Theoretical and computational studies of conformation,

natural bond orbital and nonlinear optical properties of

cis-N-phenylbenzohydroxamic acid
Saadullah G. Aziz
a
, Shabaan A.K. Elroby
a,b
, Rifaat H. Hilal
a,c
, Osman I. Osman
a,
a
Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah, Saudi Arabia
b
Chemistry Department, Faculty of Science, Benisuief University, Egypt
c
Chemistry Department, Faculty of Science, Cairo University, Giza, Egypt
a r t i c l e i n f o
Article history:
Received 20 October 2013
Received in revised form 2 December 2013
Accepted 2 December 2013
Available online 14 December 2013
Keywords:
N-phenylbenzohydroxamic acid
Traditional hybrid
Long-range-corrected
NLO properties
NBO calculations
a b s t r a c t
The gas phase conformational and nonlinear optical properties of cis-N-phenylbenzohydroxamic acid (cis-
NPBHA) keto and enol forms were studied applying traditional hybrid and long-range-corrected Density
Functional Theory(DFT) andtime-dependent densityfunctional (TD-DFT) methods. Thecalculatedgeomet-
rical parameters for the two isomers agreed satisfactorily with literature ones. The keto formwas predicted
to be more stable than the enol counterpart by 10.7012.60 kcal/mol, and the Gibbs free energies for the
conversion: enol keto were found to be 11.14 kcal/mol (B3LYP/6-311+G

), 12.53 kcal/mol
(CAM-B3LYP/6-311+G

) and 13.28 kcal/mol (xB97XD/6-311+G

). All the selected functionals have

computed larger total hyperpolarizabilities for the enol tautomer compared to those of the keto rival. The
traditional hybrid functional yielded higher total hyperpolarizabilities than those of the long-range-
corrected ones. The total hyperpolarizabilities were nicely correlated with HOMOLUMO energy gaps
and absorption maxima. The support of these molecular properties by natural bond orbital (NBO) calcula-
tions was evaluated and discussed.
2013 Elsevier B.V. All rights reserved.
1. Introduction
Hydroxamic acids (R
1
CONOHR
2
) are known for their potency
towards combining with metal cations [1]. The most important
biological use of hydroxamate moieties is their complex formation
with Fe(III) ions [2]. In addition to this vital role, hydroxamic acids
are commonly applied as reagents for colorimetric analysis [3,4], as
drugs for treating bacterial [5] and malaria diseases [6] or as agents
to inhibit urease activity [7]. The properties of hydroxamic acids
have been investigated theoretically [8]; to indicate the preference
of neutral and anionic Z-amide form of benzohydroxamic acid over
its E counterpart. Ab initio calculations of formohydroxamic and
acetohydroxamic acids showed that the E and Z isomers of the keto
form are more stable than those of the enol rival [9].
The conformational behavior of cis and trans isomers of
N-phenylbenzohydroxamic acid (NPBHA) in the gas phase and in
solution was investigated by Cioni [10] using MP2 and DFT meth-
ods using the 6-31G(d) basis set. He attributed the relative stability
of the cis form, over that of the trans one, to the possibility of exis-
tence of intramolecular H-bonds in the former. Senthilnithy et al.
[11] have complemented this conjecture and predicted the
preference for the Z-isomer of NPBHA derivatives in both gas phase
and water media using Complete Basis Set method (CBS-QB3).
We endeavour in this study, using Density Functional Theory
(DFT) methods to probe the electronic and conformational struc-
tures of cis-NPBHA keto and enol tautomers, and examine the ori-
gin of their stability using mainly natural bond orbital (NBO)
theory [12,13] that showed efcient technique to pinpoint the
radix of hydrogen bonding [14] and hyperconjugative [15] interac-
tions through second order perturbation energy (E
(2)
) given as:
E
2
DE
ij
q
i
F
2
ij
De
1
where q
i
is the donor orbital occupancy, De is the difference be-
tween the energy of an acceptor orbital (j) and a donor orbital (i)
and F
ij
is the off-diagonal (NBO) KohnSham Matrix.
The nonlinear optical (NLO) properties of cis-NPBHA isomers are
of interest indatastorageandelectro-optic applications [1618]. For
molecules, the NLO properties are related to their hyperpolarizabil-
ity (b) through the Einstein summation convention:
l
i
E l
0
i
a
ij
E
j

1
2
b
ijk
E
j
E
k

1
6
c
ijkl
E
j
E
k
E
l
2
where l
0
i
is the dipole moment in the absence of the electric eld
(E) and a is the polarizability. It was anticipated that molecules with
2210-271X/$ - see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.comptc.2013.12.001

Corresponding author. Tel.: +966 2640000x69315; fax: +966 26952709.

E-mail address: oabdelkarim@kau.edu.sa (O.I. Osman).
Computational and Theoretical Chemistry 1028 (2014) 6571
Contents lists available at ScienceDirect
Computational and Theoretical Chemistry
j our nal homepage: www. el sevi er . com/ l ocat e/ compt c
large hyperpolarizabilities give measurable NLO susceptibilities.
Fortunately organic molecules are known to exhibit extremely large
hyperpolarizabilities [19,20].
In this work, we intended also to estimate the NLO properties of
cis-NPBHA keto and enol forms using Density Functional Theory
(DFT) methods. In these calculations, although traditional func-
tionals are quite popular, long-range-corrected hybrid functionals
[LC-DFT] [21,22] tend to be relatively superior in estimating hyper-
polarizabilities [23,24]. In LC-DFT, the electron-electron Coulomb
operator (1/r
12
) is given as a sum of a short-range (SR) and a long
range (LR) component:
1
r
12

1 erf xr
12

r
12

erf xr
12

r
12
3
where erf is the error function and x is the range separation param-
eter. As a result the contribution to the exchange energy E
LC-DFT
x
is
separated into:
E
LC-DFT
x
E
SR-DFT
x
x E
LR-HF
x
x 4
As a result, the HartreeFock part, which constitutes a larger
fraction of the exchange energy, is treated exactly as the
electronelectron distances increase. It is this correction that gave
improved molecular susceptibilities.
These nding necessitated the use of both the traditional
(B3LYP) and the long-range corrected functionals (e.g. CAM-
B3LYP and xB97XD) in this DFT study. Our objective here is to
judge the advantage of these methods in evaluating the optical
properties of cis-NPBHA tautomers.
2. Methods of calculations
All calculations were performed using the Gaussian 09W
package [25]. The traditional hybrid Becke, three-parameter,
LeeYangParr (B3LYP) exchange correlation functions of the
Density Functional Theory (DFT) and the long-range-corrected
CAM-B3LYP and xB97XD functionals were applied using the split
valence triple zeta [6-311+G

] basis set. The geometries of cis-

NPBHA keto and enol forms were fully optimized at the aforemen-
tioned levels of theory. Frequency analysis calculations were per-
formed to characterize the stationary points as minima and to
evaluate zero-point energies (ZPE).
The natural bond orbital (NBO) calculations have been
performed at the B3LYP/6-311+G

level using NBO 3.1 [26] as

implemented in the Gaussian 09W software package [25]. These
calculations yielded second-order perturbation energies which
have been utilized in locating hydrogen bonding and hyperconju-
gative interactions.
B3LYP, CAM-B3LYP and xB97XD hyperpolarizability calcula-
tions were performed for the keto and enol forms of cis-NPBHA
at 6-311+G

basis set. They are reported here as total hyperpolar-

izabilities (b
tot
) dened as:
b
tot

b
2
x
b
2
y
b
2
z
q
5
where
b
i
b
iii

1
3
X
i i
b
ijj
b
jij
b
jji
6
We listed hyperpolarizabilities in atomic units (a.u.) which are
linked to electrostatic units (esu) through the conversion factor:
1 a.u. = 8.6393 10
33
esu.
Calculations of the excited states of the enol and keto isomers
were performed using time dependent Density Functional Theory
(TD-DFT) at B3LYP, CAM-B3LYP and xB97XD functionals and
6-311+G

basis set.
3. Results and discussion
3.1. Structural and thermodynamical features
Fig. 3.1 depicts the labeling scheme and the optimized bond
lengths of the keto and enol forms of cis-N-phenylbenzohydroxa-
mic acid (NPBHA) using B3LYP/6-311+G

level of theory. Table

3.1 lists the optimized bond lengths and dihedral angles of the
two tautomers which have been obtained using B3LYP, CAM-
B3LYP and xB97XD functionals at 6-311+G

basis set. Since an iso-

lated cis-NPBHA molecule encompasses two separate benzene
rings, the initial step, undertaken in this research, was to address
the coplanarity of the whole NPBHA molecule. With the aim of
characterizing the ground state conformation of NPBHA, a relaxed
potential energy surface was calculated with respect to the torsion
angle C4C7N9C11(H5). It can be seen that the two benzene rings
do not have a coplanar conguration as they have H5 of less than
20 for the keto form and less than 8 for the enol counterpart. This
behavior could be attributed to both steric and repulsion effects.
As shown in Table 3.1, the optimized geometry of the keto tau-
tomer agrees satisfactorily with that obtained by Cioni [10] using
MP2 and DFT/PBE0 methods at 6-31G(d) basis set. The main differ-
ences between the geometrical features of the keto and enol forms
are: a longer C7N9 bond of the keto form by ca. 0.045 over that
of the enol one. On the one hand, the C7O8 single bond of 1.327
in the enol form is shortened (1.235 ) as it acquired a double bond
character in the keto tautomer. On the other hand, the enol form
N9O10 double bond of 1.330 is elongated by ca. 0.078 , as a
typical single NO bond, in its keto counterpart. The typical O10
H22 single bond of 0.983 in the keto form became partially
bonded (1.714 ) in the enol form. A reverse situation occurred
for the O8H22 bond of 1.005 in the enol form and 1.869 in
Fig. 3.1. (a) Labeling of cis N-phenylbenzohydroxamic acid (NPBHA). Some selected bond lengths () of cis N-phenylbenzohydroxamic Acid (NPBHA): (b) keto and (c) enol
forms which were computed b using B3LYP/6-311+G

level of theory.
66 S.G. Aziz et al. / Computational and Theoretical Chemistry 1028 (2014) 6571
the keto tautomer. The signicance of the length of the intramolec-
ular H-bonds in these two cases will be discussed later. Apart from
H3 and H5, the dihedral angles of the two tautomers do not ex-
ceed a deviation of 1.2. H3 measures the coplanarity of one of
the six-membered rings with the intramolecularily cyclized ve-
membered ring, where the two rings in the keto form deviate from
coplanarity by 4.4 compared to those of the enol tautomer. h5
indicates the coplanarity of the two benzene rings in cis-NPBHA
which are nearly coplanar in the enol form (4 < h5 < 8) and with
a considerable deviation from planarity in case of the keto counter-
part (12 < h5 < 20).
To assess the effect of the three functionals (B3LYP, CAM-B3LYP
and xB97XD) on the optimized geometrical parameters of cis-
NPBHA enol and keto forms, one can cultivate the following obser-
vations: (a) the traditional hybrid functional B3LYP gave relatively
longer bond lengths of ca. 0.01 compared to those obtained from
the long-range corrected functionals (CAM-B3LYP and xB97XD)
(b) the two long-range corrected functionals yielded comparable
bond lengths (c) there was no general trend for all dihedral angles
and the differences between them as a result of implementing the
functionals did not exceed 1 for h1, h2 and h4; but h3 opened by
ca. 3 when using the long-range corrected functionals as com-
pared to the traditional one. As for h5, xB97XD gave smaller values
of ca. 7.28(keto) and 2.63(enol) compared to those due to B3LYP
which in turn yielded comparable values to those of CAM-B3LYP
functional.
The B3LYP/6-311+G

, CAM-B3LYP/6-311+G

and xB97XD/6-
311+G

values of DE, DH, DG, DS and K for the two isomers are
listed in Table 3.2. Comparing the results from the three DFT func-
tionals one can assess their effect on the relative stability of cis-
NPBHAketoandenol forms. It is obvious that all three functionals fa-
voured the keto form at all temperatures. This is indicated by the
negatives values of DG and the positive values of DS. It is clear also
that DG is dominated by DH with little contribution from TDS of
5.75% when using B3LYP and CAM-B3LYP and 8.21% for xB97XD
functional. The long-range corrected functionals increase DE, DH
andDG by not less than1.5 kcal/mol comparedtothose due the tra-
ditional hybridfunctional. The values of the equilibriumconstant (K)
suggest that the equilibrium concentration of the keto form is over
6.08 10
8
times that of the enol form. Inaddition, Kis very sensitive
toDG andachangeof 1 kJ/mol at 273.15 K, as aresult of implement-
ing B3LYP and CAM-B3LYP functionals, increased the value of K by a
factor of 3; anda factor of 2whenapplying CAM-B3LYP andxB97XD
functionals.
3.2. NBO Analysis
Table 3.3 lists some of the most inuential second order pertur-
bation energies of the keto and enol forms of cis-NPBHA using
B3LYP/6-311+G

level of theory. All hyperconjugative energies

due the two phenyl rings yield almost similar values for the two
tautomers and were therefore neglected. However, the most
important hyperconjugative interactions in determining the stabil-
ity preference of one tautomer over the other have fructied sub-
totals of 187.92 and 147.36 kcal/mol for the keto and enol forms
respectively. These ndings conrm the total zero-point electronic
and free energy predictions which showed that the keto form is by
far more stable than its enol counterpart. A legitimate question
then arises: what is the origin of the stability of the keto form?
Table 3.1
Selected optimized parameters (bond lengths in and dihedral angles
a
in degrees) of N-phenylbenzohydroxamic acid (NPBHA) keto and enol forms together using the elected
DFT functionals at 6-311G

basis set.
Parameter Enol Keto
B3LYP CAM-B3LYP xB97XD B3LYP CAM-B3LYP xB97XD MP2
b
PBE0
b
R(C7N9) 1.322 1.310 1.311 1.367 1.358 1.357 1.363 1.362
R(C7O8) 1.327 1.317 1.318 1.235 1.229 1.229 1.247 1.237
R(N9O10) 1.330 1.327 1.319 1.408 1.395 1.389 1.417 1.390
R(O10H22) 1.714 1.673 1.717 0.983 0.981 0.977 0.993 0.9883
R(H22O8) 1.005 1.009 1.000 1.869 1.864 1.886 1.886 1.816
h1 3.33 3.20 3.17 3.32 3.10 3.98 2.0 5.0
h2 0.58 0.73 0.62 1.36 1.74 1.92 1.7 0.8
h3 31.00 33.63 34.23 35.43 35.86 38.37 39.7 34.8
h4 53.59 51.94 54.14 52.43 52.79 51.84
h5 7.55 6.35 4.92 19.59 18.83 12.31
a
h1, h2, h3, h4 and h5 are the (O8C7N9O10), (H22O10N9O8), (C5C4C7O8), (C12C11N9O10) and (C4C7N9C11) respectively.
b
Taken from Ref. [10] at 6-31G(d) basis set.
Table 3.2
Zero-point electronic energy changes (DE/kcal/mol), enthalpy changes (DH/kcal/
mol), free energy changes (DG/kcal/mol) and entropy changes (DS/cal/mol K) for
cis-NPBHA enol Mketo isomerization which have been computed by using different
DFT functionals at 6-311+G

basis set.
Parameter B3LYP CAM-B3LYP xB97XD
DE 10.73 12.05 12.52
DH 10.50 11.81 12.19
DG 11.14 12.53 13.28
DS 2.34 2.64 3.28
K 6.08 10
8
1.061 10
10
6.706 10
10
Table 3.3
Selected second order perturbation energies of the keto and enol forms which were
calculated using B3LYP/6-311+G

chemistry level.
No Interaction Keto Enol
1 r
C1C4
!r

C7C8
14.46 5.05
2 r
O10H22
!r

N9C11
3.37 6.00
3 r
C11C15
!r

N9O10
4.50 1.61
4 r
C15C16
!r

N9C11
4.16 4.47
5 n
2O8
!r

C4C7
16.62 <0.5
6 n
1O8
!r

C7N9
1.13 40.27 4.29 54.28
7 n
2O8
!r

C7N9
22.82 49.49
8 n
2O10
!r

O8H22
a
7.62 19.00
9 n
2O10
!r

N9C11
<0.5 8.49
10 n
1N9
!r

C7O8
5.23 <0.5
11 n
1N9
!r

C7O8
34.14 53.33 <0.5 <1.5
12 n
1N9
!r

C11C15
13.96 <0.5
13 r

C1C4
!r

C7C8
30.22 58.41 1.76 <2.26
14 r

2C7O8
!r

1C7O8
28.19 <0.5
15 r

2C7N9
!r

2C4C5
<0.5 <1.0 36.03 44.70
16 r

2C7N9
!r

2C11C15
<0.5 8.67
17 Total
b
187.92 153.01 147.36 102.74
a
This is the hydrogen bonding interaction.
b
Any value less than 0.5 is considered 0.5 kcal/mol when working out the sub-
total of the second order perturbation energy for each isomer.
S.G. Aziz et al. / Computational and Theoretical Chemistry 1028 (2014) 6571 67
Cioni [10] using MP2 and DFT methods at 6-31G(d) basis set
has imputed the relative stability of cis- NPBHA form, over that
of the trans one, to the possibility of the formation of an intramo-
lecular H-bond in the former. Senthilnithy et al. [11] have reached
the same conclusion when they studied the isomers of NPBHA acid
derivatives in both gas phase and water media using Complete
Basis Set method (CBS-QB3). Our NBO studies of the two tautomers
(keto and enol) of the most stable cis-NPBHA form have not only
agreed with their conclusions but also suggested that the intramo-
lecular H-bondings are not the only source. It can be seen from
Table 3.3 that the intramolecular H-bondings (n
2O10
!r

O8H22
)
are quite substantial (7.62 and 19.00 kcal/mol for the keto and enol
forms respectively); nevertheless, they are denitely not the major
source of the cis form preference. There are other extremely aug-
mented hyperconjugative interactions (r

C1C4
!r

C7C8
giving
30.22 and 1.76 kcal/mol and n
2O8
!r

C7N9
yielding 22.82 and
49.49 kcal/mol for the keto and enol tautomers respectively) for
cis-NPBHA form, which are largely subdued for the trans
counterpart.
As for the origin of the stability of the keto tautomer over that of
the enol counterpart, it is apparent that the interactions of the two
lone pairs of the oxygen atom (O8) with the C7N9 and C4C7
bonds (n
1O8
!r

C7N9
, n
2O8
!r

C4N7
and n
2O8
!r

C7N9
) favour
the enol formby 14.01 kcal/mol; while the lone pair of the nitrogen
atom (N9) interactions with the C7O8 and C11C15 bonds
(n
1N9
!r

C7O8
and n
1N9
!r

C11C15
) support tremendously the
keto form stabilization by more than 51.83 kcal/mol. On the one
hand, the vicinal interactions between the anti-bonded C1C4
and C7O8 bonds with the anti-bonded C7O8 bond
(r

C1C4
!r

C7C8
and r

2C7O8
!r

1C7C8
) yielded subtotals of
58.41 and less than 2.26 kcal/mol for the keto and enol forms
respectively. On the other hand, the anti-bonded C7N9 bond
interactions with both anti-bonded C4C5 and C11C15 bonds
lead to the stabilization of the enol form by more than 43.7 kcal/
mol. The outcome of these major electronic delocalizations has
led to the preference of the keto form by more than 50.27 kcal/
mol. Due to the extensive electronic delocalizations in both tau-
tomers of cis-NPBHA; it would be difcult to pinpoint a specic
hyperconjugative interaction as being the origin of preference of
one tautomer over the other. Hence a comprehensive insight into
the entire delocalization scheme might be an appropriate ap-
proach. In a nutshell, the nitrogen atom lone pair interactions with
anti-bonding C7O8 and C11C15 bonds and the coupling of the
anti-bonding C1C4 and C7O8 bonds with the anti-bonding C7
O8 bond could be considered the major sources of the keto
preference.
It is worth mentioning that the enol form stronger intramolec-
ular H-bonding (19.00 kcal/mol) and a relatively weaker keto tau-
tomer H-bonding (7.62 kcal/mol) have been reected in a shorter
H O bond of 1.714 for the former and a slightly longer bond
of 1.869 for the latter. The oxygen atom lone pair strong hyper-
conjugative interactions with the C7N9 bond (54.28 kcal/mol)
shortened this bond by ca. 0.045 in the enol form relative to its
length in the keto counterpart. That is, it has acquired a double
bond character. In contrast, the nitrogen atom lone pair strong con-
jugations with C7O8 bond (39.37 kcal/mol) have forced it to con-
tract (assuming an sp
2
hybridization) by ca. 0.092 in the keto
tautomer against its length in the enol form.
3.3. Nonlinear optical properties
Table 3.4 lists the zero-point corrected energies, dipole mo-
ments, HOMOLUMO energies and their energy gaps, absorption
maxima and total hyperpolarizabilities for cis-NPBHA keto and
enol forms computed using the selected functionals of TD-DFT
and DFT methods at 6-311+G

basis set. A related data of p-nitro-

aniline (pNA) as a prototypical NLO molecule [27,28] is included
for comparison purposes. The traditional B3LYP functional gave a
slightly lower total electronic energy compared to the long-range
corrected (CAM-B3LYP and xB97XD) functionals (LC-DFT). On
the one hand, the dipole moment of the enol form is estimated
by the three functionals to be larger than that of keto form. The
LC-DFT functionals yielded higher dipole moment values compared
to those computed by the traditional hybrid B3LYP method. One
the other hand, the HOMOLUMOenergy gap (E.G.) of the keto tau-
tomer is predicted by the three methods to be higher than that of
Table 3.4
Zero-point corrected electronic energies (E/a.u.), dipole moments (l/Debye), HOMO and LUMO energies (eV) and their energy gaps (E.G./eV), absorption maxima (k
max
/nm) and
total hyperpolarizability (b
tot
/a.u.) for cis-NPBHA keto and enol forms which were computed at different functionals and a 6-311+G

basis set. Data for p-nitroaniline (pNA) is

given for comparison purposes.
Method Parameter Enol form Keto form pNA
a
B3LYP/6-311+G

E 707.125171 707.142277
M 4.75 4.05 7.16
LUMO 1.89 1.64
HOMO 5.80 6.39
E.G. 3.91 4.75 4.29
k
max
349 301
b
tot
929 331 1327
CAM-B3LYP/6-311+G

E 706.758531 706.777737
M 5.05 4.12 7.23
LUMO 0.66 0.37
HOMO 7.26 7.85
E.G. 6.60 7.48 6.78
k
max
309 266
b
tot
644 243 1350
xB97XD/6-311+G

E 706.872108 706.892154
M 4.97 4.08 7.16
LUMO 0.01 0.30
HOMO 7.72 8.33
E.G. 7.73 8.63 7.96
k
max
307 265
b
tot
634 293 1337
Experiment
b
b
||
(2x; x; x) 1072 44
a
Taken from Ref. [27].
b
Ref. [28].
68 S.G. Aziz et al. / Computational and Theoretical Chemistry 1028 (2014) 6571
the enol form. Yet, the traditional functional (B3LYP) gave a lower
value compared to those approximated by the LC-DFT functionals.
Fig. 3.2 shows that the electronic distribution of the HOMO of the
enol or the keto form is delocalized mainly over C@N p-bonding,
nitrogen and oxygen lone pairs and the benzene rings; whereas
the LUMO of either isomer is mainly constituted by the C@N
p

-anti-bonding and C@C p-bonding of the two benzene rings. It

can be seen from Fig. 3.3 that the LUMO is progressively destabi-
lized in the sequence: xB97XD > CAM-B3LYP > B3LYP; while the
HOMO is gradually stabilized in the same order. The net effect of
these changes produced energy gaps in the order:
xB97XD > CAM-B3LYP > B3LYP. All these molecular properties
are in complete agreement with previous studies [2931].
The total hyperpolarizabilities of the two isomers computed by
B3LYP are larger than those from CAM-B3LYP and xB97XD. This is
expected since traditional functionals are known to yield overesti-
mated hyperpolarizabilities [3033]. The b
tot
values estimated by
CAM-B3LYPare, inturn, larger thanthoseapproximatedbyxB97XD.
This is in good agreement with Garza et als [29] ndings.
It is worthmentioningthat the conversionof cis-NPBHAketointo
enol formis accompanied by a drastic increase of b
tot
. The three DFT
functionals computed total hyperpolarizabilities of the enol formof
ca. three times that of the keto counterpart. These results indicate
that the enol tautomer could be considered for NLO applications
[29]. The two phenyl rings are nearly co-planar (less than 8) in the
enol tautomer as compared with their mutual positions (less than
20) in the keto counterpart. This near co-planarity favours a larger
charge transfer between the enolic carbon and the oxo nitrogen
atoms in the enol form. This situation may account for the larger b
tot
of 644 a.u. for the enol formcompared to 243 a.u. for the keto tauto-
mer using CAM-B3LYP/6-311+G

level of theory. Furthermore, the

CN bond that acquired a partial p-bonding character (shorter by
ca. 0.045 ) in the enol form may facilitate charge transfer between
these moieties, compared to its partial r-bonding nature in the keto
counterpart.
It is of interest to note, however, that the large values of b
tot
computed for the enol tautomer may also be explained in terms
of specic large second-order perturbation hyperconjugative ener-
gies in this isomer compared to the keto form. These hyperconju-
gations are exemplied by the charge transfer due to the
n
2O8
!r

C7N9
and r

2C7N9
!r

2C4C5
interactions which contrib-
uted 49.49 and 22.82 and 36.03 and < 0.5 kcal/mol for the enol
and keto forms respectively. The stronger H-bonding delocaliza-
tion of 19.0 kcal/mol in the enol form compared to 7.62 kcal/mol
for the keto tautomer further favours the extremely larger b
tot
val-
ues of the former.
In Table 3.4 is also shown the inverse relationship between the
b
tot
and E.G. values. A number of theoretical [34,35] and experi-
Fig. 3.2. The molecular orbital surfaces of the HOMO and LUMO of (a) Enol form and (b) keto form which have been constructed by using CAM-B3LYP/6-311+G

level of
theory.
Fig. 3.3. Schematic molecular orbital energy level diagram of cis-NPBHA enol and
keto forms which have been calculated using B3LYP, CAM-B3LYP and xB97XD
functionals at 6-311+G

basis set.
S.G. Aziz et al. / Computational and Theoretical Chemistry 1028 (2014) 6571 69
mental [36] studies have conrmed this relationship between the
total hyperpolarizabilities and HOMOLUMO energy gaps. The link
between these two parameters can be interpreted in terms of the
endurance of charge transfer interactions, leading to higher hyper-
polarizabilities, being favoured in molecular systems having lower
HOMOLUMO energy gaps.
The NLO activity of molecules could also be shown by good
absorption and emission characteristics which can be achieved by
using TD-DFT method to compute excited state properties [37,38].
Therefore, we carried out TD-DFT B3LYP, CAM-B3LYP and xB97XD
functionals at 6-311+G

basis set to obtain the electronic vertical

singlet excitation energies for cis-NPBHA enol and keto forms. The
calculated absorption maxima (k
max
) for the enol (349, 309, and
307 nm) andketo (301, 266 and 265 nm) forms using these three se-
lected TD-DFT B3LYP, CAM-B3LYP and xB97XDfunctionals, respec-
tively, are listed in Table 3.4. It is clear that the traditional hybrid
B3LYP functional yielded relatively intense absorption bands com-
pared to those of the long-range corrected ones (CAM-B3LYP and
xB97XD). These variations in the calculated absorption maxima
can directly be correlated with the HOMOLUMO energy gaps of
the enol and keto forms and hence with their calculated total hyper-
polarizabilities using these selected levels of theory.
The total hyperpolarizabilities of cis-NPBHA enol (929, 644 and
634 a.u.) and keto (331, 243 and 293 a.u.) forms obtained by using
the B3LYP/6-311+G

, CAM-B3LYP/6-311+G

and xB97XD/6-
311+G

levels of theory, respectively, are compared with those

of pNA [27] calculated at the B3LYP/6-31G

(1327 a.u.), CAM-

B3LYP/6-311+G

(1350 a.u.) and xB97XD/6-311+G

(1337 a.u.)
levels of theory. They are all listed in Table 3.4. The results of the
two systems using the matching levels of theory (CAM-B3LYP/6-
311+G

and xB97XD/6-311+G

) indicate that the b

tot
values of
enol and keto forms are half and quarter, respectively, of those of
pNA [27] as a prototypical donoracceptor molecule. Garza et al.
[29] using xB97X/6-311++G

level have obtained the hyperpolar-

izability (b
||
(2x; x; x) of pNA of 1027 a.u. which was within an
error of 4% of the experimental value [29]. Hence they concluded
that these long range corrected functionals yield results within
10% error. Considering all these remarks and putting in mind that
the CAM-B3LYP and xB97XD functionals underestimate hyperpo-
larizabilities, we conclude that our total hyperpolarizability values
for both enol and keto forms would be within ca. 10% error of their
future experimental values. Furthermore, we anticipate that the
enol formwould have a potential of showing strong NLO character-
istics that can remarkably be enhanced and tuned [31] by attaching
some donors e.g. (CH
3
)
2
N and CH
3
O and acceptors e.g. CN, NO
2
and COOH in the different positions of the two benzene rings.
4. Conclusions
The tautomerism, NBO and NLO properties of the keto and enol
forms of cis-NPBHA are studied using DFT and TD-DFT traditional
hybrid (B3LYP) and long-range corrected functionals (CAM-B3LYP
and xB97XD) at 6-311+G

basis set. The selected functionals pre-

dicted optimized geometries which are in good agreement with
those estimated earlier. The keto tautomer is predicted to be more
stable than its enol counterpart by 10.73 (B3LYP), 12.05 (CAM-
B3LYP) and 12.58 (xB97XD) kcal/mol. The traditional hybrid func-
tional computed higher b
tot
for both isomers compared with those
calculated from long-range corrected ones. The b
tot
of the enol
form was estimated to be reasonably large, and can be enhanced
and tuned by a pushpull mechanism of donors acceptors attached
to the two benzene rings, allowing for the potency of NLO applica-
tions. NBO studies of both isomers using B3LYP/6-311+G

level
have attributed the origin of the keto form stability preference
mainly to the nitrogen atom lone pair vicinal interactions with r
anti-bonding C7O8 and C11C15 bonds. They also assigned the
larger b
tot
values of the enol tautomer to the oxygen atom lone pair
vicinal interaction with the CN r anti-bond. The calculated
absorption maxima, dipole moments and HOMOLUMO energy
gaps are nicely correlated with the b
tot
values.
Acknowledgements
This Project was funded by the Deanship of Scientic Research
(DSR) King Abdulaziz University, Jeddah, under Grant No. 69/130/
1432. The authors, therefore, acknowledge with thanks DSR sup-
port for Scientic Research.
References
[1] M. Biru, A. Budimir, M. Gabric evic , Complexation of beryllium(II) with
hydroxamic acids in aqueous medium; spectrophotometric determination of
stability constants, J. Inorg. Biochem. 75 (2) (1999) 8591.
[2] H. Boukhalfa, T.J. Brickman, S.K. Armstrong, A.L. Crumbliss, Kinetics and
mechanism of iron(III) dissociation from the dihydroxamate siderophores
alcaligin and rhodotorulic acid, Inorg. Chem. 39 (25) (2000) 55915602.
[3] L. Bauer, O. Exner, The chemistry of hydroxamic acids and N-hydroxyimides,
Angew. Chem. Int. Ed. Engl. 13 (6) (1974) 376384.
[4] K. Kobashi, K. Sakaguchi, S. Takebe, K. Hosaka, A colorimetric method for the
determination of hydroxamic acid by iodine oxidation, Anal. Biochem. 146 (1)
(1985) 712.
[5] T.A. Wencewicz, B. Yang, J.R. Rudloff, A.G. Oliver, M.J. Miller, NO chemistry for
antibiotics: discovery of N-alkyl-N-(pyridin-2-yl)hydroxylamine Scaffolds as
selective antibacterial agents using nitroso DielsAlder and Ene chemistry, J.
Med. Chem. 54 (19) (2011) 68436858.
[6] K. Brucher, B. Illarionov, J. Held, S. Tschan, A. Kunfermann, M.K. Pein, A. Bacher,
T. Grawet, L. Maes, B. Mordmuller, M. Fischer, T. Kurz, a-Substituted b-oxa
isosteres of fosmidomycin: synthesis and biological evaluation, J. Med. Chem.
55 (14) (2012) 65666575.
[7] K. Kobashi, S. Takebe, N. Terashima, J. Hase, Inhibition of urease activity by
hydroxamic acid derivatives of amino acids, J. Biochem. 77 (4) (1975) 837843.
[8] B. Garca, S. Ibeas, J.M. Leal, F. Secco, M. Venturini, M.L. Senent, A. Nino, C.
Munoz, Conformations, protonation sites, and metal complexation of
benzohydroxamic acid. A theoretical and experimental study, Inorg. Chem.
44 (8) (2005) 29082919.
[9] N.J. Fitzpatrick, R. Mageswaran, Theoretical study of hydroxamic acids,
Polyhedron 8 (18) (1989) 22552263.
[10] I. Cioni, Theoretical in investigation of the conformational bahaviour of N-
phenylbenzohydroxamic acid in solution, Magn. Reson. Chem. 42 (2004) S48
S56.
[11] R. Senthilnithy, H.D. Gunawardhana, M.D.P. De Costa, D.P. Dissanayake,
Absolute pK
a
determination for N-phenylbenzohydroxamic acid derivatives,
J. Mol. Struct. Theochem. 761 (2006) 2126.
[12] A.E. Reed, L.A. Curtiss, F. Weinhold, Intermolecular interactions from a natural
bond orbital, donoracceptor viewpoint, Chem. Rev. 88 (6) (1988) 899926.
[13] A.E. Reed, F. Weinhold, Natural bond orbital analysis of near-HartreeFock
water dimer, J. Chem. Phys. 78 (6) (1983) 40664083.
[14] K. Wang, X. Shan, X. Chen, Electron propagator theory study of 2-aminoethanol
conformers, J. Mol. Struct. Theochem. 909 (13) (2009) 9195.
[15] L. Song, Y. Lin, W. Wu, Q. Zhang, Y. Mo, Steric strain versus hyperconjugative
stabilization in ethane congeners, J. Phys. Chem. A 109 (10) (2005) 23102316.
[16] S.R. Marder, J.A. Sohn, G.D. Stucky, Materials for Non-linear Optics: Chemical
Perspectives, ACS symposium, series 455, Washington DC, USA, 1991.
[17] R.W. Boyd, Non-linear Optics, Academic Press, New York, USA, 1992.
[18] S.R. Marder, Organic non-linear optical materials: where we have been and we
are going, Chem. Commun. 2 (2006) 131134.
[19] J.L. Oudar, D.S. Chemla, Hyperpolarizabilities of the nitroanilines and their
relation to the excited state dipole moment, J. Chem. Phys. 66 (6) (1977) 2664
2668.
[20] D.R. Kanis, M.A. Ratner, T.J. Marks, Design and construction of molecular
assemblies with large second-order optical nonlinearities. Quantum chemical
aspects, Chem. Rev. 94 (1) (1994) 195242.
[21] A. Savin, H. Flad, Density functionals for Yukawa electronelectron interaction,
Int. J. Quantum Chem. 56 (4) (1995) 327332.
[22] H. Iikura, T. Tsuneda, T. Yanai, K. Hirao, A long-range correction scheme for
generalized-gradient-approximation exchange functionals, J. Chem. Phys. 115
(8) (2001) 35403544.
[23] Y. Tawada, T. Tsuneda, S. Yanagisawa, T. Yanai, K. Hirao, A long-range-
corrected time-dependent density functional theory, J. Chem. Phys. 120 (2004)
84258433.
[24] M. Kamiya, H. Sekino, T. Tsuneda, K. Hirao, Nonlinear optical property
calculations by the long-range-corrected coupled-perturbed KohnSham
method, J. Chem. Phys. 122 (2005). 234111-1-10.
[25] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato,
X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M.
70 S.G. Aziz et al. / Computational and Theoretical Chemistry 1028 (2014) 6571
Hada, M. Ehara, Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y.
Honda, O. Kitao, H. Nakai, T. Vreven, J.A. Montgomery, Jr., J.E. Peralta, F. Ogliaro,
M. Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, R. Kobayashi, J.
Normand, K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M.
Cossi, N. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken, C. Adamo,
J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C.
Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski, G.A. Voth,
P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas, J.B. Foresman,
J.V. Ortiz, J. Cioslowski, D.J. Fox, Gaussian 09, Revision A.02, Gaussian Inc.,
Wallingford CT, 2009.
[26] E.D. Glendenning, A.E. Reed, J.E. Carpenter, F. Weihold, NBO Version 3.1.,
Gaussian Inc., PA, USA, 1998.
[27] A.J. Garza, O.I. Osman, G.E. Scuseria, N.A. Wazzan, S.B. Khan, A.M. Asiri,
Nonlinear optical properties of DPO and DMPO: a theoretical and
computational study, Theor. Chem. Acc. 132 (2013) 13841390.
[28] P. Kaatz, E.A. Donley, D.P. Shelton, A comparison of molecular
hyperpolarizabilities from gas and liquid phase measurements, J. Chem.
Phys. 108 (3) (1998) 849856.
[29] A.J. Garza, G.E. Scuseria, S.B. Khan, A.M. Asiri, Assessment of long-range
corrected functionals for the prediction of non-linear optical properties of
organic materials, Chem. Phys. Lett. 575 (2013) 122125.
[30] B. Champagne, E.A. Perpete, D. Jacquemin, S.J.A. van Gisbergen, E.J. Baerends, C.
Soubra-Ghaou, K.A. Robins, B. Kirtman, Assessment of conventional density
functional schemes for computing the dipole moment and
(hyper)polarizabilities of push pull p-conjugated systems, J. Phys. Chem. A
104 (20) (2000) 47554763.
[31] R.V. Solomon, P. Veerapandian, S.A. Vedha, P. Venuvanalingam, Tuning
nonlinear optical and optoelectronic properties of vinyl coupled triazene
chromophores: a density functional theory and time-dependent density
functional theory investigation, J. Phys. Chem. A 116 (2012) 46674677.
[32] B. Champagne, E.A. Perpete, S.J.A. van Gisbergen, E.J. Baerends, J.G. Snijders, C.
Soubra-Ghaou, K.A. Robins, B. Kirtman, Assessment of conventional density
functional schemes for computing the polarizabilities and
hyperpolarizabilities of conjugated oligomers: an ab initio investigation of
polyacetylene chains, J. Chem. Phys. 109 (23) (1998) 1048910498.
[33] O. Loboda, R. Zalesny, A. Avramopoulos, J.M. Luis, B. Kirtman, N. Tagmatarchis,
H. Reis, M.G. Papadopoulos, Linear and nonlinear optical properties of
[60]fullerene derivatives, J. Phys. Chem. A 113 (6) (2009) 11591170.
[34] K.S. Thanthiriwatte, K.M. Nalin de Silva, Non-linear optical properties of novel
uorenyl derivatives ab initio quantum chemical calculations, J. Mol. Struct.
Theochem. 617 (2002) 169175.
[35] B.A. Sriyanka Mendis, K.M. Nalin de Silva, A comprehensive study of non-linear
optical properties of novel charge transfer molecular systems, J. Mol. Struct.
Theochem. 678 (2004) 3138.
[36] A.M. Asiri, S.A. Khan, M.S. Al-Amoudi, K.A. Alamry, Synthesis, characterization,
absorbance, uorescence and non linear optical properties of some donor
acceptor chromophores, Bull. Korean Chem. Soc. 33 (6) (2012) 19001906.
[37] C.M. Aikens, S. Li, G.C. Schatz, From discrete electronic states to plasmons:
TDDFT optical absorption properties of Ag n (n = 10, 20, 35, 56, 84, 120)
tetrahedral clusters, J. Phys. Chem. C 112 (2008) 1127211279.
[38] J. Kulhanek, F. Bures, A. Wojciechowski, M. Makowska-Janusik, E. Gondek, I.V.
Kityk, Optical operation by chromophores featuring 4,5-dicyanoimidazole
embedded within poly(methyl methacrylate) matrices, J. Phys. Chem. A 114
(35) (2010) 94409446.
S.G. Aziz et al. / Computational and Theoretical Chemistry 1028 (2014) 6571 71