637

ARTICLE
Density functional theory study of allopurinol
Delano P. Chong

Abstract: Allopurinol vapour is studied with density functional theory. Using the best method from past experience for each
property, we predict the equilibrium geometry, vibrational spectrum, dipole moment, average dipole polarizability, UV absorp-
tion spectrum, vertical ionization energies of valence electrons, and core-electron binding energies.
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Istanbul University on 11/05/14

Key words: density functional theory (DFT), allopurinol, dipole moment, polarizability, UV absorption spectrum, photoelectron
spectra, electron spectroscopy for chemical analysis (ESCA).

Résumé : On étudie la vapeur d’allopurinol en faisant appel à la théorie de la fonctionnelle de la densité. En choisissant, sur la
base de l’expérience passée, la meilleure méthode pour chaque propriété, on prédit la géométrie d’équilibre, le spectre de
vibration, le moment dipolaire, la polarisabilité dipolaire moyenne, le spectre d’absorption UV, les énergies d’ionisation verti-
cale des électrons de valence et les énergies de liaison des électrons de cœur. [Traduit par la Rédaction]

Mots-clés : DFT, allopurinol, moment dipolaire, polarisabilité, spectre d’absorption UV, spectres photoélectroniques, spectrosco-
pie photoélectronique (ESCA).

Introduction et al.7 gave structure E as the structure of allopurinol and a few

During the past few decades, many chemical and physical prop- websites (including Wikipedia) show structure W as the structure
erties have been studied with density functional theory (DFT). for allopurinol. According to our study, structure W is much
For personal use only.

Some workers try to design better and better functionals for all
properties, while we, among others, look for the best procedures
for each property of interest. In both cases, experimental results
are needed to validate the methods used. In this work, we wish to
predict several properties of allopurinol vapour using the best
DFT method for each property, gained from experience with other
molecules. Allopurinol was chosen for several reasons: (1) Allo-
purinol is a white solid, which melts at 350 °C according to the
online version of the CRC Handbook of Chemistry and Physics (a
value of 384 °C can be found on the Royal Society of Chemistry
website). The vapor pressure is estimated to be only 10−8 torr
(1 torr = 133.3224 Pa) at room temperature. No physical property
has been measured in the gas phase, although a Fourier transform
infrared spectrum has been obtained in an argon matrix.1 (2) It is
a common drug prescribed to persons (including myself) suffering
from gout. (3) Several different structures can be found in the
literature. A few selected ones are shown in Fig. 1. Bergmann
et al.2 studied five tautomers of allopurinol with the intermediate
neglect of differential overlap (INDO) method and concluded that
structure A is the most stable form, with structure B at 400 kJ mol−1
above A. Costas and Acevedo-Chávez3 scanned 14 tautomers with
DFT and confirmed that structure A was most stable, followed by
structure B at 15.4 kJ mol−1 and structure E (the enol tautomer) at
26.5 kJ mol−1 above structure A by the B3LYP/DVPZ method, which
is in good agreement with the Austin model 1 (AM1) results of 15.5
and 21.2 kJ mol−1, respectively, from Shukla and Mishra.4 In this
study, we used B3LYP/6-311+G(d,p) and found structures B and E at
15.3 and 25.6 kJ mol−1 above structure A, respectively. That the
order of lowest-energy structure A is followed by B is also con-
firmed by the HF/6-31G(d) result of Hernández et al.,5 as well as by
HF/6-31G** by Kassimi and Thakkar.6 On the other hand, Vargas
higher in energy (over 140 kJ mol−1 above A). Computations with
CCSD(T)/6-311+G(d,p)//B3LYP/6-311+G show similar results for
structure B at 14.3 kJ mol−1 above structure A. Thus, the equilib-
rium population of tautomer A is over 99% at room temperature
and 95% at 350 °C. Consequently, all of our predictions of proper-
ties were only calculated for structure A at the equilibrium geom-
etry optimized by B3LYP/6-311+(d,p).
Throughout this paper, we use the Pople shorthand notation of
method1/basis1//method2/basis2 to denote that method 1 with ba-
sis set 1 is used to compute the property of interest at the geome-
try optimized by method 2 with basis set 2.
Method
In this study, we used two programs: Gaussian 098 and
ADF2012.9 Within the Gaussian 09 package, many basis sets of
contracted Gaussian functions are available. Workers tend to use
Dunning’s correlation-consistent basis sets for small molecules
and split-valence sets such as 6-31G for very large systems. For
allopurinol studied in this work as well as other medium-size
organic molecules, we opt for the polarized split-valence triple-
zeta set 6-311+G(d,p). On the other hand, the ADF program pro-
vides a wide selection of basis sets of Slater-type orbitals. As in our
recent studies, we favour the two sets of our own design.10,11 For
general properties of small- to medium-size molecules, our favou-
rite choice is the even-tempered polarized quadruple-zeta set
(et-pVQZ).10 However, for polarizability and excitation calculations, a
better basis set is the augmented polarized triple-zeta (aug-TZP).11
From past experience, the smaller set of polarized triple-zeta (TZP)
functions seems to be quite adequate for vertical ionization ener-
gies (VIEs) of both valence and core orbitals.12,13

Received 21 December 2012. Accepted 22 February 2013.

D.P. Chong. Department of Chemistry, 2036 Main Mall, University of British Columbia, Vancouver, BC V6T 1Z1, Canada.
E-mail for correspondence: chong@chem.ubc.ca.
This article is part of a Special Issue dedicated to Professor Dennis Salahub in recognition of his contributions to theoretical and computational chemistry.
The author appreciates the opportunity to contribute a paper in this special volume of the Canadian Journal of Chemistry honouring Professor D.R. Salahub, who introduced him to the wonderful world of density functional
theory (DFT).

Can. J. Chem. 91: 637–641 (2013) dx.doi.org/10.1139/cjc-2012-0538 Published at www.nrcresearchpress.com/cjc on 14 March 2013.
 638 Can. J. Chem. Vol. 91, 2013

Fig. 1. Structures of selected tautomers of allopurinol: A = 1,5-dihydro-4H-pyrazolo[3,4-d]pyrimidin-4-one; B = 2,5-dihydro-4H-pyrazolo[3,4-d]pyrimidin-

4-one; W = 1,2-dihydro-4H-pyrazolo[3,4-d]pyrimidin-4-one; and E = 1-hydro-pyrazolo[3,4-d]pyrimidin-4-ol.

O10 H O10 H

H C4 C3 H C4 C3
N5 C9 N5 C9
N2 H
N2

C6 C8 N1 C6 C8 N1
N7 N7
H H
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Istanbul University on 11/05/14

A B
H

O10 H O10 H

C4 C3 C4 C3
N5 C9 N5 C9
N2 H
N2

C6 C8 N1 C6 C8 N1
For personal use only.

N7 N7
H H
H H

W E
As stated previously, all of our predictions of properties (with
the exception of the UV absorption spectra in solutions) were
calculated at the equilibrium geometry optimized by B3LYP/6-
311+(d,p). The B3LYP method has been thoroughly tested by Riley
et al.14 and Tirado-Rives and Jorgensen15 on closed-shell organic
molecules. For the geometry of solvated allopurinol, we used the
self-consistent reaction field (SCRF) model in the Gaussian 09 pro-
gram.8 For the time-dependent DFT calculation of the excitations,
we used the conductor-like screening model (COSMO) in the
ADF2012 program.9
The methods used in this work have been published many
times in the literature. Because different methods were used for
different properties, we need to give a brief description of each
method used. For the geometry optimization of the four struc-
tures in Fig. 1, we used the DFT method of B3LYP with an adequate
basis set, known as 6-311+G(d,p), available in the Gaussian 09 pro-
gram. The vibrational frequencies and IR intensities were calcu-
lated at the same B3LYP/6-311+(d,p) level of theory. However, as an
approximate correction to the harmonic approximation used, the
predicted wave numbers have been scaled by a factor of 0.98,
following the work of Gerega et al.1 For the dipole moment and
polarizabilty, as well as UV excitation spectrum, we preferred the
exchange-correlation potential (Vxc) known as statistical averag-
ing of orbital potentials (SAOP).16–18 For VIEs of valence electrons,
the method abbreviated as ⌬PBE0(SAOP) was used.19 It means the
energy difference between parent and cation calculated with the
parameter-free exchange-correlation functional (Exc) known as
PBE020–22 for the electron density computed with Vxc = SAOP.
Finally, for core-electron binding energies (CEBEs), we use the
method developed in 1999,23,24,12 namely, ⌬PW86-PW91+Crel,
which stands for the energy difference between parent and cation
calculated with the exchange functional PW86 and the correla-
tion functional PW91. A small relativistic correction (Crel), derived
empirically in 1995,25 was added. These methods have been tested
on many organic molecules. See ref. 26 and references cited
therein.
Results and discussion
The method of B3LYP is generally considered to be reliable and
efficient for optimization of geometry of individual organic
molecules, although other functionals including dispersion may
be needed for intermolecular interactions. The basis set of
6-311+G(d,p) is of polarized split-valence triple-zeta quality and
should be quite adequate for equilibrium geometry and vibra-
tions. The resulting bond lengths and bond angles of allopurinol
vapour are summarized in Table 1. The absence of imaginary fre-
quencies (see Table 2) indicates that the planar structure A is a
stationary point. Our AM1 results are almost identical to those of
Shukla and Mishra.4 For comparison, the bond lengths and bond
angles from the Hartree–Fock (HF) studies of Nonella et al.27 and
Kassimi and Thakkar6 are also included in Table 1. Our results are
closer to those of Kassimi and Thakkar6 probably because Nonella
et al.27 used a smaller basis set. Of the different methods listed in
Table 1, we believe that B3LYP/6-311+(d,p) used in this work is more
reliable.
In Table 2, we present the vibrational wave numbers of struc-
ture A with IR intensities, together with the experimental Fourier
transform infrared spectrum of allopurinol in an argon matrix
obtained by Gerega et al.1 This spectrum is closer to the gas-phase
situation than that of allopurinol in a KBr pellet measured by
Torreggiani et al.28 The agreement, especially with the calculation
of Gerega et al.,1 is almost quantitative.
It is believed that use of Vxc = SAOP provides reliable electron
densities. The dipole moments from SAOP are 3.891 D and 4.034 D
from et-pVQZ and aug-TZP basis sets, respectively, compared to

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 Chong 639

Table 1. Optimized geometry of allopurinol Table 2. Vibrational wave numbers, ␷ (in cm−1), and IR intensities,
(structure A). I (km mol−1), of allopurinol (structure A).
Present work 1993 1996 Observed in Ar
a b B3LYP/6-311+G(d,p)a B3LYP/6-31++G(d,p)b matrixb
B3LYP AM1 HF HF
N1—N2 1.360 1.341 1.402 1.350 ␷ I Assignments ␷ I Assignments ␷ Irelative
N2—C3 1.323 1.357 1.308 1.294 150 5.63 CO wag 154 6 ␶R2+
C3—C9 1.418 1.439 1.417 1.419 188 2.91 Rings 192 2 ␶RR+
C9—C8 1.400 1.441 1.378 1.378 259 0.43 Rings 261 0 ␶R3+
C8—N1 1.351 1.395 1.335 1.329 307 2.54 CO wag 307 3 Mixed
C8—N7 1.363 1.394 1.374 1.365 499 2.09 Ring 498 2 ␤R3+ 504 3
N7—C6 1.298 1.324 1.286 1.276 503 3.16 NH wag 506 2 Mixed 507, 509 3
C6—N5 1.365 1.384 1.363 1.355 526 3.63 Mixed 526 4 Mixed 532, 534 4
N5—C4 1.429 1.425 1.416 1.407 546 85.9 Mixed 550 88 ␥NH+ 549 70
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Istanbul University on 11/05/14

C4—C9 1.440 1.443 1.429 1.438 595 10.5 Mixed 594 11 Mixed 598 12
C4—O 1.215 1.241 1.217 1.195 634 63.8 NH wag 636 61 Mixed 637, 643 57
N1—H 1.008 0.994 0.992 656 3
C3—H 1.079 1.092 1.070 659 3.66 NH wag 661 2 ␶R5+ 662 3
C6—H 1.085 1.113 1.076 683 10.7 Breathe 685 10 Mixed 691 8
N5—H 1.012 0.995 0.997 716 36.6 NH wag, 715 47 Mixed 723, 725 28
⬔C9–C4–N5 109.8 113.6 110.1 109.8 ring
⬔C9–C4–O 129.9 127.9 129.9 129.9 767 20.0 NH wag 765 20 Mixed 781, 783 31
⬔N5–C4–O 120.3 118.5 120.0 120.3 869 15.3 CH wag 871 18 ␥CH 870 13
⬔C4–C9–C8 119.1 119.7 120.3 119.3 888 11.6 Mixed 887 13 ␤R1+ 897 10
⬔C4–C9–C3 136.1 135.8 134.3 136.4 928 3.34 CH wag 926 3 ␥CH 935 22
⬔C8–C9–C3 104.8 104.7 105.4 104.3 934 41.1 Mixed 934 39 ␤R4+ 942 25
⬔C9–C8–N1 106.0 105.9 107.3 106.6 1013, 1017 16
⬔C9–C8–N7 127.9 124.1 125.9 127.4 1031 40.4 Mixed 1039 36 Mixed 1047 43
⬔N1–C8–C7 126.1 130.1 126.8 126.0 1066 1
⬔C8–N1–N2 112.5 111.5 111.5 112.2 1072 28.6 Mixed 1075 31 ␷NN+ 1077 10
For personal use only.

⬔C8 –N1–H 127.5 127.3 120.3 1098 4

⬔N2–N1–H 120.0 121.2 120.4 1113 11.1 NH wag 1116 10 Mixed 1112, 1118 15
⬔N1–N2–C3 105.6 108.4 106.1 1151 2
⬔C9–C3–N2 111.0 109.6 111.1 110.8 1169 1
⬔C9–C3–H 128.7 127.8 128.4 1199 36.0 CH wag 1205 33 Mixed 1196, 1202 27
⬔N2–C3–H 120.2 122.7 120.8 1217 22.6 CH wag 1222 25 Mixed 1222, 1230 28
⬔C8–N7–C6 112.7 113.6 114.1 112.5 1269 3
⬔N7–C6–N5 124.9 127.3 124.2 125.6 1294 1.42 CH wag 1298 2 Mixed 1303 7
⬔N7–C6–H 119.4 116.4 119.1 1362 11.2 CH wag 1368 10 ␤CH+ 1355, 1360, 21
⬔N5–C6–H 115.8 116.3 115.3 1363
⬔C4–N5–C6 125.7 121.7 125.5 125.4 1382 7
⬔C4–N5–H 114.9 118.3 115.3 1389 23.1 Mixed 1397 25 Mixed 1391 21
⬔C6–N5–H 119.4 120.1 119.3 1403 0.30 Mixed 1408 1 Mixed 1412 1
Note: Bond lengths are in Ångstrom and angles (⬔) in 1438 11.5 Mixed 1443 12 Mixed 1434 7
degrees. 1450 4
aNonella et al.27 1502 4
bKassimi and Thakkar.6
1509 21.5 Mixed 1515 20 Mixed 1517 16
1554 105.8 Mixed 1561 91 Mixed 1550, 1558 115
1601 148.4 Mixed 1608 156 ␷CN+ 1597, 1603, 110
3.65 D from the BP86/DZVP calculation of Costas and Acevedo- 1610
Chávez,2 and to 3.42 D recommended by Kassimi and Thakkar6 1644 3
based on the assumption of additivity of basis set and correlation 1695 33
effects. The average polarizabilities we obtained with Vxc = SAOP 1749 728.0 CO str 1753 710 ␷CO+ 1725, 1730, 607
are 88.7 au and 89.6 au from et-pVQZ and aug-TZP sets, respec- 1744, 1747
tively, compared to the value of 86.9 au recommended by Kassimi 3113 4.25 CH str 3135 4 ␷CH
and Thakkar.6 Of the various results, we believe that the dipole 3188 0.59 CH str 3209 0 ␷CH
moment of 3.891 D from SAOP/et-pVQZ and the average polariz- 3522 74.2 NH str 3531 75 ␷NH 3430, 3432 113
abilty of 89.6 au from SAOP/aug-TZP to be more reliable. 3582 116.4 NH str 3594 113 ␷NH 3488, 3491 163
The UV excitation spectrum of allopurinol vapour is summa- aFor gas-phase allopurinol with scale factor = 0.98. Out-of-plane modes are

rized in Table 3. The UV absorptions with appreciable f values are shown in boldface.
all ␲ to ␲ excitations to 1A= excited states: 4.67 eV with an oscilla- bGerega et al.1

tor strength of 0.10, 5.19 eV (f = 0.05), and 6.16 eV (f = 0.29). The first
singlet absorption is similar to that calculated by Shukla and
Mishra4 with the AM1 method at 4.56 eV with f = 0.35. Experimen-
tally, the absorption in methanol solution was observed by Vargas
et al.7 at ␭max = 215 nm (5.77 eV) and 234 nm (5.30 eV). The other UV
absorption spectra were measured in aqueous solution by Shukla
and Mishra:4 ␭max = 210 nm (5.90 eV) and 250 nm (4.96 eV) for
pH = 7.2 and pH = 3.0, respectively, and ␭max = 261 nm (4.75 eV) for
pH = 10.6. The effects of solvent interactions with allopurinol were
treated in two different approximations. The geometry is reopti-
mized with the Gausiiaan 09 program using the SCRF model with
dielectric constants (␧) of 32.63 for methanol and 78.36 for water.8
On the other hand, the time-dependent DFT calculations with
ADF2012 was repeated using the COSMO model with ␧ = 32.6 and
78.39.9 The results in Table 3 indicate that the effect of change in
geometry from vacuum to SCRF is rather small, but the change in
environment from vacuum to COSMO has a large effect on the

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 640 Can. J. Chem. Vol. 91, 2013

Table 3. Singlet excitation energies (in eV) of allopurinol (structure A) from SAOP/aug-TZP (with SAOP/et-pVQZ results given in parentheses).
Allopurinol//vacuum A(MeOH)//vacuum A(MeOH)//SCRF A(H2O)//vacuum A(H2O)//SCRF
1 A= 1 A== f value 1 A= 1 A== f value 1 A= 1 A== f value 1 A= 1 A== f value 1 A= 1 A== f value
4.57 (4.54) 0.000 (0.000) 4.68 0.278 4.65 0.288 4.68 0.286 4.64 0.297
4.67 (4.65) 0.098 (0.100) 5.02 0.132 5.01 0.120 5.01 0.139 5.01 0.125
5.04 (5.02) 0.004 (0.003) 5.08 0.000 5.01 0.001 5.10 0.000 5.02 0.000
5.20 (5.20) 0.000 (0.000) 5.16 0.100 5.12 0.103 5.16 0.106 5.12 0.107
5.19 (5.20) 0.048 (0.050) 5.44 0.001 5.39 0.001 5.44 0.001 5.39 0.001
5.25 (5.26) 0.000 (0.000) 5.56 0.000 5.52 0.001 5.57 0.000 5.54 0.000
5.54 (5.53) 0.002 (0.002) 5.77 0.573 5.76 0.565 5.75 0.582 5.75 0.573
5.70 (5.73) 0.000 (0.000) 5.80 0.000 5.77 0.000 5.81 0.000 5.78 0.000
5.93 (5.94) 0.034 (0.036) 5.88 0.007 5.83 0.007 5.89 0.007 5.83 0.007
6.05 (6.06) 0.001 (0.001) 5.97 0.132 5.96 0.135 5.97 0.134 5.96 0.136
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Istanbul University on 11/05/14

6.16 (6.17) 0.291 (0.293) 6.21 0.001 6.19 0.001 6.21 0.000 6.19 0.000
6.24 (6.21) 0.000 (0.000) 6.63 0.390 6.62 0.429 6.62 0.393 6.61 0.430
Note: Out-of-plane modes are shown in boldface.

Table 4. Vertical ionization energies (in eV) of al- Table 5. Core-electron binding energies (CEBEs)
lopurinol (structure A). in eV and charges of allopurinol (structure A).
MOa KTb OVGFc mKT(SAOP)d ⌬PBE0(SAOP)e Hirshfeld Electrostatic MNDO
Atom CEBE charge potential chargea
6a== 9.28 8.78 10.48 9.02
5a== 10.63 9.80 11.25 10.02 O10 531.77 −0.347 22.49 −0.336
29a= 12.33 10.54 11.04 10.25 N1 402.61 −0.038 18.36 −0.143
28a= 12.77 10.94 11.60 10.72 N5 402.16 −0.092 18.38 −0.385
4a== 12.15 10.89 12.20 11.02 N2 400.98 −0.153 18.43 −0.131
27a= 13.36 11.39 11.94 11.10 N7 400.77 −0.217 18.44 −0.286
3a== 14.65 13.26 13.96 13.15 C4 290.06 0.200 14.68
26a= 16.76 14.93 14.84 14.34 C6 289.21 0.123 14.70
For personal use only.

2a== 16.45 14.57 15.17 14.44 C8 288.86 0.106 14.72

25a= 17.13 15.28 15.18 14.69 C3 287.59 0.018 14.77
24a= 17.31 15.18 15.38 14.77 C9 287.06 −0.049 14.80
1a== 17.99 15.83 16.29 15.62 aMNDO = modified neglect of differential overlap; Shel-
23a= 18.44 16.36 16.37 16.01 drick and Günther.29
22a= 19.83 17.48 17.24 16.96
21a= 20.65 18.44 18.21 18.03
20a= 21.67 18.89 18.86 TZP. All molecular orbitals (MOs) with a== symmetry have a nodal
19a= 22.86 19.81 19.95
plane at the molecular plane. Besides the molecular plane, the 1a==
18a= 24.90 21.21 21.32
17a= 25.35 21.50 21.63 MO has no other nodal surface (as expected), 2a== and 3a== MOs
16a= 29.72 24.47 24.95 have one, while 4a== has two. All MOs with a= symmetry except the
15a= 30.51 25.25 25.88 first 10 are delocalized, while the 1a= MO to 10a= MOs are mainly 1s
14a= 33.58 27.44 28.14 orbitals localized on O10, N1, N5, N2, N7, C4, C6, C8, C3, and C9,
13a= 36.33 29.51 30.44 respectively.
12a= 38.02 30.92 31.87 Finally, the core-electron binding energies (CEBEs) from our
11a= 38.51 31.22 31.99 DFT calculations are presented in Table 5, in which Hirshfeld
aMolecular orbital. charges and the electrostatic potentials from the SAOP/et-pVQZ
bKoopmans' theorm/6-311+(d,p). method are also listed for comparison. Mulliken charges are omit-
cOuter-valence Green's function/6-311+(d,p).
ted because there is a large dependence on the basis set and func-
dMeta-Koopmans' theorm(SAOP)/et-pVQZ.

e⌬PBE0(SAOP)/TZP.
intensities. The calculated lower absorptions average to about 4.9
eV, while the higher absorption is predicted to be 5.8 eV. The
results seem to be quite reasonable when one considers the fact
that both solvents are likely to form hydrogen bonds with allo-
purinol, which are completely ignored in the continuum models.
To include the effects of hydrogen bonds would require inclusion
of discreet solvent molecules and some procedure like the Our
Own N-layered integrated molecular orbital and molecular me-
chanics (ONIOM) method,8 which is beyond the scope of the pres-
ent study.
In Table 4, we compare the vertical ionization energies of va-
lence electrons computed by various methods, all calculated at
the geometry optimized by B3LYP/6-311+(d,p). No experimental
measurements are available for comparison. From our experience
with other molecules, the reliability of the prediction is ranked as
follows: Koopmans’ theorem (KT) < meta-Koopmans’ theorem
(mKT) < outer-valence Green’s function (OVGF) < ⌬PBE0(SAOP)/
tional used. The modified neglect of differential overlap (MNDO)
charges calculated by Sheldrick and Günther29 are also included
in Table 5. One can detect a qualitative correlation between the
CEBEs of nitrogen and the Hirshfeld charges. Since it is possible to
deposit allopurinol with a large excess of argon on a cold surface,1
we hope that a surface electron spectroscopy for chemical analy-
sis (ESCA) experiment with X-ray or synchrotron radiation can be
performed on the core-electron binding energies. There will nat-
urally be a shift from gas-phase values due to the difference be-
tween the Fermi level and the vacuum level.
Summary
In this study, we have relied on our experience with DFT and
predict the various properties of allopurinol with what we believe
to be the best method for each property. The properties include
(i) the equilibrium geometry, (ii) the vibrational spectrum, (iii) the
dipole moment, (iv) the average dipole polarizability, (v) the UV ab-
sorption spectrum, (vi) the vertical ionization energies of the valence
electrons, and (vii) the core-electron binding energies.

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 Chong 641

Acknowledgements Bickelhaupt, F. M.; Baerends, E. J.; Fonseca Guerra, C.; van Gisbergen, S. J. A.;
Snijders, J. G.; Ziegler, T. J. Comput. Chem. 2001, 22, 931. doi:10.1002/jcc.1056.
The financial support of the Natural Sciences and Engineering (10) Chong, D. P.; van Lenthe, E.; van Gisbergen, S.; Baerends, E. J. J. Comput.
Research Council of Canada (NSERC) is gratefully acknowledged. Chem. 2004, 25, 1030. doi:10.1002/jcc.20030.
(11) Chong, D. P. Mol. Phys. 2005, 103, 749. doi:10.1080/00268970412331333618.
References (12) Takahata, Y.; Chong, D. P. J. Electron Spectrosc. Rel. Phenom. 2003, 133, 69.
(1) Gerega, A.; Lapinski, L.; Reva, I.; Rostkowska, H.; Nowak, M. J. Biophys. Chem. doi:10.1016/j.elspec.2003.08.001.
2006, 122, 123–135. doi:10.1016/j.bpc.2006.03.002. (13) Chong, D. P. Can. J. Chem. 2011, 89 (12), 1477. doi:10.1139/v11-121.
(2) Bergmann, F.; Frank, A.; Neiman, Z. J. Chem. Soc. Perkins Trans. I 1979, 2795. (14) Riley, K. E.; Holt, B. T. O.; Merz, K. M., Jr. J. Chem. Theory Comput. 2007, 3,
doi:10.1039/P19790002795. 407–433. doi:10.1021/ct600185a.
(3) Costas, M. E.; Acevedo-Chávez, R. J. Comput. Chem. 1999, 20, 200. doi:10.1002/ (15) Tirado-Rives, J.; Jorgensen, W. L. J. Chem. Theory Comput. 2008, 4, 297–306.
(SICI)1096-987X(19990130)20:2<200::AID-JCC2>3.0.CO;2-1. doi:10.1021/ct700248k.
(4) Shukla, M. K.; Mishra, P. C. Spectrochim. Acta A 1996, 52, 1547. doi:10.1016/ (16) Gritenko, O. V.; Schipper, P. R. T.; Baerends, E. J. Chem. Phys. Lett. 1999, 302,
0584-8539(96)01662-5. 199–207. doi:10.1016/S0009-2614(99)00128-1.
(5) Hernández, B.; Lique, F. J.; Orozco, M. J. Org. Chem. 1996, 61, 5964. doi:10. (17) Gritenko, O. V.; Schipper, P. R. T.; Baerends, E. J. Int. J. Quantum Chem. 2000,
1021/jo960133w. 76, 407–419. doi:10.1002/(SICI)1097-461X(2000)76:3<407::AID-QUA9>3.0.CO;
(6) Kassimi, N. E.; Thakkar, A. J. Mol. Struct (THEOCHEM) 1996, 366, 185. doi:10. 2-A.
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Istanbul University on 11/05/14

1016/0166-1280(96)04571-X. (18)
(7) Vargas, F.; Rivas, C.; Zoltan, T.; Diaz, Y.; Alexander, I.; Padrón, L.; Izzo, C.;
López, V.; Gómez, L.; Cárdenas, Y. M. Rev. Colomb. Cienc. Quim. Farm. 2008, (19)
37, 69.
(8) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; (20)
Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.;
Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, (21)
J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.;
Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; (22)
Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, (23)
M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.;
Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; (24)
Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.;
Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, (25)
O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; (26)
Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg,
J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; (27)
Cioslowski, J.; Fox, D. J. Gaussian 09, Revision A. 02; Gaussian, Inc., Walling-
ford CT, 2009. (28)
For personal use only.
Schipper, P. R. T.; Gritenko, O. V.; van Gisbergen, S. J. A.; Baerends, E. J.
J. Chem. Phys. 2000, 112, 1344–1352. doi:10.1063/1.480688.
Segala, M.; Chong, D. P. J. Electron Spectrosc. Rel. Phenom. 2009, 171, 18. doi:10.
1016/j.elspec.2008.12.006.
Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865. doi:10.
1103/PhysRevLett.77.3865.
Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1997, 78, 1396. doi:10.
1103/PhysRevLett.78.1396.
Adamo, C.; Barone, V. J. Chem. Phys. 1999, 110, 6158. doi:10.1063/1.478522.
Cavigliasso, G.; Chong, D. P. J. Chem. Phys. 1999, 111, 9485. doi:10.1063/1.
480279.
Chong, D. P.; Aplincourt, P.; Bureau, C. J. Phys. Chem., A 2002, 106, 356.
doi:10.1021/jp0129737.
Chong, D. P. J. Chem. Phys. 1995, 103, 1842. doi:10.1063/1.469758.
Chong, D. P. J. Theor. Comput. Chem. 2013, 12, 1250096. doi:10.1142/
S0219633612500964.
Nonella, M.; Hänggi, G.; Dubler, E. J. Mol. Struct. (Theochem) 1993, 279,
173–190. doi:10.1016/0166-1280(93)90065-J.
Torreggiani, A.; Tamba, M.; Trinchero, A.; Fini, G. J. Mol. Struct. 2003, 651, 91.

(9) ADF Program System, release 2012, Scientific Computing & Modeling, NV, doi:10.1016/S0022-2860(02)00631-2.
Amsterdam, 2006. For a comprehensive description of ADF, see te Velde, G.; (29) Sheldrick, W. S.; Günther, B. Inorg. Chem. 1988, 151, 237–241.

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