Accepted Manuscript

Performance of the M06 family of functionals in predicting the charge transfer

transition energies of molecular complexes of TCNE with a series of methylated
indoles
Amit S. Tiwary, Kakali Datta, Asok K. Mukherjee
PII:
DOI:
Reference:

S2210-271X(15)00272-8
http://dx.doi.org/10.1016/j.comptc.2015.06.033
COMPTC 1867

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Computational & Theoretical Chemistry

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Accepted Date:

24 May 2015
27 June 2015
27 June 2015

Please cite this article as: A.S. Tiwary, K. Datta, A.K. Mukherjee, Performance of the M06 family of functionals in
predicting the charge transfer transition energies of molecular complexes of TCNE with a series of methylated
indoles, Computational & Theoretical Chemistry (2015), doi: http://dx.doi.org/10.1016/j.comptc.2015.06.033

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Performance of the M06 family of functionals in predicting the charge transfer transition
energies of molecular complexes of TCNE with a series of methylated indoles
Amit S. Tiwarya, Kakali Dattab and Asok K. Mukherjee*c
a

Department of Chemistry, Netaji Mahavidyalaya, Arambagh, Hooghly-712601, INDIA.

Department of Chemistry, M. U. C. Womens College, B. C. Road, Burdwan-713104, INDIA

Digital Computer System, 112 R.B. Ghosh Road, Burdwan 713101, INDIA.

Abstract:
Ground state intermolecular interactions in the molecular complexes of TCNE with a series of
methylated indoles have been predicted with almost equal efficiency by the B3LYP and the M06
family of functionals. However, TDDFT calculation with the B3LYP functional failed to find
any charge transfer (CT) absorption band of the complexes while each of the functionals M06,
M06-2X, M06-HF and M06-L succeeded; the calculated CT transition energies vary with the
calculated vertical ionization potentials of the indoles, complying with Mullikens theory of
charge transfer complexes and are fairly close to reported experimental values.

Key words: TDDFT, Charge transfer, Tetracyanoethylene, methylindoles, M06 functionals

--------------------------------*Author for correspondence
Digital Computer System, 112 R.B. Ghosh Road, Burdwan-713101, INDIA.
Email: akm_13@rediffmail.com

1. Introduction
Properties of electronically excited states of broad classes of moderately large systems are
known to be predicted reliably [1-3] by the time-dependent density functional theory (TDDFT)
[4-7]. Charge transfer (CT) complexes are long known to be difficult for DFT [8,9] and use of
the traditional spatially local functionals in TDDFT calculations often fails to make satisfactory
prediction of CT excitation energies [10-13]. The sources of such failure are presumably the
spurious self-interaction [14] and missing derivative discontinuities [15,16] which, in some
applications, are eliminated by using a range-separated hybrid functional [17-19]. On the other
hand, the M06 family of functionals developed by Truhlar et. al.[20-23] are not range-separated
but reduce the errors of self-interaction and self-correlation by incorporating kinetic energy
density into the generalized gradient approximation (GGA) and in three of the cases

by

also incorporating different extents of HartreeFock exchange; these functionals are of hybrid
meta-GGA type (i.e., they depend not only on the gradient of the charge density but also on the
kinetic energy of the electrons). In the M06 suite of functionals the percentages of HF exchange
are 0, 27, 54, and 100 for M06-L, M06, M06-2X, and M06-HF, respectively [24]. They are
showing improved performance when applied to a wide range of fields such as thermochemistry
of transition metal complexes [25], prediction of electronic excitation energies of main-group
compounds by TDDFT [23], description of NMR chemical shielding constants [26], adsorption
of gases on solids [27], weak intermolecular interactions involving charge transfer and Hbonding in biomolecules [28-30] and electronic excitation energy of Rydberg and charge transfer
states [21, 31]. In a recent work [32] the M06 family of functionals were shown by TDDFT
calculation to yield two CT absorption bands for each of the complexes of tetracyanoethylene
(TCNE) with naphthalene and pyrene in satisfactory agreement with reported experimental
2

results while the B3LYP functional [33, 34] failed. In the present paper the efficiency of the four
above mentioned members of the M06 family as compared with the B3LYP functional has been
tested for predicting the CT excitation energies of the molecular complexes of TCNE with indole
and a series of methylated indoles in dichloromethane medium by using TDDFT in the
polarizable continuum model (PCM) [35, 36] for solvation. The CT transition energies of seven
complexes in the series have been computed by TDDFT and tested against Mullikens theory of
charge transfer complexes [37] and the computed values have been compared with
experimentally reported ones [38]. With this objective, ground state intermolecular interaction
(molecular complex formation) between TCNE and the indoles in dichloromethane solvent was
verified first by optimizing the geometries of the complexes (molecular adducts) and calculating
the electronic charge densities and

13

C and

15

N NMR chemical shifts of the atoms in TCNE

moiety and also of the indolic N atom in the complexed and isolated states. Formation of
molecular complexes in the ground state being thus established, TDDFT calculations were
performed on the optimized geometries (again in dichloromethane medium) for estimation of CT
transition energies of the complexes.
2. Computational Details
All computations were carried out by using the Gaussian 09 Revision A.02 suite of programmes
[39]. The functionals used were M06-L, M06, M06-2X and M06-HF and also B3LYP which is a
combination of Beckes three-parameter hybrid [33] exchange potential with the correlation
functional of Lee, Yang and Parr [34]. The 6-31++G** basis set was used throughout.
Optimization of the ground state geometry of each molecule under study was carried out in
dichloromethane solution, solvation effects being taken into account by the PCM. In this model
a solvent reaction field cavity is created by a series of overlapping spheres and the solute is
3

placed in the cavity. The 15N and

13

C NMR chemical shifts and natural charges on the atoms of

the isolated indoles, TCNE and their complexes were calculated by using the ground state
optimized geometries obtained with all the above mentioned functionals. Electronic transition
energies were calculated by TDDFT using the universal force field radii scaled by 1.1 (default of
Gaussian 09) together with the linear response method [40] for taking solvation effect into
account.
3. Results and Discussion
3.1 Computational evidence for complex formation in the ground state
The molecules studied in the present work are TCNE, indole, monomethyl indoles with methyl
group at 1, 2 and 3- positions and dimethyl indoles with methyl groups at 1,2-, 2,3-, and 2,5positions. The molecular adduct of TCNE and each indole, considered as a single supermolecule,
was subjected to geometry optimization in vacuo. These optimized structures were then further
optimized in dichloromethane medium using the PCM model to incorporate the effect of solvent.
Absence of imaginary frequencies confirmed that the optimized geometries did correspond to
real minima and not to saddle points on the potential energy surface. Optimized structure of one
complex produced by the M06-2X functional is shown in Fig.1 as a typical case and coordinates
of the atoms in the optimized geometries of the other complexes are given in supporting
information (Tables ST1 ST7). In each complex the molecular plane of TCNE is parallel to the
indole ring, the interplanar separation being in the range 3.0-3.5, typical of -donor- -acceptor
complexes. The calculated dipole moment vectors (one being shown in Fig.1) are directed from
indole towards the TCNE moiety of each complex. This indicates that some amount of electronic
charge is transferred to TCNE even in the ground state of each complex (in the Gaussian, dipole
moments are taken from the negative to the positive end of the dipole). Calculated electronic
4

charges (obtained by natural population analysis, NPA) on the atoms of isolated TCNE are given
in Table 1; the charges are found to be grouped as demanded by symmetry. The calculated
electronic charges (NPA) on the atoms of the TCNE moiety in the optimized geometry of the
indole-TCNE complex are shown in Table 2 with reference to the atomic labels as in Fig.2. For
the other complexes these are given in supporting information (Tables ST8 ST13). The isolated
TCNE molecule has a symmetrical distribution of electronic charge, sum of the charges being
zero as expected. But in the ground states of the molecular adducts this symmetry of electronic
charge distribution is somewhat lost. Further, the sum of the natural charges on the atoms of the
TCNE moiety of each complex is negative, thereby confirming the transfer of some electronic
charge to the TCNE moiety even in the ground states of the complexes. Thus, with the M06-2X
functional, 0.118 a.u. of electronic charge is transferred to TCNE. The large dipole moments of
the complexes in spite of small charge separation are due to large interplanar separation. 15N and
13

C NMR chemical shifts were calculated with the optimized geometries in CH2Cl2 medium

using all the functionals mentioned. Unfortunately the results cannot be compared with
experiment owing to non-availability of data. However, it transpires from the calculations
(Tables ST14-ST16 in supporting information) that the changes in chemical shift () of the
indolic N on complexation (all with increasing ) are in conformity with the changes in
electronic charges (Q) on this N (all with decreasing Q, deshielding). Molecular complex
formation between TCNE and each of the indoles is thus indicated by all the functionals used
including B3LYP.
3.2 TDDFT calculation of CT transition energies of the indole-TCNE series of complexes
Attempts were made to calculate the vertical CT excitation energies of the complexes by the
linear response TDDFT method using all the four members of the M06 family of functionals
5

mentioned earlier and also with the commonly used B3LYP. In each case, the same functional
and basis set as used for geometry optimization of the complexes were used for the
corresponding TDDFT calculations. It was found that B3LYP failed to predict any CT transition
with non-vanishing oscillator strength (i.e., the experimentally observed CT absorption band
could not be found by simulation with TDDFT calculation using B3LYP), although this
functional did establish some intermolecular interaction between each indole and TCNE in the
ground state. Success in finding CT absorption band, however, was achieved with all the four
M06-type of functionals for the seven molecular complexes under study. Results are given in
Table 3 together with reported [38] experimental values for comparison. The results obtained
from the four M06 type of functionals and the experimental values are more easily compared in a
bar diagram (Fig. 3). A typical CT absorption spectrum, simulated by TDDFT, is shown in Fig.4
where epsilon in the abscissa means molar absorptivity of the complex. The individual
molecules (indoles and TCNE) were also subjected to similar TDDFT calculation for their
valence transition energies in CH2Cl2 medium. It was found that each molecular complex
exhibits an absorption peak in the UV-Vis range different from those of the component
molecules (indoles and TCNE) in the series under study. That these new absorption peaks are
really CT peaks is established by the fact the transition electric dipole moment has major
component(s) along the axis/axes directed from indole to TCNE moiety in each complex. Also,
according to Mullikens theory of CT complexes [37] the following relation between CT
transition energy (hCT) and vertical ionization potential of the donor (IdV) must hold:
hCT = IdV C1 + C2/( IdV C1)
C1 = EAV + G1 + G0

(1)
(2)

Here, EAV is the vertical electron affinity of the acceptor (here, TCNE), G0 is the sum of several
energy terms ( like dipole-dipole, van der Waals interaction, etc.) in the no-bond state; in most
cases G0 is small. G1 is largely the energy of electrostatic attraction between D+ and A- (the
positively charged donor and the negatively charged acceptor) in the dative state of the
complex . The term C2 in eqn. (1) is related to the resonance energy of interaction between the
no-bondand dative forms in the ground and excited states and for a given acceptor it may be
supposed constant [37]. In summary, C1 and C2 are constants for a given solvent and a given
electron acceptor in a series of complexes with structurally similar donors. A rearrangement of
eqn.(1) gives
2 IdV hCT = (1/ C1) IdV(IdV hCT) + C1 + ( C2/ C1)

(3)

The CT transition energies and the ionization potentials (= negative of the highest occupied
orbital energies, according to Koopmans theorem) computed using the M06-2X functional give
an excellent linear plot (Fig. 5) as expected from eqn. (3) and the linear regression equation,
2IDv hCT = (0.186 0.005) IDv(IDv - hCT) + (5.625 0.139)

... (4)

is obtained with a correlation coefficient of 0.999. This establishes the CT nature of the
calculated absorption band. The CT nature of the transitions is revealed more convincingly when
the concerned orbitals of the complexes are considered. In all the cases under study, the long
wavelength absorption bands which have been assigned as CT are due to transitions from the
second highest occupied to the lowest unoccupied orbital of the molecular complexes. The
electron density plots (Gaussview pictures) of these orbitals are shown in Fig.6 for one typical
complex. It is clear that before transition electron density is concentrated mostly on the indole
(donor) moiety of the complex and after (vertical) transition it is concentrated mostly on the
acceptor (TCNE) moiety. Regarding quality of the results, M06-2X overestimates the CT
7

transition energies by about .07 to 0.5 eV while M06-HF overestimates it by 0.4 to 1.1 eV as
compared with experimental values; the functionals with lower HF exchange, namely, M06 and
M06-L, underestimate the same by about 0.005 to 0.7 eV and 0.4 to 0.75 eV respectively.
4. Conclusion:
Owing to their wrong asymptotic behavior, standard exchange functionals (like B3LYP)
significantly underestimate CT excitation energies [14] in TDDFT calculation. In the present
case the B3LYP functional fails to detect any CT absorption band by TDDFT calculation for all
the seven molecular complexes studied. Each of the four members of the M06 family of
functionals, however, is successful in this respect; a CT absorption band, very close to the
experimental one, is found by simulation using each of the M06 functionals separately. The
vertical CT transition energies obtained by TDDFT comply with Mullikens theory of charge
transfer complexes.
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13

Figure Captions:
Fig. 1. Optimized Structure of Indole-TCNE complex with dipole moment, calculated at
DFT/M06-2X/6-31++G(d,p) level in dichloromethane medium using PCM. Arrow
shows the direction of calculated dipole moment.
Fig.2. Labels for atoms in the TCNE moiety of the complexes and also in isolated
TCNE molecule
Fig.3. Comparison of theoretically obtained and experimental CT transition energies of the
TCNE complexes with (1) indole, (2) 1-methyl indole (3) 2-methyl indole (4) 3-methyl
indole (5) 1,2-dimethyl indole (6) 2,3-dimethyl indole (7) 2,5-dimethyl indole.
Fig. 4. UV-Vis spectrum of 2,5-dimethyl indole-TCNE complex in CH2Cl2 medium
calculated at TDDFT/M06-2X/6-31++G(d,p) level of theory using the polarizable
continuum model.
Fig. 5. Correlation between the vertical ionization potentials of the indoles (donors)
calculated by DFT/M06-2X/6-31G** and CT transion energies of the indole-TCNE
complexes calculated by TDDFT/M06-2X/6-31G**, both in dichloromethane medium
using the PCM formalism. (Verification of Mullikens theory using theoretical hCT
values).
Fig. 6. Gaussview pictures of (a) the second highest occupied and (b) lowest unoccupied orbitals
of the 2,3-dimethyl indole-TCNE complex.

14

Table 1. Natural charges (q/a.u.) on relevant atoms of isolated (i.e., uncomplexed) TCNE
molecule in CH2Cl2 medium calculated using different functionals.

Functional

N atoms

C atoms
Ethylenic

Cyano

M06-2X

-0.22

-0.11

0.27

M06-L

-0.24

-0.12

0.30

M06-HF

-0.19

-0.11

0.24

M06

-0.24

-0.12

0.23

B3LYP

-0.22

-0.11

0.28

15

Table 2. Natural charges (q/a.u.) on the atoms of TCNE moiety in IndoleTCNE complex (in CH2Cl2 medium); atom labels refer to Fig. 2

Functional

M06-2X

N atoms

C atoms

qc = - 0.24, qf = - 0.24

qg = 0.28, qh= 0.28

qe = - 0.23, qd = - 0.25

qj = 0.28, qj = 0.28
qb = - 0.14, qa = - 0.13

M06-L

qd= - 0.29, qe = - 0.28

qg= 0.30, qi= 0.30,

qc = - 0.29, qf = - 0.29

qj = qh = 0.30,
qa = qb = - 0.17

M06-HF

qe = -0.20, qf = -0.21

qh= 0.25, qg= 0.26,

qc = -0.21, qd= -0.21

qi = 0.25, qj = 0.26,
qa = -0.11, qb = -0.14

M06

B3LYP

qc = qf = - 0.28,

qg = qi = qh = qj = 0.31

qd = qe = - 0.28,

qa = - 0.12, qb = - 0.16

qe = -0.25, qc= - 0.26,

qj = 0.30, qi = 0.29

qd = qf = - 0.26

qg = qh = 0.29
qa = qb = - 0.15

16

Table 3. CT transition energies of the complexes of TCNE (acceptor) with indole and
methylindoles (donors) calculated in dichloromethane medium at TDDFT/6-31++G(d,p)
level of theory using the PCM formalism and the M06 family of functionals; in parenthesis
are given the calculated values of IDv; experimental CT transition energies are taken from
literature (ref. [37]) for comparison.

Calculated CT transition energy/eV; in parenthesis, calculated I Dv/eV

Donor

M06

M06-HF

M06-L

M06-2X

Expt.

Indole

1.861(6.117)

2.932 (8.794) 1.769 (5.198) 2.543 (7.107)

2.472

1-methyl indole

1.912 (6.019)

3.036 (8.600) 1.660 (5.097) 2.466 (6.989)

2.364

2-methyl indole

1.997 (5.968)

3.060 (8.630) 1.790 (5.070) 2.487 (6.966)

2.230

3-methyl indole

1.864 (5.942)

3.064(8.590)

1.704 (5.006) 2.430 (6.929)

2.359

1,2-dimethyl indole

1.893 (5.886)

2.902 (8.483) 1.680 (4.973) 2.384 (6.863)

2.051

2,3-dimethyl indole

1.817 (5.799)

2.941 (8.463) 1.690 (4.870) 2.407 (6.792)

1.880

2,5-dimethyl indole

1.954 (5.925)

3.045 (8.585)

2.149

17

1.781(5.006)

2.389 (6.922)

Fig. 1. Optimized Structure of Indole-TCNE complex with dipole moment, calculated at

DFT/M06-2X/6-31++G(d,p) level in dichloromethane medium using PCM. Arrow
shows the direction of calculated dipole moment.

18

Fig.2. Labels for atoms in the TCNE moiety of the complexes and also in isolated
TCNE molecule

(e)
N

(c)
N
(i)
C

(a)

(g)
C

C
(j)

C
(b)

C
(h)

N
(f)

(d)

19

Fig.3. Comparison of theoretically obtained and experimental CT transition energies of the

TCNE complexes with (1) indole, (2) 1-methyl indole (3) 2-methyl indole (4) 3-methyl
indole (5) 1,2-dimethyl indole (6) 2,3-dimethyl indole (7) 2,5-dimethyl indole.

Expt
M06
M06-HF
M06-L
M06-2X

3.0

hCT/eV

2.5
2.0
1.5
1.0
0.5
0.0

Donors (1 to 7)

20

Fig. 4. UV-Vis spectrum of 2,5-dimethyl indole-TCNE complex in CH2Cl2 medium

calculated at TDDFT/M06-2X/6-31++G(d,p) level of theory using the polarizable
continuum model; Epsilon in abscissa means molar absorptivity.

21

Fig.5. Correlation between the vertical ionization potentials of the indoles (donors)
calculated by DFT/M06-2X/6-31G** and CT transion energies of the indole-TCNE
complexes calculated by TDDFT/M06-2X/6-31G**, both in dichloromethane
medium using the PCM formalism. (Verification of Mullikens theory using
theoretical hCT values).

11.7

11.6

11.4

2ID -hCT

11.5

11.3

11.2

11.1
29.5

30.0

30.5

31.0

31.5

ID (ID -hCT)

22

32.0

32.5

Fig. 6 Gaussview pictures of (a) the second highest occupied and (b) lowest unoccupied
orbitals of the 2,3-dimethyl indole-TCNE complex.

(a)

(b)

23

Graphical Abstract

24

Highlights

CT bands & NMR chemical shifts of complexes of TCNE with a series of

methylated indoles were found by TDDFT/PCM.

B3LYP cannot predict CT absorption bands for these complexes.

M06, M06-2X, M06-HF and M06-L predict one CT band for each complex in the
series.

The predicted CT excitation energies comply with Mullikens theory of Charge Transfer

B3LYP and the M06 family predict 13C and 15N NMR chemical shifts almost
equally.

25