17092 J. Phys. Chem.

B 2010, 114, 17092–17101

DFT Study on the Standard Electrode Potentials of Imidazole, Tetrathiafulvalene, and

Tetrathiafulvalene-Imidazole

Tugba Tugsuz*
Department of Chemistry, Hacettepe UniVersity, Beytepe, Ankara 06800, Turkey
ReceiVed: July 19, 2010; ReVised Manuscript ReceiVed: October 28, 2010

Extensive DFT calculations on the standard electrode potentials of imidazole (Im), tetrathiafulvalene (TTF),
and 2-, 4-, and 5-TTF-Im were carried out. Geometries and Gibbs free energies of H-bonded dimer, anion,
protonated cation, and neutral structures of Im, mono- and dication, and neutral structures of TTF in gas and
acetonitrile solvent were computed by using 10 hybrid density functionals (B3LYP, TPSSH, PBEH1PBE,
M06, M062X, X3LYP, BMK, B1B95, M05, M052X) combined with the TZVP basis set. CPCM and SMD
solvation models were applied to predict the Gibbs free energies of molecules in acetonitrile solvent. Frequency
calculations were carried out for all structures, and none of them has been found to exhibit any imaginary
frequency. Finally, the BMK hybrid functional was selected for computation of the standard electrode potential
of TTF-Im, because it gives the most accurate values in both Im and TTF, differing by 0.05 V from the
experimental ones. Moreover, frequencies from the BMK functional are reasonably close to the experimental
ones. The standard electrode potentials of 2-, 4-, and 5-TTF-Im predicted for two-electron oxidation are
0.946, 0.870, and 0.839 V in CPCM and 0.927, 0.866, and 0.824 V in SMD. For one-electron oxidation these
are 0.491, 0.421, and 0.400 V in CPCM and 0.476, 0.377, and 0.360 V in SMD, respectively.

Introduction by adding HBF4. Reductions occur by 2n electrons in oligomers

Imidazole (Im) is a five-membered planar ring structure
(C3H4N2), which has two tautomeric forms, because hydrogen
can be located in either of the two nitrogen atoms. Im forms
strong and directional H-bond interactions, while nitrogen
functions as a proton donor/acceptor. This feature of Im has
attracted the interest of experimentalists as well as theoreticians.1-8
The unique ring structure of Im permits the pick up of a proton
on one of its N atoms to form a cation and deliver another
hydrogen from the other N to the second site, causing the proton
transfer process. Because of this process Im plays a significant
role in biological systems, especially for enzyme actions and
determination of protein structures.1
Im and some of its derivatives form a class of nucleophilic
and general base catalysts.2 It is used as a ligand to the metal
ions in B12 coenzyme.3 It consists of a crystalline structure with
parallel chains of Im molecules, and its electric conductivity
along one crystallographic axis was found to be higher than
along the other ones.4 Various experimental investigations have
been carried out for the structure and relative energies of
H-bonded Im molecules. The electrochemical reduction poten-
tials of Im and its monoprotonated compound in acetonitrile
have also been calculated by considering infinite chain struc-
tures. The values reported are -1.77 and -0.73 V, respectively.5
It was also shown that the electrochemical reduction potentials
of n dimer-Im can be reduced with 2n electrons through 2n
anions of Im (Im-) and nH2 in the gas form in the presence of
TBABF4 (tetrafluoroborate) versus Ag/AgCl electrode, respec-
tively. When Im is protonated with HBF4, the peak can be
reduced at a more positive potential, giving rise to additional
reduction peaks at -0.73 V.5 In another study the H-bond
capability and electroreducibility of aminobenzimidazoles in the
presence of TBABF4 and their protonated forms were shown
* To whom correspondence should be addressed. Phone: 00903122976297.
Fax: 00903122992163. E-mail: ttugsuz@hacettepe.edu.tr.
10.1021/jp106705d  2010 American Chemical Society
Published on Web 12/07/2010
and 2 electrons in protonated structures with release of H2 gas.6
Hydrogen-bonding studies for Im structures have also been
investigated in theoretical calculations. Brédas et al. studied
monomer, dimer, and infinite chain structures of Im with ab
initio techniques.7 Tafazzoli and Amini studied hydrogen
bonding on Im and its 4-nitro derivative with calculated chemical
shielding by ab initio and density functional theory (DFT)
methods.8 Both have shown that the DFT method gives better
results than the Hartree-Fock (HF) method.
Moreover, the strong and directional H-bond interactions of
Im have attracted much attention in molecular conductors
because they can be modified by bonding to donor molecules
(such as, tetrathiafulvalene (TTF)) to give them H-bond capabil-
ity.9 TTF is an excellent π-electron donor, and its association
with electron-accepting compounds has attracted considerable
attention for development of organic conducting materials since
the 1970s.10 The TTF unit and its derivatives have recently
appeared as key constituents for new applications to molecular
sensors, redox-fluorescent switches, molecular electronic switches,
spectroelectrochemical cells, etc.11
Over the past few years, the geometry of TTF has been
extensively studied theoretically.12 According to these studies,
the most stable conformation of TTF is boat-like, in agreement
with gas-phase electron diffraction data.13 Wartelle et al. have
shown that this boat-like structure is folded along the S2-S3
axes of the rings by an angle of 12.9°. For the radical cation,
TTF•+, the conformation obtained is a fully planar geometry,
while the conformation for the TTF2+ dication is a structure in
which two planar rings have been twisted around the C1-C1′
bond by a torsional angle of 35.9°.14
TTF is a nonaromatic 14 π-electron molecule and can be fully
and reversibly oxidized in two steps to TTF•+ and TTF2+. These
cationic species possess aromaticity with one and two 6
π-electrons, respectively. Both oxidation steps are reversible,
which account for the good stability of both cationic species.
DFT Study on Standard Electrode Potentials
Figure 1. Molecular geometries of (a) dimer and (b) anion (Im-) structures of Im.
Figure 2. Molecular geometries of (a) monoprotonated cation and (b)
neutral structures of Im.
Thus, the electron-donating ability of the TTF system can be
tuned, and this point is critical when aiming for switchable
systems. Canevet et al. studied TTF derivatives for switchable
processes. They have shown that the first (E11/2) and second
(E21/2) oxidation potentials with two successive one-electron
oxidation steps of TTF to TTF•+ and TTF2+ were 0.34 and 0.78
V in acetonitrile versus Ag/AgCl electrode, respectively.11a
Wartelle et al. not only studied the geometries of TTF in neutral
cation dication states but also evidenced the occurrence of IR
signals. They analyzed the IR spectra of the oxidation process
of TTF with the aid of B3P86/6-31G**, and the most relevant
changes found were asymmetric stretching of the lateral CdC
bonds which have undergone a frequency downshift (TTF, 1564
cm-1; TTF+, 1502 cm-1; TTF2+, 1431 cm-1).14
The TTF-Im has both π-electron-donating ability and inter-
molecular H-bonding functionality. The hydrogen bond can
cause production of a number of highly conductive molecules
having various acceptors with a wide range of electron accept-
ability. Murata and Morita et al. explored new molecular
conductors electronically and structurally modulated by H bond.
They investigated the donor-acceptor charge transfer complexes
of TTF-Im with several acceptors. Moreover, the cyclic volta-
mmetric measurements of TTF derivatives at the 2- and
4-position of the imidazole ring showed two-stage one-electron
reversible oxidation behavior: -0.06, 0.20 V and -0.11, 0.15
V in DMF versus Fc/Fc+ electrode, respectively.9,15
Figure 3. Molecular geometries of (a) neutral (TTF), (b) radical cation (TTF+•), and (c) dication (TTF2+) structures of TTF.
J. Phys. Chem. B, Vol. 114, No. 51, 2010 17093
Theoretical prediction of electrode potentials based on
quantum mechanical calculations has been an area of interest
in recent years.16 The present work aims at calculation of the
standard electrode potential of the two-electron reduction of
H-bonded dimer (Figure 1a) and the one-electron reduction of
protonated cationic structure of Im (Figure 2a) and two- and
one-electron oxidation of TTF (Figure 3a) and TTF-Im (Figure
4) using the methods developed by Namazian et al.,16a-c Kelly
et al.16d and Song et al.16e,f for calculating the standard electrode
potential. The basis of our calculation is DFT. However,
although in principle this theory is exact both for the ground
and excited states,17 there is no exact expression for the exchange
and correlation functional Exc, and although many such func-
tionals have been proposed, they give relatively exact results
for special cases.18 Therefore, it was necessary to find the
appropriate functional for electrochemistry. For this purpose,
we calculated the standard electrode potentials of Im and TTF
by using 10 hybrid density functionals (B3LYP, TPSSH,
PBEH1PBE, M06, M062X, X3LYP, BMK, B1B95, M05,
M052X) combined with the TZVP basis set in gas and
acetonitrile. We found BMK the most appropriate functional
for both methods used and adopted it for prediction of the
standard electrode potentials of one- and two-electron oxidation
of 2-, 4-, and 5-TTF-Im.
Methods and Theoretical Considerations. The standard
electrode potentials can be obtained theoretically by employing
different methods. In the present work the following two have
been used.16a-f
Method 1. Calculation of the electrode potential of Im(d,p)
(dimer and protonated cation structures of Im), compared to
NHE (normal hydrogen electrode), is possible through the Gibbs
free energy change of the following reaction
+
Im(d,p)(sol) f 2Im(a,m)(sol) + 2H(sol) (1)
where Im(a,m) is the anion and monomer structures of Im.
17094 J. Phys. Chem. B, Vol. 114, No. 51, 2010 Tugsuz

Figure 4. Stable 2-, 4- and 5-TTF-Im structures.

Reaction 1 involved the following two half-reactions ∆G*i ) ∆G(i,gas)

o
+ ∆G*(i,sol) (9)

-
Im(d)(sol)(2Im(p)(sol)) + 2e(gas) f 2Im(a)(sol)(2Im(m)(sol)) + Finally, ∆G*2,4,5 was calculated using the equation
H2(gas) (2)
∆G*2,4,5 ) ∆G*(i) + n∆Gof (10)
+ -
2H(sol) + 2e(gas) f H2(gas) (3)
f
where n is the number of electrons transferred and ∆Go is the
The same method was used for the electrode potentials of TTF correction for the change in standard state from 1 atm for gas-
and TTF-Im compared to NHE for the following reactions. phase calculations “o” to 1 mol L-1 for the solution phase “*”
For TTF and TTF-Im of 7.9 kJ/mol for each component (RT ln(24.46)).19
Then, the standard reduction potential of Im (E2o) and
2+
TTF(sol) f TTF(sol) +
(TTF(sol) -
) + 2e(gas) -
(e(gas) ) (4) oxidation potentials of TTF and TTF-Im (E4oand E5o) are related
to the standard free energy change relative to the NHE (∆G3o)
of the redox reactions through the following eqs 11 and 12,
+ - -
2+
TTF-Im(sol) f TTF-Im(sol) (TTF-Im(sol) ) + 2e(gas) (e(gas) ) respectively.
(5)
SCHEME 1: Thermochemical Cycles for Method 1
Then with NHE, the overall reactions like reaction 1 are

+ + +
TTF(sol) + 2H(sol) (H(sol) 2+
) f TTF(sol) (TTF(sol) )+
H2(gas)(1/2H2(gas)) (6)

+ + +
TTF-Im(sol) + 2H(sol) (H(sol) 2+
) f TTF-Im(sol) (TTF-Im(sol) )+
H2(gas)(1/2H2(gas)) (7)

o
∆G2,4,5 was obtained from the following equation

o
∆G2,4,5 ) ∑ νi∆Gio (8)

where ∆Goi is the change of Gibbs free energy for each

component of reactions 2, 4, and 5.
We calculated the gas-phase Gibbs free energies, ∆Goi , using
a standard-state gas-phase pressure of 1 atm. For the solution-
phase Gibbs free energies, ∆G*,
i a standard-state solution-phase
concentration of 1 mol L-1 was used.
Thus, ∆G*i values were calculated through a thermochemical
cycle in Scheme 1 by the following equation
DFT Study on Standard Electrode Potentials J. Phys. Chem. B, Vol. 114, No. 51, 2010 17095

∆G*2 - n∆Go3 SCHEME 2: Thermochemical Cycles for Method 2

Eo2 )- (11)
nF

◦
◦
n∆Go3 - ∆G4,5
E4,5 )- (12)
nF

Here, n is the number of electrons transferred (n ) 2 and 1 in

these cases) and F is the Faraday constant (F ) 96485 C mol-1).
The value of ∆G3o is known to be 4.48 eV.16d
Method 2. In this method, reactions 1, 6, and 7 have been
used directly. The redox reaction in solution has been designed
as thermochemical cycles, which are illustrated in Scheme 2.
The standard transformed Gibbs free energies of reactions 1,
6, and 7 in solution are

∆Go1 ) ∆Ggas
o
- ∆Gsol(Im
o
(d,p))
+ ∆Gsol(Im
o
(a,m))
+ ∆Gsol(H
o
+) +

n∆Gof (13)

∆Go6 ) ∆Ggas
o
- ∆Gsol(TTF)
o
- ∆Gsol(H
o
+) + ∆Gsol(TTF2+) +
o

n∆Gof (14)
∆Go7 ) ∆Ggas
o
- ∆Gsol(TTF-Im)
o
- ∆Gsol(H
o
+) +
2+) + n∆G
o of
∆Gsol(TTF-Im (15)
For the total gas-phase free energy of the proton from 0 to 298
K, we used a value of -6.28 kcal mol-1 for a pressure of 1 atm
from the well-established approaches of Tawa et al.20 The
absolute solvation free energy of the proton in acetonitrile was
taken from the article of Kelly et al. as 260.2 kcal mol-1.16d
f
The ∆Go correction, which was not included originally in
method 2 calculations, was added to the Gibbs free energy of
reactions 1, 6, and 7.
In order to calculate standard electrode potential (Eo) of the
half-reduction reaction of 2 and half-oxidation reactions of 4
and 5, eqs 16 and 17 were used, respectively
∆Go1
Eo2 ) - (16)
nF
o neutral structures of TTF, using 10 hybrid DFT functionals
∆G6,7
o
E4,5 ) (17)
nF
This method requires the reference electrode potential E3o of
NHE, which is equal 0.00 V in SI units. Moreover, both methods
mentioned above have been developed for the 1e- reduction of
protonated cation of Im and 1e- oxidation processes of TTF
and TTF-Im structures, respectively.
Computational and Theoretical Background. In this work
all calculations were performed by density functional theory
(DFT) using the Gaussian 09 Rev. A.02-SMP software pack-
age.21 The geometries of dimer, anion, protonated cation, and
neutral Im and mono- and dication and neutral TTF in gas and
acetonitrile have been fully optimized using the following 10
hybrid density functionals: B3LYP,22 TPSSH,23 PBEH1PBE,24
M06,25 M062X,25 X3LYP,26 BMK,27 B1B95,28 M05,29 M052X30
of DFT.17,31 The valence triple-ζ quality with polarization
function basis set TZVP32 has been selected mainly for its
increasing convergence criteria and because it gives more
accurate energies than double-ζ quality basis sets. Frequency
calculations have been carried out for all the structures, and
none of them was found to exhibit any imaginary frequency.
To calculate solvation energies, choosing an efficient model of
solvation is certainly very important. In the present study, two
models of solvation, the conductor-like polarizable continuum
model, CPCM,33 and universal solvation model, SMD,34 have
been employed for considering the solvent contribution at the
above level of theory. The radii of the universal force field (UFF)
for CPCM and SMD-Coulomb for SMD have been used.
Results and Discussion
Before discussion of the electrode potentials, it is helpful to
have a thorough knowledge of the optimization of geometries,
since the thermochemical values are controlled by molecular
geometries. The results are summarized in the following order:
First, the most stable molecular geometries without any
imaginary frequency for the H-bonded dimer, anion, protonated
cation, and neutral structures of Im and mono- and dication and
(B3LYP, TPSSH, PBEH1PBE, M06, M062X, X3LYP, BMK,
B1B95, M05, M052X) combined with the TZVP basis set in
gas and acetonitrile phases, were calculated. Then, we adopted
the functional giving values closer to the experimental ones for
calculation of the electrode potentials for two- and one-electron
reduction and oxidation for dimer, protonated Im, and mono-
and dication of TTF. At this stage, experimental and theoretical
IR results were discussed. Finally, the standard electrode
potentials of 2-, 4-, and 5-TTF-Im structures were predicted.
Molecular Geometries and IR Results.
Imidazole. Figure 1a shows the structure of dimer Im. The
H-bond distances, angles between N3-H9′-N1′, and dihedral
angles between two rings, as C2-N3-N1′-C2′ of the optimized
dimer Im structures from up to down gas, acetonitrile (CPCM),
and acetonitrile (SMD) are given in Table 1. The H bonds found
are approximately ∼2.0 Å, in agreement with experimental and
theoretical results.4-8,35-37 Short H bonds tend to have wide
Im-H-Im bond angles (ca. 180°).35 The planes of the Im rings
17096 J. Phys. Chem. B, Vol. 114, No. 51, 2010 Tugsuz

TABLE 1: Computed H-Bond Lengths, Angles, Frequencies, and Gibbs Free Energies, ∆G, of Dimer Im and Anion (Im-)
Structures in (from top to bottom) Gas, Acetonitrile (CPCM), and Acetonitrile (SMD)
∆G° (hartree)
H-bond length H-bond angle dihedral angle frequencies
functional (Å) N3-H1′ (deg, ∠N3H1′N1′) (deg, ∠C2N3N1′C2′) (cm-1) dimer Im Im-
B3LYP 1.966 178.8 86.50 3327 -452.500654 -225.690899
1.873 179.8 87.73 3121 -452.518027 -225.785223
1.874 178.7 86.00 3109 -452.531879 -225.791314
TPSSH 1.930 178.2 86.48 3263 -452.523121 -225.699440
1.834 179.6 88.02 3029 -452.540426 -225.793236
1.832 178.5 86.07 3009 -452.553785 -225.800153
PBEH1PBE 1.917 177.4 86.87 3314 -452.017714 -225.447942
1.824 179.7 87.93 3081 -452.035749 -225.542791
1.819 178.5 85.98 3057 -452.049916 -225.549264
M06 1.960 179.3 84.15 3363 -452.172378 -225.528085
1.879 179.3 84.50 3185 -452.188706 -225.621471
1.879 178.9 85.13 3173 -452.202495 -225.628255
M062X 1.947 177.8 82.32 3347 -452.307103 -225.597181
1.857 179.9 82.50 3134 -452.324974 -225.692615
1.855 177.6 94.86 3122 -452.340758 -225.699866
X3LYP 1.956 178.8 86.37 3328 -452.296359 -225.588296
1.865 179.8 87.71 3120 -452.313764 -225.682630
1.866 178.6 85.98 3108 -452.327686 -225.689386
BMK 1.986 178.1 88.19 3451 -452.210580 -225.547061
1.887 178.9 90.52 3277 -452.228574 -225.642468
1.889 178.8 85.21 3267 -452.243493 -225.649004
B1B95 1.976 178.8 86.49 3381 -452.302145 -225.590179
1.880 179.8 87.72 3178 -452.319895 -225.684818
1.880 178.6 94.74 3164 -452.331045 -225.691972
M05 1.981 178.3 90.42 3433 -452.167519 -225.525511
1.904 179.0 91.42 3263 -452.184536 -225.619408
1.906 178.1 95.23 3252 -452.197948 -225.626360
M052X 1.969 174.7 84.52 3405 -452.441602 -225.662956
1.882 180.0 83.12 3170 -452.460754 -225.759004
1.885 177.9 94.93 3172 -452.475518 -225.766442

are almost orthogonal (∼90°) for structures in both the gas and
the acetonitrile phases.
Figure 2a shows the monoprotonated ImH+ structure. The
ImH+ structure shows that protonation of Im occurs on the lone
pair of nitrogen (in the plane of the ring), while the number of
π-electron delocalizations do not change. The selected bond
lengths and angles of Im and ImH+ structures are listed in Table
2. The calculated Im and ImH+ geometries are in good
agreement with the literature data.36
Tables 1 and 2 contain calculated frequencies of dimer and
protonated Im using the CPCM and SMD solvation models in
acetonitrile solution. The vibrational stretching mode of N-H · · · N
of dimer Im is significant. It was pointed out in ref 6 that the
stretching frequency for this bond in acetonitrile solvent is 3359
cm-1. The nearest frequency found from the BMK hybrid
functional calculation is 3277 cm-1 at CPCM and 3267 cm-1
at SMD solvation models. The modes most affected by
hydrogen-bond formation are the N-H stretching modes of Im.
According to Table 2, these modes have a frequency range of
3700-3640 cm-1 in all hybrid functional calculations. In the
BMK functional for Im and ImH+ they are 3693, 3678 cm-1 at
CPCM and 3661, 3643 cm-1 at SMD, respectively. It must be
noted that because of the strong hydrogen-bond formation, the
N-H · · · N stretching frequency has been shifted toward the
lower frequencies.
TTF. The geometries of TTF, TTF+, and TTF2+ (Figure
3a-c) structures in the gas and acetonitrile phase have been
computed using B3LYP, TPSSH, PBEH1PBE, M06, M062X,
X3LYP, BMK, B1B95, M05, and M052X. Table 3 shows the
most important geometrical results, such as folding along the
S2-S3 axes of TTF rings and torsional angle between the rings
of TTF+ and TTF2+ structures.
It also contains the calculated frequencies of TTF, TTF+, and
TTF2+ in acetonitrile. The out of phase stretching of the outer
C4dC5 double bonds coupled with the bending of the C-H
bonds has been given for the most fundamental frequency with
an intense peak. This stretching has been recorded experimen-
tally for a neutral TTF molecule as 1530 cm-1.38 According to
computational results, the frequency for this mode has been
overestimated by 50, 40, 55, 58, and 61 cm-1 by the TPSSH,
B3LYP, X3LYP, M05, and BMK hybrid functionals at CPCM,
respectively. SMD results have been found to be similar to those
of CPCM results.
For TTF+ in solution, the experimental band corresponding
to the vibrational mode explained above has been observed at
1474 cm-1 for the TTFClO4 salt39 while from computational
results the nearest band has been observed from TPSSH
calculation at 1537 and 1536 cm-1 at CPCM and SMD,
respectively, a deviation of ∼63 cm-1. The B3LYP, BMK, and
X3LYP calculations overestimated the experimental value by
70, 71, and 75 cm-1 in both CPCM and SMD. For the dication,
TTF2+, the calculated intense peaks have been compared with
the experimentally observed value at 1435 cm-1. Similarly to
TTF and TTF+, the nearest calculated intense peak has been
taken from TPSSH, calculated by CPCM as 1479 cm-1 and by
SMD as 1471 cm-1 with ∼40 cm-1 discrepancy. The other
nearest results taken from B3LYP, BMK, and X3LYP have been
calculated as 1486, 1487, and 1490 cm-1 by CPCM and 1479,
1480, and 1483 cm-1 by SMD solvation models.
TTF-Im. Inspection of all the Im and TTF results obtained
by methods 1 and 2 has shown that the calculated electrode
potentials obtained by the BMK hybrid functional are in good
agreement with experimental results. Frequencies of the Im and
TTF structures have also shown that the values taken from BMK
DFT Study on Standard Electrode Potentials J. Phys. Chem. B, Vol. 114, No. 51, 2010 17097

TABLE 2: Selected Bond Lengths, Angles, Frequencies for N-H Bond Stretching, and Computed Gibbs Free Energies, ∆Go, of
the Neutral Im (Im) and Monoprotonated Cation (ImH+) Structures in (from top to bottom) Gas, Acetonitrile (CPCM), and
Acetonitrile (SMD)
bond lengths (Å) N1-H9 bond angles (deg) (∠N1C2N3) frequencies (cm-1) N-H bond stretching ∆G° (hartree)
+ + +
functional Im ImH Im ImH Im ImH Im ImH+
B3LYP 1.006 1.012 111.5 107.0 3652 3599-3607 -226.250620 -226.610313
1.008 1.011 111.4 107.2 3640 3606-3623 -226.261440 -226.698666
1.011 1.013 111.2 107.1 3606 3578-3590 -226.269958 -226.718320
TPSSH 1.008 1.013 111.6 107.0 3638 3586-3593 -226.261477 -226.628285
1.010 1.012 111.5 107.1 3628 3598-3617 -226.272223 -226.711658
1.012 1.015 111.3 107.0 3597 3572-3582 -226.280667 -226.731097
PBEH1PBE 1.005 1.011 111.6 107.0 3694 3636-3643 -226.008345 -226.368781
1.007 1.010 111.5 107.2 3676 3641-3660 -226.019448 -226.457223
1.009 1.012 111.3 107.1 3645 3615-3626 -226.028190 -226.477027
M06 1.005 1.011 111.9 107.3 3657 3602-3613 -226.086478 -226.443776
1.007 1.010 111.7 107.4 3646 3607-3631 -226.096844 -226.532029
1.010 1.013 111.5 107.3 3613 3583-3594 -226.105096 -226.551364
M062X 1.006 1.012 111.6 107.1 3693 3598-3624 -226.153701 -226.509784
1.008 1.012 111.5 107.2 3660 3613-3624 -226.165128 -226.598286
1.011 1.014 111.3 107.2 3613 3567-3600 -226.174060 -226.618303
X3LYP 1.006 1.012 111.5 107.1 3658 3604-3612 -226.148101 -226.507184
1.008 1.011 111.4 107.2 3646 3610-3627 -226.158943 -226.595593
1.010 1.013 111.2 107.1 3612 3582-3594 -226.167501 -226.615321
BMK 1.006 1.012 111.6 107.1 3708 3654-3664 -226.106357 -226.467227
1.008 1.011 111.4 107.2 3694 3659-3678 -226.117925 -226.555628
1.011 1.013 111.2 107.1 3661 3634-3643 -226.126780 -226.575441
B1B95 1.003 1.009 111.6 107.0 3699 3639-3647 -226.151620 -226.511926
1.006 1.008 111.5 107.2 3681 3644-3664 -226.162551 -226.600346
1.008 1.011 111.3 107.1 3649 3619-3629 -226.171210 -226.620053
M05 1.004 1.009 111.9 107.1 3698 3637-3660 -226.083858 -226.439754
1.005 1.008 111.7 107.2 3692 3641-3679 -226.094282 -226.528056
1.008 1.010 111.6 107.2 3659 3624-3640 -226.102697 -226.547641
M052X 1.003 1.009 111.6 107.2 3744 3650-3665 -226.220135 -226.577963
1.005 1.008 111.4 107.3 3715 3662-3672 -226.232056 -226.666548
1.007 1.011 111.2 107.2 3668 3615-3643 -226.241209 -226.686658

calculation have been found to be reasonably close to the
experimental values. For this reason, the BMK/TZVP level of
theory has been selected for computing the standard electrode
potential of 2-, 4-, and 5-TTF-Im structures.
To further understand the bonding effect of 2-, 4-, and 5-TTF-
Im on the electrode potentials, full geometry optimizations of
both tautomeric species of 2-, 4-, and 5-TTF-Im structures have
been computed in their a and b forms (Supporting Information)
by the BMK/TZVP level of theory. The a form of 2- and 4-TTF-
Im and b form of 5-TTF-Im have been found to be energetically
stable structures. Figure 4 displays the calculated structures. The
one- and two-electron oxidations of 2-, 4-, and 5-TTF-Im+, TTF-
Im2+ structures have also been computed at the same level of
theory. Table 4 shows N-H stretching modes of frequencies
and Gibbs free energies of the stable 2-, 4-, and 5-TTF-Im
structures. The N-H stretching modes for neutral, cationic, and
dicationic structures have been found in the range 3630-3710
cm-1.
Standard Electrode Potentials. The standard Gibbs free
energies of Im and TTF structures in the gas and solution
phases computed using B3LYP, TPSSH, PBEH1PBE, M06,
M062X, X3LYP, BMK, B1B95, M05, and M052X are given
in Tables 1-3. That of H2 computed from 10 hybrid
functionals are given in the Supporting Information. The
standard electrode potentials (Eo) calculated from the change
in standard Gibbs free energies for dimer and protonated
cationic structures of Im in methods 1 and 2 are given in
Table 5. It was found that dimer structures have been shifted
to lower potentials because of H bonding. For this reason,
dimer structures reduced earlier than the protonated cationic
structure. The calculated electrode potentials for dimer Im
obtained by M05, PBEh1PBE, BMK, and B1B95 with
method 1 (in both CPCM and SMD calculation) are found
reasonably close to the experimental value (deviations are
equal and less than 0.05 V). On the other hand, calculations
from method 2 have shown that only the TPSSH result is
close to the experimental value with 0.03 and 0.04 V relative
Eo values from CPCM and SMD, respectively. For the
protonated cation ImH+, all results obtained by method 1
with CPCM have shown that the electrode potential calculated
by the present model is close to the experimental value with
MAD at 0.06 V, whereas the calculated electrode potentials
with SMD differ on average by more than 0.28 V from
experimental values. In method 2 CPCM and SMD calcula-
tions of the standard electrode potential of protonated Im
for the same hybrid functional are consistent with those of
method 1. The MADs obtained are about 0.10 and 0.20 V
for CPCM and SMD, respectively.
The standard electrode potentials (Eo) for two- and one-
electron oxidation of TTF in methods 1 and 2 are given in
Table 6. These are relative Eo values. Although some of them
are more than 0.10-0.30 V different from the experimental
value, M062X, BMK, and M052X results are in good
agreement with the experimental value in both methods and
both solvation models. The relative Eo results obtained by
M062X, BMK, and M052X hybrid functionals for the two-
electron oxidation of the TTF structure with CPCM are 0.04,
0.06, 0.05 V and 0.09, 0.06, 0.06 V by methods 1 and 2,
respectively. With SMD solvation models, these values are
0.05, 0.07, 0.06 V and 0.07, 0.05, 0.05 V with methods 1
17098 J. Phys. Chem. B, Vol. 114, No. 51, 2010 Tugsuz

TABLE 3: Folding Along S2-S3 Axes θ, Torsional Angles, Most Intense C4dC5 Vibration Frequencies, and Computed Gibbs
Free Energies, ∆Go, of TTF, TTF+, and TTF2+ Structures in (from top to bottom) Gas, Acetonitrile (CPCM), and Acetonitrile
(SMD)
torsional angles C4dC5 vibration frequencies ∆Go (hartree) gas acetonitrile(CPCM)/
folding S2-S3 axes θ (deg, ∠S2C1C1′S2′) (cm-1) acetonitrile(SMD)
functional TTF TTF+ TTF2+ TTF TTF+ TTF2+ TTF TTF+ TTF2+
B3LYP 10.96 0.00 37.23 1601 1542 1473 -1823.857432 -1823.622919 -1823.214884
10.09 0.00 36.38 1601 1544 1486 -1823.864686 -1823.691879 -1823.480665
7.74 2.89 34.96 1605 1543 1479 -1823.870470 -1823.698334 -1823.486963
TPSSH 14.58 0.00 33.46 1591 1535 1466 -1823.887256 -1823.656424 -1823.252895
14.24 0.01 33.35 1590 1537 1479 -1823.894574 -1823.725523 -1823.517630
14.01 2.82 30.21 1592 1536 1471 -1823.900589 -1823.733637 -1823.524679
PBEH1PBE 13.18 0.02 37.82 1626 1565 1494 -1823.070897 -1822.838221 -1822.430331
12.84 0.02 36.81 1624 1567 1507 -1823.078486 -1822.906722 -1822.695764
11.85 2.52 35.11 1628 1566 1500 -1823.085448 -1822.914634 -1822.702558
M06 12.58 0.00 36.94 1625 1569 1492 -1823.547187 -1823.313508 -1822.908002
12.30 0.00 35.67 1623 1571 1504 -1823.554244 -1823.381744 -1823.173273
8.54 2.53 33.06 1628 1570 1494 -1823.559840 -1823.388881 -1823.179176
M062X 12.50 0.01 43.73 1631 1564 1500 -1823.637763 -1823.395953 -1822.985811
12.01 0.01 46.66 1630 1565 1515 -1823.646079 -1823.464562 -1823.251251
8.33 0.96 45.76 1646 1563 1510 -1823.651047 -1823.472943 -1823.257196
X3LYP 10.99 0.00 37.18 1607 1546 1478 -1823.562615 -1823.329531 -1822.922817
10.06 0.00 36.47 1606 1549 1490 -1823.569917 -1823.398515 -1823.188737
7.75 3.09 34.97 1610 1547 1483 -1823.575731 -1823.405646 -1823.195060
BMK 11.08 0.00 37.73 1606 1544 1476 -1823.188913 -1822.949681 -1822.539022
10.10 0.02 36.70 1606 1545 1487 -1823.196624 -1823.018545 -1822.803965
8.84 3.01 35.45 1609 1543 1480 -1823.202033 -1823.026062 -1822.810564
B1B95 14.85 0.01 38.46 1630 1569 1499 -1823.888784 -1823.659378 -1823.257001
14.60 0.05 36.87 1629 1571 1511 -1823.896166 -1823.727752 -1823.522613
14.44 2.06 34.78 1631 1569 1504 -1823.902382 -1823.736424 -1823.529376
M05 7.75 0.00 40.49 1618 1558 1487 -1823.653789 -1823.425909 -1823.022203
7.45 0.00 39.35 1616 1560 1501 -1823.660810 -1823.494109 -1823.287123
7.21 3.36 39.95 1620 1559 1496 -1823.667034 -1823.501377 -1823.293456
M052X 12.50 0.02 44.80 1653 1571 1502 -1823.752422 -1823.512936 -1823.103980
12.16 0.04 47.42 1639 1572 1516 -1823.763454 -1823.582375 -1823.369725
8.28 1.33 46.14 1644 1571 1511 -1823.768354 -1823.591300 -1823.375502

TABLE 4: Frequencies of N-H Bond Stretching and Gibbs Free Energies of the Stable 2-, 4-, and 5-TTF-Im Structures in
(from top to bottom) Gas, Acetonitrile (CPCM), and Acetonitrile (SMD)
frequencies (cm-1) N-H bond stretching Gibbs free energies, ∆Go (hartree)
+
TTF-Im complexes TTF-Im TTF-Im TTF-Im 2+
TTF-Im TTF-Im+ TTF-Im2+
2-TTF-Im (a) 3684 3683 3655 -2048.111516 -2047.874252 -2047.487726
3669 3674 3661 -2048.125605 -2047.945931 -2047.732781
3650 3648 3628 -2048.137085 -2047.957962 -2047.745667
4-TTF-Im (a) 3705 3687 3645 -2048.113227 -2047.885145 -2047.500714
3684 3682 3679 -2048.129634 -2047.952549 -2047.742396
3664 3662 3650 -2048.143151 -2047.967683 -2047.756218
5-TTF-Im (b) 3711 3680 3648 -2048.110854 -2047.886761 -2047.505478
3692 3676 3669 -2048.130318 -2047.953987 -2047.745428
3658 3652 3642 -2048.145033 -2047.970185 -2047.761198

and 2, respectively. For one-electron oxidation of TTF
structure in method 1, the results taken from the CPCM
solvation model differ by more than 0.10 V from SMD model.
By method 2 the one-electron oxidation of TTF structure with
CPCM is 0.08, 0.00, and 0.06 V and with SMD 0.01, 0.05,
and 0.05 V from M062X, BMK, and M052X functionals,
respectively.
All Im and TTF results obtained by methods 1 and 2 show
that selection of the functional for calculation of the electrode
potentials is very hard due to the close values. The best approach
is to find the appropriate functional by intersection of the
functionals having the closest results with experimental data
calculated from both methods. In Im calculations M05 and BMK
functionals and in TTF calculations M062X, M052X, and BMK
functionals close to experimental values with small differences.
BMK is in both results and differing by 0.05 V from its
experimental value. Moreover, frequencies of Im and TTF
structures, computed from the BMK functional, are reasonably
close to the experimental values. For this reason, the BMK/
TZVP level of theory was selected for computing the standard
electrode potentials of 2-, 4-, and 5-TTF-Im structures. Due to
tautomerization, for selection of the most stable one, the
geometries of these structures were computed in their a and b
forms, see Supporting Information. Thus, the a form of 2- and
4-TTF-Im and the b form of 5-TTF-Im were found as the
energetically stable structures. Table 7 shows the electrode
potentials of stable 2-, 4-, and 5-TTF-Im structures. For method
1 and the CPCM solvation model, the standard electrode
potentials of 2-, 4-, and 5-TTF-Im were computed for two-
electron oxidation as 0.946, 0.870, and 0.839 V and for one-
electron oxidation as 0.491, 0.421, and 0.400 V, respectively.
For method 2 these values are approximately 0.12 V above those
DFT Study on Standard Electrode Potentials J. Phys. Chem. B, Vol. 114, No. 51, 2010 17099

TABLE 5: Standard Electrode Potentials (Eo) of Dimers Im/Im- and ImH+/Im Calculated with Methods 1 and 2 in CPCM and
SMD Solvation Models
CPCM SMD
Eo dimer rel Eo dimer Eo ImH+/ Eo dimer rel Eo dimer
Im/Im- (V) Im/Im- Im (V) rel Eo ImH+/Im Im/Im- (V) Im/Im- Eo ImH+/Im (V) rel Eo ImH+/Im
method 1
expa -1.54 -0.50 -1.54 -0.50
B3LYP -1.39 0.15 -0.39 0.11 -1.41 0.13 -0.69 0.19
TPSSH -1.48 0.06 -0.46 0.04 -1.48 0.06 -0.76 0.26
PBEH1PBE -1.57 0.03 -0.55 0.05 -1.59 0.05 -0.85 0.35
M06 -1.48 0.06 -0.46 0.04 -1.48 0.06 -0.76 0.26
M062X -1.43 0.11 -0.43 0.07 -1.45 0.09 -0.74 0.24
X3LYP -1.48 0.06 -0.46 0.04 -1.49 0.05 -0.76 0.26
BMK -1.49 0.05 -0.56 0.06 -1.51 0.03 -0.86 0.36
B1B95 -1.59 0.05 -0.58 0.08 -1.55 0.01 -0.88 0.38
M05 -1.52 0.02 -0.46 0.04 -1.52 0.02 -0.76 0.26
M052X -1.47 0.07 -0.46 0.04 -1.46 0.08 -0.76 0.26
MADb 0.07 0.06 0.06 0.28
method 2
expa -1.54 -0.50 -1.54 -0.50
B3LYP -1.42 0.12 -0.42 0.08 -1.44 0.10 -0.73 0.23
TPSSH -1.51 0.03 -0.48 0.02 -1.50 0.04 -0.78 0.28
PBEH1PBE -1.45 0.09 -0.44 0.06 -1.47 0.07 -0.74 0.24
M06 -1.39 0.15 -0.37 0.13 -1.40 0.14 -0.67 0.17
M062X -1.31 0.23 -0.31 0.19 -1.33 0.21 -0.61 0.11
X3LYP -1.43 0.11 -0.41 0.09 -1.44 0.10 -0.71 0.21
BMK -1.37 0.17 -0.44 0.06 -1.39 0.15 -0.73 0.23
B1B95 -1.46 0.09 -0.44 0.06 -1.41 0.13 -0.74 0.24
M05 -1.39 0.15 -0.33 0.17 -1.39 0.15 -0.63 0.13
M052X -1.35 0.19 -0.35 0.15 -1.35 0.19 -0.65 0.15
MADb 0.13 0.10 0.13 0.20
a
Reference 5. b Mean absolute deviation.

TABLE 6: Standard Electrode Potentials (Eo) of TTF/TTF2+ and TTF/TTF+ Calculated with Methods 1 and 2 in CPCM and
SMD Solvation Models
CPCM SMD
o o o o o
E TTF/ rel E dimer E TTF/ rel E TTF/ rel E dimer
TTF2+ (V) TTF/TTF2+ TTF+ (V) TTF+ Eo TTF/TTF2+ (V) TTF/TTF2+ Eo TTF/TTF+ (V) rel Eo TTF/TTF+
method 1
expa 1.01 0.58 1.01 0.58
B3LYP 0.83 0.18 0.30 0.28 0.82 0.19 0.29 0.29
TPSSH 0.73 0.28 0.20 0.38 0.72 0.29 0.15 0.43
PBEH1PBE 0.81 0.20 0.28 0.30 0.81 0.20 0.25 0.33
M06 0.79 0.22 0.30 0.28 0.78 0.23 0.25 0.33
M062X 0.97 0.04 0.54 0.04 0.96 0.05 0.45 0.13
X3LYP 0.79 0.22 0.27 0.31 0.78 0.23 0.23 0.35
BMK 0.95 0.06 0.46 0.12 0.94 0.07 0.41 0.17
B1B95 0.68 0.33 0.19 0.39 0.68 0.33 0.12 0.46
M05 0.69 0.32 0.14 0.44 0.68 0.33 0.11 0.47
M052X 0.96 0.05 0.53 0.05 0.95 0.06 0.42 0.16
MADb 0.19 0.26 0.20 0.31
method 2
expa 1.01 0.58 1.01 0.58
B3LYP 0.79 0.22 0.27 0.31 0.79 0.22 0.25 0.33
TPSSH 0.71 0.30 0.18 0.40 0.69 0.32 0.12 0.46
PBEH1PBE 0.92 0.09 0.39 0.19 0.93 0.08 0.37 0.21
M06 0.87 0.14 0.38 0.20 0.87 0.14 0.34 0.24
M062X 1.10 0.09 0.66 0.08 1.08 0.07 0.57 0.01
X3LYP 0.84 0.17 0.31 0.27 0.83 0.18 0.28 0.30
BMK 1.07 0.06 0.58 0.00 1.06 0.05 0.53 0.05
B1B95 0.82 0.19 0.32 0.26 0.81 0.20 0.25 0.33
M05 0.82 0.19 0.27 0.31 0.81 0.20 0.24 0.34
M052X 1.07 0.06 0.64 0.06 1.06 0.05 0.53 0.05
MADb 0.11 0.18 0.12 0.23
a
Reference 14. b Mean absolute deviation.

of method 1. Moreover, in methods 1 and 2 the SMD solvation All redox potentials reported here are relative to the normal
model shows results similar to CPCM. hydrogen electrode (NHE). Experimentally determined values
17100 J. Phys. Chem. B, Vol. 114, No. 51, 2010
TABLE 7: Standard Electrode Potentials (Eo) of TTF-Im/
TTF-Im2+ and TTF-Im/TTF-Im+ Calculated with Methods 1
and 2 in CPCM and SMD Solvation Models
CPCM SMD
o
E TTF-Im/ o
E TTF-Im/ o
E TTF-Im/ Eo TTF-Im/
TTF-Im2+ (V) TTF-Im+ (V) TTF-Im2+ (V) TTF-Im+ (V)
method 1
2-TTF-Im (a) 0.946 0.491 0.927 0.476
4-TTF-Im (a) 0.870 0.421 0.866 0.377
5-TTF-Im (b) 0.839 0.400 0.824 0.360
method 2
2-TTF-Im (a) 1.069 0.614 1.050 0.599
4-TTF-Im (a) 0.993 0.543 0.989 0.500
5-TTF-Im (b) 0.962 0.523 0.947 0.483
relative to the silver/silver chloride electrode (Ag/AgCl) are
converted to those of NHE by adding 0.23 V.40
Conclusion
In the present work, the standard electrode potentials of two-
and one-electron reduction of Im and two- and one-electron
oxidation of TTF and TTF-Im structures have been computed
by extensive DFT calculations. The Im and TTF results have
been obtained employing 2 different methods, 2 different models
of solvation (CPCM and SMD), and 10 hybrid functionals
(B3LYP, TPSSH, PBEH1PBE, M06, M062X, X3LYP, BMK,
B1B95, M05, M052X) combined with the TZVP basis set. All
calculations have been performed by DFT calculations using
the Gaussian 09 Rev. A.02-SMP software package on a dual
2.33 GHz Intel Xeon processor with 3.0 GB RAM. One hundred
twenty calculations for Im, 90 calculations for TTF, and 30
calculations for TTF-Im structures have been done. A single
geometry optimization without any negative frequency calcula-
tions for dimer Im, TTF, and TTF-Im structures in solvation
models given above takes between 2-5 h of CPU time.
The minimum-energy geometries obtained for Im in the
dimer, anion, cation, neutral, and for TTF in the neutral, cation,
and dication states are in good agreement with available
experimental data. The geometry of the molecules has been
optimized in acetonitrile using CPCM and SMD solvation
models at the above levels of theory. While dimer structures
require a considerable amount of computing time, about 5 h of
CPU time, anion, cation, and neutral structures are computed
up to 1 h. For dimer Im, the motion of the proton between the
two Im rings has been observed for the N-H stretching mode
with a frequency of about 3300 cm-1.
Theoretical calculations show that neutral TTF is folded along
the S2-S3 axes with θ between 8° and 15°. The conformation
obtained for the cation structure, TTF+, was found to be fully
planar. For the dication structure, TTF2+, two dithiolylidene
rings have not only remained planar but also twisted around
the central C1-C1′ bond by a torsional angle (33-47°).
Concerning vibrations, the most intense C4dC5 frequency is
downshifted, in agreement with that of ref 13.
According to the results of all 10 hybrid functionals, the most
appropriate result for the electrode potential of Im is obtained
from method 1 as M05 and from method 2 as TPSSH differing
by 0.02 and 0.03 V from the experimental value. Calculations
with PBEH1PBE, BMK, and B1B95 functionals are also close
to the experimental value with deviations equal to or less than
0.05 V. TTF calculations with M062X, M052X, and BMK
functionals are close to experimental values with very small
differences. Finally, BMK is in both results and differs by 0.05
V from the experimental value. Moreover, frequencies of Im
Tugsuz
and TTF structures computed from the BMK functional are also
reasonably close to their experimental values.
A comparison between the calculated electrode potentials of
Im and TTF structures obtained by CPCM and those obtained
by SMD solvation models, employing methods 1 and 2, show
that except for the SMD results of ImH+/Im and TTF/TTF+ in
method 1, both CPCM and SMD in method 1 for Im, and in
methods 1 and 2 for TTF, give values closer to the experimental
ones. Method 2 for Im gives better results for TPSSH,
PBEH1PBE, BMK, and B1B95 functionals, while the other
functionals used give values which deviate significantly from
the experimental ones in both CPCM and SMD models. The
difference in SMD results of ImH+/Im and TTF/TTF+ in method
1 comes from the SMD-CDS (cavity dispersion solvent)
(nonelectrostatic) energy term contributions into energies of
cationic and monomer molecules with approximately 0.2 and
0.1 V, respectively. However, in method 2 TTF/TTF+ calcula-
tion, M062X, BMK, and M052X functionals with SMD, gives
results closer to the experimental values with 0.01, 0.05, and
and 0.05 V relative energies, respectively. Selection of the most
appropriate functional for electrode potential calculations of both
Im and TTF structures is very hard. For this reason, the
functional giving values closer to the experimental ones, which
is BMK here, has been chosen.
Using BMK/TZVP vibrational signals corresponding to the
neutral, cation, and dication structures and standard electrode
potentials of 2-, 4-, and 5-TTF-Im were computed. According
to method 1 results, the standard electrode potentials of 2-, 4-,
and 5-TTF-Im in acetonitrile solution predicted for the standard
electrode potentials of two-electron oxidation are 0.946, 0.870,
and 0.839 V in CPCM and 0.927, 0.866, and 0.824 V in SMD.
For one-electron oxidation these are 0.491, 0.421, and 0.400 V
in CPCM and 0.476, 0.377, and 0.360 V in SMD, respectively.
According to method 2 results, two- and one-electron oxidation
values in CPCM and SMD have been found to be higher by
0.1 V than those of method 2.
In all calculations, method 1 gives results closer to the
experimental values than method 2, because it uses solvation
Gibbs free energy changes of the reference electrode (NHE) in
acetonitrile as 4.48 eV. In method 2 instead of the Gibbs free
energy the electrode potential of the NHE value, which is equal
to 0.00 V in SI units, is directly used. Method 1 includes addition
f
of the correction ∆Go for the change in standard state from 1
atm, for gas-phase calculations, to 1 mol L-1 for the solution
phase of 7.9 kJ mol-1 to each component. In this study, we
also added this correction in method 2 to get results closer to
experimental values. Thus, we conclude that the present
methods, especially method 1, are useful for prediction of
unknown standard electrode potentials.
In the present work, we found that H-bond formation
enhances the electron-donating ability of TTF-Im. When TTF-
Im are linked to electron acceptors to form the corresponding
D-A dyads, intramolecular charge transfer or photoinduced
electron transfer may occur. By performing redox reactions on
TTF-Im, it is possible to switch on/off the intramolecular charge
or electron transfer process.
Acknowledgment. This study was supported by the Research
Centre Office of Hacettepe University through grant no.
09D07601003. I thank Prof. Dr. Fatma Sevin for her very
constructive suggestions. Special thanks are also due to Prof.
Andreas K. Theophilou for helping with the manuscript.
Supporting Information Available: Gibbs free energies of
H2(g) computed from 10 hybrid density functional and optimized
DFT Study on Standard Electrode Potentials
geometries of the most stable 2-, 4-, and 5-TTF-Im structures
with their tautomeric forms, such as a and b, at the BMK/TZVP
level of theory. This material is available free of charge via the
Internet at http://pubs.acs.org.
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