Journal of Molecular Structure (Theochem) 468 (1999) 209–221

Density functional studies of aniline and substituted anilines

Mariana E. Vaschetto*, Bernardo A. Retamal, Andrew P. Monkman
OEM, Department of Physics, University of Durham, Durham DH1 3LE, UK
Received 22 October 1998; received in revised form 2 December 1998; accepted 4 December 1998

Abstract
In this work, we present an exhaustive study of the structural as well as the electronic properties of aniline obtained using
several DFT based methods. The geometry of aniline obtained using the hybrid DFT methods (B3LYP, B3P86 and B3PW91)
shows better agreement with the experimental values, than the methods containing the gradient corrected exchange functional
(Becke 88). The new feature of the hybrid methods is that the exact Hartree–Fock exchange functional was taken in account.
Negative highest occupied and lowest unoccupied Kohn–Sham orbitals (we shall call them as HOMO, LUMO) seem to provide
a fair estimation of the experimental IPs and EAs values (particularly those obtained by using the gradient correct exchange
functional Becke 88). IPs and EAs from DFT calculations present systematic errors are observed owing to the HOMO and
LUMO, which do not correspond formally to any molecular orbital.We, also, study in a systematic way the influence of a wide
range of s – p electron donor-withdrawing substituent groups on the structural and electronic properties of aniline. In this kind
of systems, the position of the substituent group in the benzene ring as well as its electron donor–acceptor capabilities play a
very important role on the molecular structural and electronic properties. We also find that the intramolecular hydrogen bonds
are responsible for many particular experimental features. q 1999 Elsevier Science B.V. All rights reserved.
Keywords: Aniline; Polyaniline and derivatives; Density functional calculations; DFT; Hydrogen bond

1. Introduction microwave spectroscopy [8,9] and in the solid state by

Aromatic amines are very important in biological
as well as in materials science [1,2]. Particularly,
aniline was studied because of its technological appli-
cation in a vast amount of industrial processes [3,4].
In fact, it was used as a precursor for the synthesis of
dye and sensitizer molecules, for the synthesis of
molecules having potential large non-linear optical
responses, etc [5,6].
Aniline is the classic molecular model for aromatic
amines [7]. Its structure is known in the gas phase by
* Corresponding author. Tel.: 144-191-374-2159; fax: 144-
191-374-3749.
E-mail address: m.e.vaschetto@dur.ac.uk (M.E. Vaschetto)
0166-1280/99/$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
PII: S0166-128 0(98)00624-1
X-ray crystallography [10]. Moreover, several theore-
tical studies including semiempirical [11–13] and ab
initio calculations [6,14–16] were carried out to deter-
mine the structural and electronic properties of
aniline. However, the conformation of the amine
group and its degree of tilting related to the phenylene
plane are still a matter of study. This large amount of
previous data available on aniline provides an ideal
basis for using this compound as a model compound
to test the accuracy of the density functional theory
(DFT) based-on methods. Subsequently, the most
precise algorithms can be applied to a family of
anilines in order to generalize the trends of the physi-
cochemical properties.
The inclusion of a substituent group in the aniline
210 M.E. Vaschetto et al. / Journal of Molecular Structure (Theochem) 468 (1999) 209–221
leads to the variation of the charge distribution in the
molecule, and consequently this greatly affects the
structural as well as the electronic parameters. Parti-
cularly, it is expected that large modifications of the
ionization potential (IP), electronic affinity (EA) and
excitation energies should be found. Determination of
the excitation energies of finite and infinite systems
have been a subject of many research during the last
50 years [17,18].
In principle, there are several ways to calculate the
excitation energies. The first, and the simplest one,
involves the difference between the highest occupied
molecular orbital (HOMO) and the lowest unoccupied
molecular orbital (LUMO) of a neutral system. This
form corresponds to the frozen orbital approximation,
as the ground state properties are used to calculate
excitation values. This method is very practical, parti-
cularly for calculating large systems; however, the use
of DFT one-electron energy differences to estimate
excitation energies is still a matter of debate [19].
Rigorously, the density functional methods (which
are based on Hohemberg and Kohn theorem [20])
are designed to yield total energies, for example, as
a function of structure. However, the orbitals in this
case (Kohn–Sham orbitals [21]) are not electronic
orbitals but mathematical arrangements and their
eigenvalues are not directly related to the electronic
excitation energies. Nevertheless, it is often a good
approximation to neglect these formal inconsistencies
and consider them as electronic orbitals and orbital
energies, as they are in the HF framework [22].
The second way to obtain the excitation energies
involves the difference between the IP and the EA. In
this case, accurate IPs and EAs are obtained as the
total energy difference between the system with N21
or N11 electrons. This form of calculation is very
efficient, but in some cases can become very difficult
because of the inclusion of open shell considerations
in the calculations.
The third option is computationally more expensive
and involves the rigorous inclusion of electronic
correlation. This requires either extended multiple
reference configuration interaction (MR–CI)[23], or
complete active space plus perturbation theory to
second order (CAS–PT2)[24] type calculations.
Equation of motion coupled cluster (EOM–CC) treat-
ment achieves high accurate results as well [25].
Finally, in the last few years a new development for
the treatment of electronic excitations has emerged.
Ahlrichs and Bauernschmitt [26] consider the time
dependent density functional formalism (TDDFT)
within the adiabatic approximation. They consider
that the excitation energies and the oscillator strengths
are given as poles and residues of the response func-
tion as a function of frequency (v ). Results given by
this method show that, although there is a constant
shifting of the values obtained for the excitation ener-
gies, the TDDFT is a very promising and new
approach for studying electronic excitations [27].
For a detailed description of this method the reader
is referred to Refs. [26] and [28].
In this work, we present the excitation energies of
aniline and substitute anilines using the simplest and
less computationally expensive methods. The most
advanced way of calculating the excitation energies
will be considered in future work.
This work is mainly divided in two parts. The first
is a systematic analysis of the DFT methods, by apply-
ing them to analyze the geometry of aniline (model
compound) and its electronic parameters, such as, the
IP, the EA, and the first electronic excitation. We shall
compare the results obtained by using the gradient-
corrected exchange and the hybrid exchange func-
tional Becke three parameters. We will show that
the inclusion of Hartree–Fock exchange into the
DFT calculation, to give the so-called hybrid meth-
ods, leads to a significant improvement of the
predicted structures.
In the second part of this work, we will apply the
DFT-hybrid scheme to calculate the structural para-
meters as well as the electronic properties of aniline
and aniline derivatives. In fact, we will present a
detailed study of anilines substituted with a wide
range of s – p electron-donor to electron-withdrawing
groups (–NH2, –OH, –OCH3, –CH3, –CO2H, –Cl, –
CF3, –CN, –NO2) [29–32]. The purpose of this study
is to show in a systematic manner the variation of the
geometrical parameters depending on the substituent
considered. Also, the electronic consequences of
including a substituent on position ortho, meta or
para in aniline will be presented. Moreover, we will
try to connect our calculated results with the experi-
mental parameters, such as pKb in order to determine
the predictive capability of the theoretical method
employed.
In Section 2, we summarize the theoretical methods
 M.E. Vaschetto et al. / Journal of Molecular Structure (Theochem) 468 (1999) 209–221 211

Table 1
Structural parameters of aniline calculated at several theoretical levels. The basis set used is 6-31G*. Reported bond lengths are in Å and the
angles are in degrees. See Fig. 1 for more details

RHF-AM1 B3LYP B3P86 B3PW91 BLYP BP86 BPW91 Expt. a

r(N1–C1) 1.400 1.400 1.392 1.394 1.411 1.404 1.403 1.402

r(C1–C2) 1.415 1.405 1.402 1.404 1.416 1.414 1.413 1.397
r(C2–C3) 1.390 1.393 1.390 1.391 1.403 1.401 1.399 1.394
r(C3–C4) 1.394 1.397 1.393 1.394 1.407 1.405 1.403 1.396
a (N1–C1–C2) 120.7 120.7 120.7 120.7 120.7 120.7 120.7 120.3
a (C6–C1–C2) 118.5 118.5 118.5 118.5 118.6 118.5 118.5 119.26
a (C1–C2–C3) 120.3 120.5 120.5 120.5 120.4 120.5 120.5 120.7
a (C2–C3–C4) 120.7 120.8 120.8 120.8 120.8 120.8 120.8 120.4
a (C3–C4–C5) 119.5 118.9 118.8 118.8 118.9 118.9 118.9 118.55
g 1b 25.8 26.5 25.7 25.6 27.1 26.6 26.5
g 2c 158.2 156.5 157.1 157.1 156.1 156.5 156.6
ud 4.6 2.9 2.7 2.7 3.3 3.2 3.1
de 45.4 40.3 40.2 41.0 40.2 40.0 37.2
a
From Ref. [8].
b
Torsion angle defined by H1–N1–C1–C6.
c
Torsion angle defined by H2–N1–C1–C6.
d
Angle defined by the plane of the benzene ring and the nitrogen.
e
Angle defined by the plane of the amine group and the plane of the benzene ring (see Fig. 1).

employed to carry out these calculations. In Section expressed as:

3.1 we present the theoretical results of the aniline,
meanwhile, Section 3.2, we introduce the theoretical A × ExSlater 1 12A† × ExHF 1B × ExBecke 1C
results of substituted anilines. Finally, conclusions are
provided in Section 4. × EcLYP 1EcVWN :

B3P86 and B3PW91 are defined analogously

2. Computational methods
The geometry of aniline was completely optimized
using the DFT schemes described later. No geometri-
cal constraints were imposed to obtain the minimum
energy structure of aniline. Optimized geometries
were also determined using the semiempirical
Hartree–Fock AM1 [33] in order to compare the
results obtained using the DFT methods.
The methods employed are based on DFT and we
considered various combinations of exchange-corre-
lation functionals. The exchange functionals used are:
Becke 88 (B) [34], and the Becke three parameters
hybrid (B3) [35]. Meanwhile, the correlation func-
tionals used are: Lee–Yang–Parr (LYP) [36], Perdew
(P86) [37], and Perdew and Wang (PW91) [38,39].
B3LYP indicates that Becke’s three-parameter hybrid
functional is used in combination with the LYP corre-
lation functional, etc. This functional can be
and differ only in the use of the respective corre-
lation functional Ec. The values of A, B, and C are
0.80, 0.72 and 0.81 as determined by Becke. The
main difference from the other exchange func-
tionals lies in the incorporation of the exact
Hartree–Fock exchange with a weight of 20%.
The calculations were carried out using 6-31G*
basis set, as well as using the Stephens–Basch–
Krauss ECPs with split valence basis set augmen-
ted with polarization function (CEP-31G*). The
‘fine grid’ option was used to avoid numerical
inaccuracies in the energy calculations. Spin
restricted theory is used.
Substituted anilines were fully optimized using
the restricted version of B3P86 and B3PW91. In
these cases, only the basis set 6-31G* were
employed. All the calculations were performed
using Gaussian 94 [40] and the Cerius 3 package
[41].
212 M.E. Vaschetto et al. / Journal of Molecular Structure (Theochem) 468 (1999) 209–221

3. Results and discussion

3.1. Theoretical calculations of aniline

Table 1 depicts the calculated and experimental

structural parameters of aniline. In order to compare
the accuracy of several theoretical methods, we opti-
mized the geometry of aniline using manifold of DFT
methods. Earlier, Johnson et al. [42] and Mannfors et
al. [43] found that all functionals containing the gradi-
ent corrected exchange (Becke 88) consistently
produces bond lengths between heavy atoms (i.e. C,
N, etc) which are too long for about 0.01–0.02 Å. The
inclusion of a Hartree–Fock component in the hybrid
methods that consider the Becke three parameters
exchange functionals give better agreement with the
experimentally determined bond lengths. This
improvement in the prediction of the bond lengths
using hybrid methods is observed in our aniline calcu-
lations (see Table 1). The explanation of this is
obvious and is related to the fact that at the
Hartree–Fock level the bond lengths are calculated
too short, while at the DFT level they are overesti-
mated. Related to the employed basis set, when the
CEP-31G* is used an important overestimation of the
bond lengths (around 0.01–0.02 Å) is observed
compared to the experimental values. Therefore,
here we shall present some selected results obtained
with the 6-31G* basis set, which gives structural
values in quite good agreement with the experimental
ones [8–10].
One of the most remarkable features of these calcu-
lations is the accurate prediction of the degree of non-
planarity of the amine group. The experimental
results, obtained from microwave spectroscopy
[8,9], show that the angle d between the plane defined
Fig. 1. Schematic representation of aniline molecule.
by the amino group and the plane of the ring was
37.58 ^ 28 in gas phase (see Fig. 1). Unfortunately,
this estimation was made considering that the
nitrogen atom lies in the same plane as the ring.
However, X-ray measurements [10], previous ab
initio calculations [7,14–16] and results reported
here predict that the nitrogen atom is out of the
ring plane for about 28–38. In fact, this value is in
good agreement with that determined by Fukuyo
et al. [9] by X-ray crystallography. In this case,
the nitrogen atoms are out of the plane by about
0.113 and 0.122 Å, which yields to a d angle of
378 ^ 48 and 388 ^ 48, very close to that deter-
mined in the gas phase and also very close to the
value obtained by DFT calculations. Our predicted
d angle, around 408, is very close to the experi-
mental value. This angle does not show any
remarkable variation with the used combination
of exchange-correlation functionals. However, we
should mention here that when the CEP-31G*

Table 2
Energy of the frontier orbitals of aniline calculated at several theoretical levels. The used basis set is 6-31G*. All values are in eV.

RHF-AM1 B3LYP B3P86 B3PW91 BLYP BP86 BPW91 Expt.

HOMO 28.523 25.391 26.025 25.467 24.360 24.661 24.572 7.72 a

LUMO 0.639 0.251 20.366 0.185 20.344 20.632 20.527
DE(LUMO-HOMO) 9.162 5.642 5.629 5.652 4.016 4.029 4.045 4.4 b
Eanion c2Ecation c 5.111 6.360 4.720 4.4
a
From Ref. [59].
b
From Ref. [60].
c
Total energy
 M.E. Vaschetto et al. / Journal of Molecular Structure (Theochem) 468 (1999) 209–221
basis set is used an increase in the d angle of
about 18–28 is found, which is, actually, a devia-
tion from the experimental value.
A selected group of calculated electronic para-
meters of aniline determined by using several differ-
ent methods are given in Table 2. Owing to the
analogy between the highest occupied and the lowest
unoccupied Kohn–Sham orbitals and the frontier
molecular orbitals, we name them as HOMO and
LUMO respectively. According to the Koopmans
theorem, it is possible to obtain IP as the absolute
value of the HOMO [44]. It is well known, that
Hartree–Fock methods are characterised by their
accurate predictions of the IP [31], while methods
based on the DFT scheme largely underestimate the
IP [17,18]. However, better values of IP could be
achieved depending on the exchange-correlation
functional combination used. In fact, the IP values
obtained using the hybrid methods are better than
the IPs achieved when using the gradient corrected
exchange functional, Becke 88. Also, the correlation
functional plays an important role in the IP calcula-
tions. The B3P86 method shows the best IP value
compared to the experimental one than the B3LYP
and the B3PW91 methods.
The EA of a system is related to its LUMO.
Hartree–Fock methods show a large overestimation
of the LUMO. However, the DFT methods give more
accurate EA than the Hartree–Fock methods. Here,
again the value predicted using the Perdew 86 corre-
lation functional gives the most accurate EA [22].
Previous studies [18,45] have shown that the IP and
EA calculated using the DFT have almost the same
error, which produces a shift of the frontier orbitals
through less negative energies. These systematic
errors of the IP and EA values compensate when
calculating excitation energies, giving a good approx-
imation to this parameter. In Table 2, it can be seen
that the methods based on the DFT give excitation
energies that are in relatively good agreement with
the experimental value. Several authors [18,22,45]
have claimed those hybrid methods, particularly
those that included P86 as the correlation functional
give accurate IP and band gap values, while the LSDA
method give better EA’s. In our case, the BP86 func-
tional combination is superior to the rest of methods
for calculating excitation energies, while hybrid meth-
ods overestimate it. In all cases, errors larger than
213
10% are found. One of the most probable explanations
of this deviation of the excitation energies can be
found in the Kohn–Sham theoretical formulation.
Despite this, this form of calculation of the IP and
the excitation energy is very controversial owing to
the consideration of the Kohn–Sham orbitals as elec-
tronic orbitals, as was mentioned earlier, we can
consider it as a good first approximation. Table 2
shows some selected values of excitation energies
calculated as the difference between the total energy
of the cation and the anion of the aniline. Although
there are some improvements to the values, the
computational cost is, at least, three times larger
than in the first case (direct difference between
LUMO and HOMO in the neutral state). The advan-
tage of this method is, however that it accounted for
any structural changes suffered by the system when
the oxidation state changes.
In summary, we have shown that the DFT calcula-
tions that employ the Becke three parameters
exchange functional reproduce accurately the geome-
try of aniline compared to the methods based on the
Becke 88 (non-hybrid) exchange functional. Also, the
LYP correlation functional appears to give the most
accurate N-ring distance. Therefore, the B3LYP
combination of exchange correlation functionals
seems to be most precise in order to estimate struc-
tural properties of aniline. However, the evaluation of
DFT based methods for predicting the electronic
properties is not so direct. Considering the adiabatic
approximation, Becke three parameters exchange
functional gives the closest IP values, however the
most accurate excitation energies are obtained by
using the Becke 88 functional. In these cases, the
Perdew 86 correlation functional gives better IP
values. This relative improvement of the excitation
energy values obtained by using BP86, could be asso-
ciated to an unrealistic structure predicted by this
method (see Table 1). Therefore, the better electronic
properties predicted by BP86 could be an artifact
originating from the structural distortions arising
from this method. Consequently, based on this
previous analysis we have selected the B3LYP
method, which provides reliable structural properties
that are critical when analyzing a family of
compounds, particularly conjugated systems. As our
main aim is to compare the physicochemical para-
meters of a family of anilines, and although the
214 M.E. Vaschetto et al. / Journal of Molecular Structure (Theochem) 468 (1999) 209–221

Table 3 B3LYP shows some weakness for predicting electro-

Selected structural parameters of substituted anilines, calculated nic properties, trends predicted by this method will be
using B3LYP (basis set 6-31G*). Distances are in Å, angles in
degrees
qualitatively correct. Following these results, we used
B3LYP in order to predict structural and electronic
Substituent Position r N1–C1 g1 g2 d u effects of the substituents covalentely added to an
aniline molecule.
NH2 ortho 1.411 39.4 165.3 43.3 3.8
meta 1.401 26.3 156.1 2.9
para 1.411 28.8 153.5 43.8 3.2 3.2. Theoretical calculations of aniline derivatives
OH ortho 1.398 22.4 153.0 41.1 2.8
meta 1.400 27.7 157.8 2.9 The interaction of a molecule of aniline with a
para 1.408 28.1 154.9 3.1 substituent group is of great importance in determin-
CH3 ortho 1.403 33.0 162.5 40.8 2.8 ing its structural and electronic properties [31,32,46–
meta 1.401 26.9 156.6 40.5 3.0
para 1.403 27.1 156.0 41.1 3.1
48]. As aniline and polyaniline are very relevant in the
OCH3 ortho 1.397 22.3 152.9 41.1 2.9 field of biological and materials science, we shall try
meta 1.399 25.3 155.5 40.2 2.9 to elucidate the influence of several substituent groups
para 1.408 27.2 154.1 42.9 3.1 on their physicochemical properties [49]. In this
Cl ortho 1.389 23.0 157.3 37.0 3.0 section, three aspects about substitution in aniline
meta 1.396 25.2 157.2 39.0 2.8
para 1.397 25.9 157.0 2.9
are investigated in detail. The first one is the influence
CN ortho 1.378 17.7 159.7 30.3 2.8 of these substituents on the structural conformation of
meta 1.393 24.0 157.6 37.1 2.8 aniline, including the flattening of the amine group.
para 1.385 22.6 160.0 33.8 2.6 Secondly, we focus our discussion on the electronic
CF3 ortho 1.388 26.8 162.1 36.1 2.5 properties of anilines, mainly we shall be concerned
meta 1.395 24.7 157.1 38.1 2.5
para 1.391 23.9 158.4 36.4 2.8
about the excitation energies and the ionization poten-
COOH ortho1 1.366 11.2 165.8 21.1 2.2 tial of these systems and their relation with the charge
ortho2 1.376 16.3 163.0 26.8 3.2 distribution in the molecule. In addition, we will
meta 1.396 24.1 155.9 2.8 concentrate our attention in those substituents that,
para 1.387 22.8 159.6 34.4 2.5 in the ortho position, could make an intramolecular
NO2 ortho 1.356 1.81 177.2 2.0 3.1
meta 1.391 23.4 157.7 36.5 2.8
hydrogen bond with the amine group.
para 1.380 20.8 161.6 31.0 2.4
3.2.1. Structural properties of substituted anilines
Table 3 shows some selected structural parameters
of aniline substituted in the ortho, meta or para posi-
tions. The investigated substituents cover a wide
range of s – p electron donor-withdrawing capability.
The torsion angles defined by H1–N1–C1–C2 and
H2–N1–C1–C2 (g 1 andg 2), the u angle, and the d
angle (see Fig. 1) represent the extent of the interac-
tion between the pz orbitals of nitrogen and the p
system of the benzenoid ring. It is particularly inter-
esting that additional planarity of the amine group is
observed when an electron-withdrawing substituent
group is added to the ring. In particular, the nitro
group shows the strongest effects on the aniline
geometry, with all the atoms of o-nitroaniline lying
(almost) in the same plane as the benzenoid ring (see
Fig. 2). When a carboxylic or cyano group is added to
the ring, a similar effect is observed but to a lesser
Fig. 2. Optimized structure of o-nitroaniline. extent. In fact, in these cases coplanarity is not
 M.E. Vaschetto et al. / Journal of Molecular Structure (Theochem) 468 (1999) 209–221 215

Fig. 3. Optimized structures of the two stable conformers of o-

aminobenzoic acid.

reached. This additional planarity was reported before

in some experimental and theoretical studies
[32,33,49–54]. This flattening of the amine group is
coupled with a shortening of the bond length between
the nitrogen and the benzene ring (yielding a quinoid
like structure). Fig. 4. Relative total energy of substituted aniline against the
Anilines substituted with nitro and carboxy groups substituent position. All cases were scaled by a constant factor in
in ortho position deserves special attention. As these order to plot them in one graph.
groups contain an oxygen atom that lies next to the
hydrogen of the amine group, an intramolecular
hydrogen bond is probably formed [49,55]. In fact,

Table 4
Mulliken charges of aniline and ortho substituted anilines (in me). Hydrogen charge is summed over the corresponding carbon atoms of the
benzene ring. Calculations were performed using the DFT-B3LYP method with the basis set 6-31G*

Aniline NH2 OCH3 Cl CF3 CO2H (I) CO2H (II) NO2

N1 2786.31 2783.16 2789.37 2791.55 2803.60 2822.20 2815.02 2816.81

H1 317.93 302.49 a 333.70 a 339.24 a 338.25 a 374.84 a 362.74 a 381.99 a
H2 317.93 315.80 315.21 324.57 325.49 325.64 326.03 336.19
C1 306.87 262.23 259.06 322.15 291.32 314.31 294.43 353.30
C2 258.42 262.23 347.60 2118.22 244.47 34.48 43.49 252.46
C3 210.41 274.05 275.92 10.92 229.87 217.41 27.37 22.06
C4 218.77 223.38 228.36 23.90 210.06 217.26 215.35 210.46
C5 210.41 223.38 216.75 21.70 9.83 8.60 9.53 27.07
C6 258.42 27405 269.23 242.76 252.24 258.75 258.02 259.89
N2 2783.16 365.38
C7 2210.94 794.60 555.53 546.61
Cl 238.75
O1 2534.57 2523.43 c 2482.52 2447.91 c
O2 2584.93 2617.21 c 2403.38
X1 b 302.49 c 165.12 2287.18 c 410.58 412.62
X2 b 315.80 153.73 2267.25 d
X3 b 150.72 2264.82
a
Adjacent to the substituent group.
b
X ˆ H or F.
c
Adjacent to amine hydrogen.
d
F adjacent to benzene hydrogen.
 216

Table 5
Total energy and some selected electronic properties of aniline and substituted anilines, obtained employing the DFT-B3LYP with the basis set 6-31G*

Substituent Position Total energy (atomic units) Charge NH2(umeu) HOMO (eV) LUMO (ev) DE(HOMO2LUMO) (eV) m (Debyes)

H 2287.60176 2150.41 25.391 0.251 5.642 1.713

NH2 ortho 2342.94974 2182.19 24.976 0.491 4.484 2.453
meta 2342.95488 2157.15 25.022 0.587 5.609 2.604
para 2342.95112 2162.71 24.645 0.291 4.936 0.0
OH ortho 2362.81737 2138.03 25.111 0.418 5.29 1.479
meta 2362.81813 2152.02 25.319 0.394 5.713 2.741
para 2362.81469 2157.98 24.990 0.123 4.8676 2.1188
CH3 ortho 2326.91964 2152.67 25.327 0.364 5.691 1.736
meta 2326.91974 2153.08 25.319 0.326 5.644 1.622
para 2326.91900 2153.53 25.233 0.266 5.499 1.551
OCH3 ortho 2402.12460 2140.44 25.043 0.509 5.552 1.705
meta 2402.12474 2152.48 25.325 0.416 5.741 1.168
para 2402.12142 2158.45 24.944 0.187 5.131 1.814
Cl ortho 2747.19900 2127.9 25.658 20.124 5.534 2.053
meta 2747.19869 2139.0 25.733 20.151 5.582 3.155
para 2747.19798 2142.6 25.573 20.188 5.384 3.593
CN ortho 2379.84981 2132.25 25.984 21.110 4.874 4.2047
meta 2379.84638 2136.00 26.061 21.184 4.877 5.621
para 2379.84900 2128.77 26.005 20.826 5.180 6.752
CF3 ortho 2624.64116 2139.86 25.811 20.467 5.344 2.541
meta 2624.64030 2139.38 25.853 20.533 5.320 3.705
para 2624.64173 2136.60 25.895 20.250 5.645 4.484
COOH ortho1 2476.18251 2121.65 25.555 21.063 4.492 1.137
ortho2 2476.17770 2126.20 25.638 21.036 4.601 3.130
meta 2476.17578 2142.00 25.722 21.118 4.603 2.384
para 2476.17899 2133.3 25.814 20.804 5.010 3.9176
M.E. Vaschetto et al. / Journal of Molecular Structure (Theochem) 468 (1999) 209–221

NO2 ortho 2492.10951 2101.02 26.041 22.164 3.877 4.759

meta 2492.10497 2132.03 26.135 22.244 3.891 5.656
para 2492.10870 2122.67 26.253 –1.955 4.299 7.118
 M.E. Vaschetto et al. / Journal of Molecular Structure (Theochem) 468 (1999) 209–221
Fig. 5. Charge of the amine group (me) versus pKb of aniline and
substituted aniline (for additional details see Table 5).
this hydrogen bond is observed in both cases, it
induces an additional planarity in the whole system,
and in principle, should induce an increase in the
electronic delocalization of the molecule. This inter-
action originates a kind of six-member ring fused to
the benzenoid ring, which should confer special elec-
tronic properties to the whole system. Fig. 2 shows the
optimized structure of o-nitroaniline, which has a
remarkable short distance between the hydrogen
(from the amine group) and the oxygen (from the
nitro group). Also, particular consideration deserves
the o-aminobenzoic acid. In this case, there are two
possible conformations of the carboxylic substituent
as is shown in Fig. 3. Structure I depicts the strongest
interaction with the hydrogen of the amine group, this
being the most stable conformation (see Table 4 and
Fig. 4). Also, hydroxy, methoxy, trifluoromethyl and
chlorine substituent groups interact with the hydrogen
of the amine group, although in these cases the inter-
action is weaker [32,33,49,56–58]. In o-methoxyani-
line, the distance between the oxygen and the
hydrogen is 2.251 Å, and in o-aminophenol this
length is 2.288 Å, while in o-chloroaniline the chlor-
ine–hydrogen distance is 2.593 Å, which is very short
considering the radius of chlorine. Also, o-trifluoro-
methylaniline shows particularly short distances
217
between a fluorine atom (1) and a hydrogen from
the amine group (2.161 Å) and between fluorine (2)
and the hydrogen bonded in meta position (2.332 Å).
The meta and para trifluoromethylaniline, also, show
a short distance (around 2.390 Å) between one of the
fluorine and the adjacent benzene hydrogen. All these
interactions (resembling hydrogen bonds) are electro-
static, therefore, we should expect large modifications
in the charge distribution of these systems, i.e.,
unequal charge on the hydrogens of the amine group.
3.2.2. Electronic properties of substituted anilines
The charge distribution of aniline and some ortho
substituted anilines are shown in Table 4. The para
and ortho carbon atoms of aniline have the largest
negative charges compared to the other carbon
atoms [11,13,51]. This is in agreement with the
ortho and para directing power of the amine group
for electrophilic substitution known from the experi-
ment. The ortho carbon atoms show the greatest nega-
tive charge, attributed to a large mesomeric effect
(1M) owing to the non-bonding electrons of the
amine group. This charge distribution is strongly
affected by substituents. There exists a compromise
between the strength of the substituent and its position
in the ring, i.e., considering that the meta position is
deactivated. Considering the substituent position, the
unequal charge distribution on the carbons of the ring
will induce differences in the relative stabilization of
each particular system. Hence, anilines substituted
with an electron-withdrawing group should be more
stable when the substituent is placed in the ortho or
para positions, whereas electron donor substituted
anilines show a minimum total energy when the
group is bonded at the para position. This effect is
illustrated in Fig. 4 where the relative differences
between the total energy of all anilines studied are
plotted against the substituent position in the ring. In
all cases, the tendency is clear, although some addi-
tional stabilization is observed for ortho substituted
anilines, when the substituent are OCH3, OH, Cl or
COOH (I). Particularly, a stabilization of 3 kcal/mol is
observed when comparing the two possible conforma-
tions (I and II) of the o-aminobenzoic acid. This
energy difference indicates the extent of the interac-
tion between the amine group and the oxygen of the
substituent adjacent to it.
The lack of electrons in the benzene ring produced
218 M.E. Vaschetto et al. / Journal of Molecular Structure (Theochem) 468 (1999) 209–221
Fig. 6. (a) Plot of the energy of the HOMO of substituted anilines
against the substituent position in the benzene ring. The HOMO of
aniline is denoted by a dotted line. (b) Plot of the energy of the
LUMO of substituted anilines against the substituent position in the
benzene ring. The LUMO of aniline is denoted by a dotted line.
by electron-withdrawing substituents is the main
reason for the extra planarity of the amine group,
and it produces the shortening of the nitrogen–carbon
bond distance, which is characteristic of the charged
anilines. However, not only the strength of the substi-
tuent group is important, but also its position plays an
important role in the induced conjugation.
By analyzing the charge distribution of ortho
substituted anilines, it is possible to explain some of
the special behavior reported experimentally (ortho
effect) [49]. In fact, in all substituted anilines reported
in Table 5 the hydrogens of the amine group support
different amounts of charge. Having the hydrogen
next to the substituent the lowest electronic density.
Moreover, the oxygen atoms of o-nitroaniline also
exhibit an asymmetric charge distribution. These
facts, together with the short distance between oxygen
and hydrogen, support the assumption of intramole-
cular hydrogen bond formation, which induces addi-
tional stabilization to the molecule [59,60]. A similar
effect is reported in o-aminobenzoic acid. In this case,
the electronic density on the oxygen atoms depends on
the conformation of the carboxy group (I or II, see Fig.
3). There exists a more positive electrostatic interac-
tion between the hydrogen of the amine and the
oxygen from the carbonyl group (more than with the
hydroxyl group). In contrast, the fluorine atom of o-
trifluoromethylaniline next to the amine group shows
a more negative charge than the rest of the fluorine
atoms. Although, in this case the electrostatic effect is
less significant than in carboxy and nitroanilines, an
interaction between the substituent and the amine
group is observed. Similar behavior is found for o-
methoxyaniline and o-chloroaniline. Finally, the
opposite effect is observed in o-diaminobenzene
where the amine groups repel each other. As the
charge of the amine group is related to the basicity
of the aromatic amines, we plotted the charge of the
amine group against the experimental pKb of several
amines [49,61] in order to compare our results (see
Fig. 5). In fact it is possible to establish a quite linear
relationship between our calculated charges and the
experimentally determined pKb, and therefore it is
possible to consider the intramolecular electrostatic
interaction as a very plausible explanation for the
ortho effect. It is known that DFT, particularly at
the LDA level, overestimate the hydrogen-bond
energy [62,63]. However, our calculations show that
 M.E. Vaschetto et al. / Journal of Molecular Structure (Theochem) 468 (1999) 209–221
Fig. 7. Plot of the difference between the HOMO and the LUMO
energies against the substituent position in the benzene ring. The
DE(HOMO2LUMO) of aniline is denoted by a dotted line.
the results obtained are comparable to those obtained
by AM1 [31] (which is quite accurate at predicting
hydrogen bonds). Further, the explanation of the
experimental ortho effect is one of the most powerful
arguments in favour of hydrogen bonds predicted by
B3LYP. Moreover, as B3LYP is a hybrid method it is
not so unexpected that an improvement in the predic-
tion of the hydrogen bonds is found compared to non-
hybrids methods.
Although, the aniline orbitals were largely
described before [6,64–68], we will briefly mention
here some relevant aspects in terms of our discussion.
First, the HOMO shows a large contribution from the
amine group and the benzene ring, whereas the
LUMO corresponds mainly to the benzene ring
having a very small contribution from the meta
carbons. Therefore, it is expected that the IP and EA
of aniline will be strongly affected by substitution.
There is a very close relationship between the strength
of the substituent, the charge of the amine group, the
IP, and the basicity of the system [32]. Consequently,
the IP, as well as the charge distribution of substituted
anilines, should contain a lot of information relevant
to practical purposes. Table 5 shows the HOMO of
aniline and its derivatives, which can be directly
219
related to the vertical IP by applying Koopmans theo-
rem. Although, as was explained earlier, IP values
calculated by using the adiabatic approximation
depict large error, we expect that the relative trends
of the experimental IP will be adequately described by
this approximation. A variation of the IP in agreement
with the electron donor-withdrawing capability of the
substituent group is observed [49].
Electron-donor groups, especially the amino group,
interact mainly with the HOMO orbital of aniline,
whereas their interaction with the LUMO is minor
(see Fig. 6 a,b). The HOMO perturbation is particu-
larly strong when the substituent is placed at position
ortho or para in the benzene ring, as is well known.
When considering electron-withdrawing groups, there
is a stabilization of the HOMO orbital but the stron-
gest perturbation is produced between LUMO of the
substituent and the LUMO of aniline. In most cases
the final IPs and EAs obtained agree with the electron
donor-withdrawing capability of the substituent
group.
Large variations of the excitation energies are
induced when a substituent group is bonded to the
benzene ring, owing to a large perturbation between
orbitals. Fig. 7 shows the first excitation energy of a
family of anilines calculated as DE(HOMO-LUMO).
Even though it was demonstrated that there is a large
error in the absolute value of the excitation energies
calculated in this way, it is possible to consider this
procedure as an appropriate first approximation. In
general, most of the substituents diminish the first
electronic transition. Particularly, anilines substituted
with strong electron-withdrawing groups (such as
nitro) depict the smallest excitation energies. More-
over, anilines substituted in the position ortho or para
with electron-donor groups, show that the HOMO
perturbation is so large that this produces a substantial
lowering of the first excitation energy.
Finally, we shall mention that anilines substi-
tuted with electron withdrawing groups show a
large permanent dipolar moment (m ). Anilines
substituted in the para position have attracted
considerable interest because of their possible
application in electro-optic modulation and second
and third harmonic generation (SHG, and THG).
The dipolar moments of the studied systems are
included in Table 5, which shows p-nitroaniline
and p-cyanoaniline as the most suitable
220 M.E. Vaschetto et al. / Journal of Molecular Structure (Theochem) 468 (1999) 209–221
compounds of this family to be utilised in such
applications. In fact these molecules have already
been experimentally studied, showing them to
have large m and b values
4. Conclusions
In this work, we have shown calculations of aniline
performed using density functional methods. We have
compared several kinds of exchange-correlation func-
tionals. The hybrid schemes (such as B3LYP, B3P86,
and B3PW91) have proved to be very accurate in
predicting the structural properties. Electronic proper-
ties calculated using the gradient-corrected exchange
seem to be more accurate, however it could be a
product of its poor structural prediction (change in
the structure ; change in the electronic properties).
The ionization potentials as well as the excitation
energies are estimated by applying the adiabatic
approximation, which provides a very good first
approach to the experimental values, i.e. calculated
excitation energy 5.1–5.6 eV, experimental excitation
energies 4.4 eV.
Substituents attached to the benzene ring of
aniline produce large structural as well as electro-
nic distortions. Particularly nitro groups, which
exert the most radical effects over the charge
distribution and consequently over the IP, EA,
and excitation energies. In general, substituents
in the ortho position show additional interactions
with the amine group. Nitro and carboxy groups,
in particular produce strong intramolecular hydro-
gen bonds with the amine group. Despite such
particular structural features, there is a linear rela-
tionship between the charge on the amine group
and the experimental pKb, which allows us to
conclude that these intramolecular hydrogen
bonds could be the origin of the experimentally
well-known ‘‘ortho effect’’.
In general, the electronic properties predicted
here have a small error, which is a consequence
of the well-known ‘overall shifting’ of the orbital
diagram observed in DFT calculations. We hope to
improve these results in the near future by using
more sophisticated methods such as MR–CI or
TDDFT.
Acknowledgements
This work was supported by EPSRC through the
grant GR/L76037. Also, we are very grateful for the
reviewer’s useful comments and suggestions.
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