RCP and
HOMA, and a somewhat worse correlation with NICS(1)ZZ.
It is noted that in the rst paper only one family of
compoundspolycyclic aromatic hydrocarbons (PAH)was
considered, and in the second paper a smaller number of
FAHs and a few quasi-aromatic rings were considered. There
was no attempt to investigate a more general spectrum of
aromatic and antiaromatic molecules and ions. Thus, the
correlations that were found in these two papers are rather
specic.8
NICS-scan was shown to produce very dierent (opposite)
plots for systems that show diatropic (aromatic) and paratropic
(antiaromatic) ring currents. As mentioned above, if a two
dimensional description of aromaticity (and antiaromaticity)
is wished, the r at and above the RCP (which is the parameter
that FSR chose) should also show a dierent behavior for
aromatic vs. antiaromatic systems. Is this really the case?
Figures FSR-S-3,9 that show the change of r as a function
of distance above the RCP, clearly suggest that this is not the
case. Figure FSR-S-3-2 shows that the lines of cyclopentadienyl
anion, benzene and tropylium cation (all with (4n + 2) p
electrons, i.e., aromatic) overlap with the lines of cyclopentadienyl cation, benzene dication and tropylium anion (all having
4n p electrons, i.e., antiaromatic), respectively. Furthermore,
whereas the three aromatic rings have 6p electrons, two of the
antiaromatic species have 4p electrons and one 8p electrons,
and the overlap is not aected by this dierence. The rs at the
RCP are dierent for the dierent rings. They are ca. 0.05,
0.024 and 0.01 e Bohr 3 for the ve-, six- and seven-membered
rings, respectively. These two sets of data suggest that
although the r is unaected by the number of p electrons, it
is aected by the distance to the atoms and/or the bonds.
Figure FSR-S-3-1 shows that there is a considerable r
dierence between the cyclopropyl anion and cation and a
much smaller r dierence between cyclobutadiene and the
cyclobutadiene dication. However, this may be the eect of
the dierent geometries within the two couples, and, since the
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rings are smaller, the dierent geometries cause a signicant

dierence in the distances between the RCPs and the bonds
and atoms.
To test this hypothesis we have run a few calculations.
Indeed, the CC bond length in cyclopropyl cation (D3h) is
1.3582 A, whereas the bond lengths in cyclopropyl anion (C2v)
are 1.2900 and 1.5921 A.10 AIM200011 was used for obtaining
the rs. In our hands, the rs are quite dierent than those
reported by FSR, and are 0.1000 and 0.2650 e Bohr 3 for the
cyclopropyl cation and anion, respectively. However, the r
of the cyclopropyl anion at cyclopropyl cation geometry is
0.1045 e Bohr 3, namely, almost identical to that found for the
cyclopropyl cation (a 4.5% dierence) and very dierent from
the same anion at its optimized geometry. These calculations
prove univocally that the rs at the RCPs are sensitive to
the distance to the atoms and/or bonds but completely
insensitive to the number of p electrons and therefore cannot
be used as an aromaticity index.
The dependence of the r at and above the RCP on distance
alone (but not on the number of p electrons) can also be
exemplied by the following. The distance between the RCP of
the D5h-cyclopentadienyl anion and a carbon atom is 1.2000 A,
and the reported electron density is approximately
0.05 e Bohr 3 (Figure FSR-S-3-2). By simple trigonometry,
the same distance from a carbon atom in the cyclopropyl
cation is 0.91 A above the geometrical center. Figure FSR-S-3-1
shows that at this point the electron density is also ca. 0.05
electrons. Thus, for these two very dierent systems, with
dierent charges and dierent numbers of p electrons, the
electron density is a function of (almost) only the distance
from the atoms (and probably the bonds).
If, indeed, the r at the RCP is a function of the distance
from the bonds and atoms it should correlate to these distances.
The following crude analysis was undertaken. For a ring of a
size m in Dmh symmetry, the distances between the atoms and
the center of the bonds to the middle of the ring are XR and
YR respectively, where R is the CC bond length. X and Y are
given in Table 1. Since (to a rst approximation) the average
CC bond lengths are equal in the dierent systems, it should
be possible to describe the r at the RCP with X and Y only. Fig. 1
shows the rs at the RCPs of 37 membered rings (as taken from
FSR-Figure-S-3) vs. X/Y. The linear correlation coecient that
this crude model produces is 0.9965, proving again that the rs at
the RCP are not a function of the number of p electron, therefore
not suitable to serve as an aromaticity index.
Finally, as yet more evidence, Fig. 2 shows the NICS-scan
of benzene and D4h cyclooctatetraene,12 however, not in the

Fig. 1 r as a function of Y/X (see Table 1).

format that it was presented,5c but rather in the format that

FSR use, replacing r by distance (top) or the logarithm of the
distance (bottom) on the Y axis. Since r does not change
linearly or exactly logarithmically with the distance, the plots
in Fig. 2 are not identical to Figures FSR-1 but they are very
similar. Furthermore, there is no aromaticity-related information
that can be retrieved from Figures FSR-1 and cannot be
retrieved from gures like Fig. 2.
The above clearly demonstrate that r at the RCP and above
it is unaected by aromaticity (and antiaromaticity) and
therefore should not be used as an aromaticity criterion. This
renders most of the conclusions of the FSR paper (e.g., see
above citation from FSR abstract) wrong.
The induced magnetic eld is traditionally explained by
electrons moving (under magnetic eld) in the circumference
(but not center) of an aromatic or an antiaromatic ring. Also,
it was found that r at the bond critical point (BCP) show good
linear correlation to the bond length within a particular family
of compounds,6 and generally, r at the BCP is larger than r at
the RCP. These led us to carry out a preliminary investigation
of whether BCP or the transition between RCP and BCP could
be used in an FSR-like approach. To do that, we rst looked

Table 1 Some geometrical ratios in rings of size m at Dmh symmetry

vs. r.
Ring size (m)

X/Ra

Y/Rb

Y/X

rb

3
4
5
6
7

0.5770
0.7071
0.8507
1.0000
1.1528

0.2885
0.5000
0.6882
0.8660
1.0386

0.5000
0.7071
0.8090
0.8660
0.9010

0.2215
0.1020
0.0505
0.0234
0.0094

The distance between the middle of the ring and the atoms or bonds
(see text) in R units. b Average values as obtained from gures FSR-S-3.

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Fig. 2 NICSzz of benzene (left, B) and D4h-cyclooctatetraene (right, J)

vs. (a, top) distance and (b, bottom) log(distance) from the molecular plane.

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Fig. 3 NICSzz values on the line connecting the center of the rings to the middle of the bonds 1.5 and 2 A above the molecular plane in (a, left)
benzene, (b, middle) D4h-cyclooctatetraenecenter of the double bond and (c, right) D4h-cyclooctatetraenecenter of the single bond.

Fig. 4 The change in electron densities on the line connecting the

RCP and the BCPs at dierent heights (0.0, 0.5, 1.0 and 1.5 A) from
the molecular plane in (a, left) a cyclopentadienyl anion and (b, right)
a cyclopentadienyl cation.

of the same ring sizes, but they are very small to begin with
(0.022 and 0.045 e Bohr 3 for tropylium and cyclopentadienyl,
respectively, at the molecular plane) and become negligible at
ca. 1 A above the plane (0.005 and 0.0196 e Bohr 3 for
tropylium and cyclopentadienyl ions, respectively), a distance
at which NICSzz values are still very large. Adding to the
above the considerations the fact that r highly depends on the
computational level,13 it is concluded that r at the BCP is also
not a good aromaticity index.
In summary, it has been shown that electron density at the
ring critical point (and at the bond critical point) is an
inadequate measure of aromaticity. There is no connection,
certainly not any inuence between the electron density at the
ring critical point and NICSzz, as claimed by FSR. Thus, the
method presented by FSR in their paper should not be used as
a measure for aromaticity.

References
Fig. 5 The average electron density above the BCP in (a, left) a
tropylium cation and anion and (b, right) a cyclopentadienyl cation
and anion.

at how NICSzz changes along the lines connecting the middle

of the ring to the middle of the bonds. Fig. 3 shows these
changes 1.5 and 2.0 A above the rings (where s contributions
are negligible or 0) in benzene and D4h-cyclooctatetraene. The
picture that is obtained qualitatively agrees with the classical
model for ring current, that is, the p electrons move in the
circumference of the ring, much like a current in a coil,
producing an induced magnetic eld that is largest in the
middle of the ring. Next, the change in electron density on
going from the RCP to the BCP was studied for a cyclopentadienyl anion and cation (Fig. 4). Since there is a symmetry
change (and therefore dierent bonds show dierent densities
at their BCPs) Fig. 4 reports the average values at dierent
heights above the rings. Please note that, as expected, the
maximum density is at the bonds, but although showing
dierent values, the functional behavior in the aromatic and
antiaromatic rings is identical. Last, the change in r above the
BCP for aromatic and antiaromatic ve- and seven-membered
ring ions was studied (Fig. 5). Indeed there are some
dierences between the BCPs of 4n p and (4n + 2) p systems

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Phys. Chem. Chem. Phys., 2011, 13, 1265212654

1 For a critical review see A. Stanger, Chem. Commun., 2009,

19391947.
2 S. Fias, P. W. Fowler, J. L. Delgado, U. Hahn and P. Bultinck,
Chem.Eur. J., 2008, 14, 30933099 and references therein.
3 C. Foroutan-Nejad, S. Shahbazian and P. Rashidi-Ranjbar, Phys.
Chem. Chem. Phys., 2010, 12, 1263012637.
4 (a) See ref. 1 and references therein. See also; (b) N. S. Mills and
K. B. Llagostera, J. Org. Chem., 2007, 72, 91639169; (c) A. Stanger,
J. Org. Chem., 2010, 75, 22812288.
5 (a) I. Morao and F. P. Cossio, J. Org. Chem., 1999, 64, 18681874;
(b) H. Fliegl, D. Sundholm, S. Taubert, J. Jeselius and W. Klopper,
J. Phys. Chem. A, 2009, 113, 86688676; (c) A. Stanger, J. Org.
Chem., 2006, 71, 883893.
6 S. T. Howard and T. M. Krygowski, Can. J. Chem., 1997, 75,
11741181.
7 M. Palusiak and T. M. Krygowski, Chem.Eur. J., 2007, 13,
79968006.
8 It is rather clear from FSRs study, ref. 3, that aromatic and
antiaromatic rings of the same size have similar to identical r at the
RCP (see below).
9 For clarity, gures from FSRs paper (ref. 3) are referred to as
Figure FSR.
10 At B3LYP/cc-pVTz which is the computational level that was
employed by FSR.
11 (a) R. F. W. Bader, Atoms in Molecules: A Quantum Theory,
Oxford University Press, New York, 1990; (b) F. Biegler-Konig,
J. Comput. Chem., 2000, 21, 10401048.
12 At GIAO-B3LYP/6-311+G*//B3LYP/6-311G*. Data taken from
ref. 4c.
13 M. Jablonski and M. Palusiak, J. Phys. Chem. A, 2010, 114,
22402244.

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