View Article Online / Journal Homepage / Table of Contents for this issue

PCCP Dynamic Article Links

Cite this: Phys. Chem. Chem. Phys., 2011, 13, 1727317283

www.rsc.org/pccp PAPER
Spectral and intramolecular charge transfer properties in
terminal donor/acceptor-substituted all-trans-a,x-diphenylpolyenes
and a,x-diphenylpolyynesw
Published on 30 August 2011. Downloaded by FAC DE QUIMICA on 18/08/2016 19:44:56.

Xiaonan Ma, Linyin Yan, Xuefei Wang, Qianjin Guo* and Andong Xia*
Received 4th April 2011, Accepted 12th August 2011
DOI: 10.1039/c1cp21036j

The absorption spectra and intramolecular charge transfer (CT) properties of terminal donor/
acceptor-substituted all-trans-a,o-diphenylpolyenes (DPE) and a,o-diphenylpolyynes (DPY)
molecules with dierent conjugated bridge length and substitution modes were investigated by
using quantum chemical calculations. We calculated the ground state structures and energy of
two series of terminal donor/acceptor DPE and DPY by DFT method. The dependence of
conjugation length and substitution modes of the electronic absorption spectra was obtained by
TDDFT calculation. The hybrid-GGA XC-functional PBE0 employed in this work was selected
from several functionals by comparing the calculated electronic spectral data with experimental
value. The CIS-based generalized Mulliken-Hush (GMH) approach was further used to calculate
coupling values HAD of the CT process. The calculation shows that both the HOMOLUMO
energy gaps and average bond length alternations between unsaturated multiple (CRC and
CQC) and saturated single bonds (CC) decrease regularly with the extension of conjugation.
The eective conjugated length (ECL) of DPE and DPY with the same order MM 4 MP/PM 4
PP is found together with the regular red shift of the electronic absorption spectra with the
extension of conjugation, resulting from the dierent p-electron delocalization and conjugation
eciency. The GMH analysis further suggests that the CT process in both DPE and DPY is
predominated by the through-bond mechanism. The remarkable dierence of the conjugated
length dependence of squared CT coupling between substituted DPE and DPY is the result of the
energetic matching degree of the frontier molecular orbitals between donor/acceptor and the
conjugated bridge.

1. Introduction mechanism of CT process is essential for understanding the

Charge transfer (CT) plays an important role in chemical and
biological systems,19 as well as the organic functional materials1013
and electronic devices.14,15 Determination of the molecular
The State Key Laboratory of Molecular Reaction Dynamics, Institute
of Chemistry, Chinese Academy of Sciences, Beijing 100190,
P. R. China. and Beijing National Laboratory for Molecular Sciences
(BNLMS), Institute of Chemistry, Chinese Academy of Sciences,
Beijing 100190, P. R. China. E-mail: andong@iccas.ac.cn,
guoqj@iccas.ac.cn
w Electronic supplementary information (ESI) available: The perfor-
mance of seveal DFT XC-functionals are displayed in S1 by compare
the calculated absorption wavelength values with the experimental
data. All the TDDFT calculated electronic absorption spectra of DPE
and DPY mentioned in this work are shown in S2. S3 shows the
dierent features of LE and CT states of substituted DPE and DPY
species, which is identied by the charge dierence density and
transition density representations of the correponding transitions.
The CIS-GMH calculated coupling values and the correspongding
donoracceptor distance of DPE and DPY species are shown in S4.
See DOI: 10.1039/c1cp21036j.
biological function and designing synthetic energy transducing
systems. Generally, a typical molecule with intramolecular
charge transfer contains the electronic donor (D) and electronic
acceptor (A) groups.16,17 However, in many systems of interest,
the donor and acceptor are spatially separated, where the direct
coupling between the donor and acceptor is very weak.18,19
Therefore, a conjugated bridge (B) is required for connecting
donor and acceptor to promote the CT process,2,46 so that the
transfer of the electron can be regulated in a controlled
manner, in which the CT process is inuenced remarkably
by the donoracceptor distance, and by structure of the conjugated
bridge.2023 Typically, the photoinduced CT process generally
includes three steps: (1) the ground state (GS) of donor unit is
photoexcited to form a locally excited (LE) state; (2) CT
occurs through the bridge or/and space to reach the CT state;
(3) charge recombination, i.e. CT state relaxation brings
system back to GS.
According to Marcus theory,1,24 in long-range CT systems
the CT coupling matrix element, HDA, describing the transition

This journal is c the Owner Societies 2011 Phys. Chem. Chem. Phys., 2011, 13, 1727317283 17273

Scheme 1 Molecular structures of the terminal D/A substituted DPE
(a) and DPY (b) compounds.
Published on 30 August 2011. Downloaded by FAC DE QUIMICA on 18/08/2016 19:44:56.
between the initial and nal electronic states, and primarily
governs the CT rate,25 which can be described as,
2p
kET jHDA j2 DWFC 1
h
where DWFC is the FranckCondon factors weighted by the
density of states, and is related to the nuclear motion spectrum
of the donor-p-acceptor system and its surroundings.
To calculate electronic coupling of the CT process involving
excited states, Newton and Cave developed the generalized
MullikenHush (GMH) approach to estimate the donor
acceptor interactions,26,27 based on the early models developed
by Mulliken and Hush.28,29 This approach has been used to
calculate the coupling values for both ground and excited-state
CT reactions. The signicant advantage of this approach is
that one can calculate the electronic coupling without the
transition state geometry,30 making GMH a useful method
for calculating electronic coupling of the charge transfer process
of large systems.31 In the early applications,32,33 the semi-
empirical ZINDO/S calculation has been used to estimate the
CT coupling in the GMH scheme. Recently, several ab initio
calculated methods such as CASSCF27 and TDDFT34 have been
developed to calculate the CT coupling. Unlike the semi-empirical
method, ab initio calculation did not depend on the empirical
parameters, therefore always supply more accurate coupling
values.35 However, although DFT methods show high accuracy
in predicting molecular grometries and vibrational frequencies,
plenty of studies indicated that TDDFT methods lead to
signicant problems in the description of CT states in large
conjugated molecules.34 Since the exact XC-functional is unknown,
approximate XC-functionals need to be employed in practical
calculation. The TDDFT calculations based on the approximate
XC-functionals usually tend to underestimate the excitation
energies, especially for large p-conjugated systems, doubly
excited states and CT states.34,36 Moreover, the potential
energy curve of CT state calculated by TDDFT often shows
wrong sharp, in which the 1/R asymptotic behavior along the
charge-separation coordinate R does not show the correct
electrostatically attractive pattern when standard XC-functionals
are empolyed.34 On the other hand, Hsu and her co-works
developed CIS-based GMH framework and its variants to
compute the coupling for charge transfer,18,30 excitation
energy transfer37 and triplettriplet energy transfer.38 Especially,
they demonstrated that the CIS based GMH scheme is able to
characterize both through-bond and through-space CT coupling,
with results close to experimentally derived values.30 Therefore,
in this work, we employed the similar calculated framework
based on the CIS method to estimate the CT coupling in the
17274 Phys. Chem. Chem. Phys., 2011, 13, 1727317283
View Article Online
donorbridgeacceptor systems, meanwhile the TDDFT was
restricted in calculations of the vertical excitation transition.
Recently, the terminal donoracceptor substituted conjugated
oligomers have been studied widely which are expected to have
special optoelectronic eects.3944 As the long conjugated stilbene
derivatives, all-trans-a,o-diphenylpolyene (DPE) compound
plays important roles in biological systems such as light-harvesting
antennas and triggering the vision signal.45 The conjugation
length dependent photophysics has been studied widely by both
experimental and theoretical methods.4651 Meanwhile, during the
past years, the study of one dimensional conjugated molecules
such as a,o-diphenylpolyyne (DPY) has also attracted the
interest of a number of research groups because of its unique
function as a simple linear molecule in nanoscale devices.52,53
As a unique class of molecules with the simplest conjugated
bridge, both DPE and DPY represent the right model for
probing CT process with less inuence from the conguration
limitations.54 Although the conjugation length dependence of
the 11Ag(S0) - 11Bu transition of linear polyenes has been
successfully interpreted in terms of the one-electron HOMO -
LUMO transitions in the molecular orbital model,46 the
characterizing of CT coupling mechanism between terminal
donor/acceptor substituted DPE and DPY compound is still
challenged and lack of quantitative description, in which the CT
can be regulated in a controlled manner through such two kinds of
conjugated molecular bridges.55 In other words, the relationship
among the structural character, conjugation property and the
long-range CT coupling by through-bond and/or through-space
mechanisms within donor/acceptor substituted DPE and DPY
compounds are still not understood. Scheme 1 shows the
molecular structures of the donor/acceptor substituted a,o-
diphenylpolyene (DPE) and diphenylpolyyne (DPY) studied
in this work. The substitution modes considered in this work
are listed in Table 1. Obviously, the DPE and DPY systems
with dierent conjugated length and substitution modes
provide right model to address the question mentioned above.
In this article, we calculate the ground state structures and
energy of two series of terminal donor/acceptor substituted
a,o-diphenylpolyene and diphenylpolyyne by DFT method.
The dependence of conjugation length and substitution modes
of the electronic absorption spectra is obtained by TDDFT
calculation. The hybrid-GGA XC-functional PBE0 employed
in this work was selected from several functionals by comparing
the calculated electronic spectral data with experimental value.
The two-state generalized Mulliken-Hush (GMH) approach
based on the CIS wave functions is further used to calculate
CT coupling HDA. We found that the eective conjugated
length (ECL) of DPE and DPY series shows distinct dierence
with each other due to their dierent p-delocalization and
Table 1 Substitution modes of the donor and acceptor in DPE and
DPY studied in this work
Donor Acceptor
HH H H
MM mata-NMe2 meta-CN
PM para-NMe2 meta-CN
MP mata-NMe2 para-CN
PP para-NMe2 para-CN
This journal is c the Owner Societies 2011

conjugation eciency, which is also reected by the dierent
CT coupling strength. The GMH analysis indicates that the
CT process in both DPE and DPY is predominated by
the through-bond mechanism. The remarkable dierence of
the conjugated length dependence of squared CT coupling
between DPE and DPY is the result of the energetic matching
degree of the frontier molecular orbitals between donor/
acceptor and the conjugated bridge.
2. Computational methods
Published on 30 August 2011. Downloaded by FAC DE QUIMICA on 18/08/2016 19:44:56.
The ground state geometries and corresponding absorption
spectra were calculated by DFT and TDDFT methods in
6-31g* level, respectively. In TDDFT calculations, the calculated
excited state properties are strongly dependent on the fractions
of orbital exchange in the used hybrid XC-functional. The
functionals with small orbital exchange fraction (such as
B3LYP, 20%) tend to overestimate the CT properties,
therefore favor zwitterionic-like states with strong CT
character. On the contrary, functionals with large oribital
exchange fraction (such as BHandHLYP, 50%) is more
suitable to treat the neutral-base electronic excitation.56
In this work, the hybrid-GGA functional PBE0 was employed
in the structural and spectral calculations of terminal DA
substituted conjugated systems, which is made up by the pure
PBE XC-functional and 25% percentage of orbital exchange. Here
the PBE0 functional was selected from eleven well-established
functionals by comparing the calculated electronic spectral data
with experimental value in references The detail information is
shown in ESI S1.w The line shape of the calculated electronic
absorption spectra is broaden with the multiple Gaussian
function related to the corresponding excitation energy and
oscillator strength from the TD-PBE0 calculations. The
UVvis spectra peak half-width at half height tentatively sets
as 0.3 eV (2419.66 cm1).
The CT couplings are calculated by means of the two-state
generalized MullikenHush (GMH) approximation in this work.
Fig. 1 Bond length alternation parameters (ab) and HOMOLUMO energy gap (cd) versus the number of repeat units (n) obtained from the
DFT calculation. The (a) and (c) are for DPE series, (b) and (d) are for DPY series.
This journal is c the Owner Societies 2011
View Article Online
In principle, the coupling factor is an o-diagonal Hamiltonian
matrix element between the initial and nal diabatic states in
the CT process.35 Solving the Schrodinger equation yields a set
of eigenstates, but the coupling is the Hamiltonian element in a
charge-localized space. Therefore, the GMH scheme empolys
an additional dipole operator to dene the charge-localized space,
then the coupling can be calculated by transforming the two-state
Hamiltonian accordingly. On the basis of the consideration
above, in GMH scheme, the coupling factor HDA between
the initial donor LE state and the nal CT state can be
given by,31,35
m12 DE12
HDA q
2
m1  m2 2 4m212
where m12 is the transition dipole moment between the two
adiabatic states in the charge transfer, (m1m2) is the dierence
in adiabatic state permanent dipole moments, and DE12 is the
energy dierence between the initial and nal adiabatic states.
Due to the existence of the principle error of TDDFT
methods in the description of CT state in large conjugated
systems, all of these values are obtained by CIS calculations in
6-31g* level with the DFT optimized ground state geometries.
Previous studies have shown that the CIS method yields
reliable coupling values for a variety of CT processes.30,35
All of the calculations were carried out by the method
implemented in GAUSSIAN 03 E.01 package.57
3. Results and discussion
3.1. Structure and energy of ground state
The most stable molecular structures of DPE and DPY in the
ground states are fully optimized under the DFT method
without any symmetry constraint. The bond length alternation
parameters (BLA) for DPE and DPY are calculated, where the
BLA is dened as the dierence between the averages of the
Phys. Chem. Chem. Phys., 2011, 13, 1727317283 17275
 View Article Online

saturated (CC) and the unsaturated (CQC in DPE and 3.2. Absorption spectra
CRC in DPY) bond lengths:58,59
The electronic absorption spectra of DPE and DPY series
%
BLA(DPE) = R(CC) %
 R(CQC) (3) were calculated at TD-PBE0/6-31G(d) level based on the
optimized ground state geometries. The performance of the
%
BLA(DPY) = R(CC) %
 R(CRC) (4) PBE0 functional in the calculation of electronic spectra is
shown in ESI S1.w As an example, the multiple gaussian
The evolution of the calculated BLA of DPE and DPY is function (the half-width at half-height tentatively sets as
plotted as a function of the number of repeat units (n) in 0.3 eV) broaden absorption band shapes of DPE/DPY series
Fig. 1(a) and (b) respectively. The BLA values in D/A with the conjugated bridge length (n = 6) and dierent
substituted species is slightly smaller than that in non-
Published on 30 August 2011. Downloaded by FAC DE QUIMICA on 18/08/2016 19:44:56.

donoracceptor substituted modes are shown in Fig. 2. For

substituted DPE and DPY, resulting from the ICT by association DPE, there are two well-established low-lying excited states
donor and acceptor units, and the possible reduction of 21Ag and 11Bu. The rst one is optically forbidden due to the
isomerization of DPE and DPY after substitution.60 Furthermore, same symmetry with the ground state, whereas the second one
it is found that the BLA values in dierent D/A substitutions is symmetry allowed.46,64 The intense absorption band of
of DPY and DPE at the same number of repeat units DPE is seen, which is corresponding to the symmetry allowed
decreases in the order MM 4 MP/PM 4 PP. Meanwhile, transition 11Ag (S0) - 11Bu.60 However, for DPY, two
the BLA of both DPE and DPY decreases in an exponential absorption bands are symmetry allowed corresponding to
pattern with the extension of the conjugated chain, which is the transitions of 11Ag (S0) - 11B1u and 11Ag (S0) - 21B1u,
consistent with other similar calculated studies.59,60 The respectively.65,66 One more allowed transition corresponding
exponential tting values of the BLA evolution are listed in to 11Ag (S0) - 11Au is dicult to be observed because of
Table 2. The BLA value of DPY is larger than that of the overlap with the S0 - 11B1u transition band.60 As shown in
corresponding DPE due to the intense p-bonding character of Fig. 2, the electronic absorption spectra of PP-substituted
DPY, which is related to the larger energy gap between species shows a bathochromic shift by about 59 nm (for DPE)
HOMO and LUMO than that of DPE. and 36/14 nm (for the rst/s band of DPY) compared to that
The energy gap values of DPE and DPY calculated by DFT of MM-substituted species, respectively. The degree of red
is shown in Fig. 1(c) and (d) as a function of the number of shift increases in the order MMoMP/PMoPP in both DPE
repeat units (n). The conjugated length dependence of energy and DPY series as shown in Fig. 2. The red shift in DPE series
gaps of both DPY and DPE shows the exponential decrease is more evident than that in DPY series due to the higher
trends as described in literature,61 indicating the extension of conjugation eciency of DPE backbone.
conjugation. Table 2 lists the exponential tting values of the Similar to the evolutions of HOMOLUMO energy gap
energy gap evolution with the number of repeat units (n). DPY with the conjugated length increases, the absorption
series exhibits larger energy gap than DPE series, because of the
smaller p-electron delocalization and less eective conjugation
length in DPY than that of DPE. Moreover, because of the
very low rotational barrier about 0.05 eV per cylindrical triple
bond,62,63 the twisting about the cylindrical triple bond in DPY
interrupts the conjugation of rod-like oligomers, leading to a
larger HOMOLUMO energy gap relative to that of DPE.
In addition, compared to the cases of non-substituted
species, the terminal donor/acceptor substitutions in both
DPE and DPY further lower the energy gaps due to the ICT
eect, which reorganizes the charge distribution in conjugated
chain.36 On the other hand, the ICT eect becomes weak with
increasing distance between donor and acceptor, where a
reduction in the ICT eects accordingly shifts the absorption
band to longer wavelengths.

Table 2 Fitting parameters of the evolution of bond length alternation

(BLA/A) and HOMOLUMO energy gap (gap/eV) with the conjugated
bridge extension

DPE DPY
BLA/A gap/eV BLA/A gap/eV
n=1 n=N n=1 n=N n=1 n=N n=1 n=N
HH 0.117 0.0645 4.313 1.7599 0.208 0.1062 4.436 1.9854
MM 0.118 0.0640 3.596 1.3156 0.208 0.1045 3.736 1.6850
PM 0.110 0.0626 3.499 1.5546 0.203 0.1048 3.711 1.6207 Fig. 2 The calculated absorption spectra of DPE (a) and DPY
MP 0.114 0.0635 3.414 1.2596 0.206 0.1057 3.352 1.7495 (b) series with conjugated bridge length (n = 6) and dierent
PP 0.105 0.0617 3.328 1.5326 0.200 0.1046 3.479 1.6726 donoracceptor substituted modes.

17276 Phys. Chem. Chem. Phys., 2011, 13, 1727317283 This journal is c the Owner Societies 2011

wavelength for both DPE and DPY series shows regular red
shift with the increasing p-conjugated bridge length (See the
ESI S2)w, resulting from the increase of the p-electron
delocalization along the conjugated chain.61,67 Meanwhile, the
oscillator strengths of the main absorption band for both DPE
and DPY show the signicant increase with the prolongation of
conjugated bridge length, indicating that the extension of the
p-electronic system leads to strong oscillator strength.62 In the
description of the eective conjugated length introduced by
Meier,67 the absorption wavelength of conjugated oligomers
Published on 30 August 2011. Downloaded by FAC DE QUIMICA on 18/08/2016 19:44:56.
could be tted by the empirical exponential equation,
ln = lN  (lN  l1)eb(n  1)
(5)
where Dl = (lN  l1) are the absorption wavelength dierence
between the polymer and monomer, n represents the number of
repeat units in conjugated chain, and parameter b indicates how
fast ln will saturate towards lN. From these parameters, one
can calculate the eective conjugated length (ECL) of the
oligomer series with eqn (6), which is dened as the value of
n for which the dierence between lN and ln is less than
1 nm.68 The ECL values oer a quantitative measurement for
the conjugation eciency of DPE/DPY backbone as well as
the CT characters between donor and acceptor.5859,62
ln Dl
ECL 1 6
b
Fig. 3 shows the conjugated length dependence of the absorption
wavelength and oscillator strength values of S0 - 11Bu band
(for DPE) and S0 - 11B1u, S0 - 21B1u bands (for DPY). It is
found that, the absorption wavelengths (in nm) of S0 - 11Bu
band (for DPE in Fig. 3(a)) and S0 - 21B1u band (for DPY in
Fig. 3(b)) are tted well by the eqn (5) as a function of the
number of repeat units (n). The tted parameters and ECL
Fig. 3 Conjugated length dependence of the absorption spectroscopy of DPEs and DPYs. The (a)(c) are for absorption wavelength and the
(d)(f) are for the corresponding oscillator strength. The solid line stand for the tting data, the dash line is the ordinary connected line.
This journal is c the Owner Societies 2011
View Article Online
values estimated by eqn (6) are listed in Table 3. Because of
low calculation accuracy of PBE0 functional for the S0 -
11B1u band of DPY (see the ESI S1)w, we did not t the
spectral data of this band to estimate the ECL value, although
the absorption wavelength of this band also shows regular red
shift with the extension of conjugation (as shown in Fig. 3(c)).
Obviously, the DPE shows much longer ECL value than that
of DPY. As suggested by Luthi and his co-workers that,58,59
the conjugation eciency, i.e., the ability to promote electron
delocalization along the conjugated backbone, determines the
ECL of conjugated oligomers. The relative short ECL results
from the much lower conjugation eciency of polyyne
conjugated chain than that of polyene chain due to the
relatively weak p - p* orbital interactions. In addition,
because of the very low rotational barrier about 0.05 eV per
cylindrical triple bond,62,63 twisting the cylindrical triple bond
in DPY should break the conjugation of a single polymer
chain, also resulting in the shorter ECL in DPY.
Furthermore, it is found that the terminal donoracceptor
substitution of DPE and DPY oligomers have remarkable
eect on the ECL value. That is also reected by the BLA
evolution as well as by the dierence in HOMOLUMO
energy gap with respect to the D/A substitutions. Particularly,
the ECL values of both of donor/acceptor substituted DPE
and DPY also show the order MM 4 MP/PM 4 PP. This
order is consistent well with the order of HOMOLUMO
energy gap of D/A substituted DPE and DPY species. It is
known that HOMOLUMO energy gap of D/A substituted
series could be contributed from two parts, the energy from
p-conjugated bridge and the correction term from the CT
eect as described in references.6970 Therefore, the dierent
ECL value in the D/A substitution series shows the summation
of the alternation degree of conjugated eciency in conjugated
Phys. Chem. Chem. Phys., 2011, 13, 1727317283 17277

Table 3 Fitted parameters of the absorption wavelength and
calculated ECL values for DPE and DPY Series
DPE S0-11Bu DPY S0-21B1u
lN l1 ECL lN l1 ECL
HH 1277.0 302.7 B179 561.3 173.8 B54
MM 1182.7 310.4 B151 724.7 186.8 B98
PM 1080.7 355.6 B124 602.8 188.5 B68
MP 1113.3 325.2 B132 655.3 187.2 B77
PP 1025.5 372.8 B106 583.6 197.4 B61
Published on 30 August 2011. Downloaded by FAC DE QUIMICA on 18/08/2016 19:44:56.
systems and CT eects, where the extension of the conjugated
part is helpful for decreasing the energy gap, and the D/A-
substitution brings a diminished bathochromic eect. As
shown in Table 3, compared to the non-substituted species,
ECL becomes a little shorter after DPE was substituted with
D/A, whereas the ECL become a little longer after DPY was
substituted with D/A. This could be explained that the D/A
coupling could be modulated with dierent conjugated
bridges, where the conjugated polyene chain is more suitable
for D/A communicating than conjugated polyyne chain.
Furthermore, the CT coupling magnitude of substituted
DPE/DPY in the order MM 4 MP/PM 4 PP will be expected
in following CIS-GMH analysis which would give a more
quantitative description for the CT mechanism.
However, it is nessesary to note that the ECL values presented
here are less accurate due to the principle error of the TDDFT
methods mentioned in previous sections. Therefore, the
obtained ECL values could be taken as qualitative or
semi-quantitative results. The more accurate quantitative
result relies on the future application of highly accurate excited
state calculate methods (such as CASPT2 and MRCI) on such
complex systems, which are applicable only to small molecules
up to 20 atoms nowadays.
The conjugation length dependence of the corresponding
oscillator strength is shown in Fig. 3(d)(f). Generally, in
conjugated system, the oscillator strengths of S0 - 11Bu band
of DPE series and S0 - 21B1u band of DPY series, increase with
the extension of the p-conjugation system,62 and follow regular
increase with the increase of the number of repeat units (n).
However, for S0 - 11B1u band (ICT band) of DPY, the
oscillator strength increases with the increasing number of
repeat units (n) in the rst, and then decays with the extension
of conjugation. To understand this peculiar dependence of
oscillator strength of S0 - 11B1u transition of DPY series, we
turn to investigate the detailed transition properties of these
transitions mentioned above. Table 4 shows the TDDFT
calculated vertical excitation energies, oscillator strengths,
and the corresponding transition components of the important
transitions of typical substituted DPE and DPY. The results
indicate that the excitation of S0 - 11Bu (DPE) and S0 -
11B1u (DPY) are dominated by the HOMO - LUMO
transition. For substituted DPE and DPY, HOMO is a p-type
orbital located on donor and conjugated bridge, and LUMO is a
p*-type orbital contributed from the acceptor and conjugated
bridge. The transitions HOMO - LUMO corresponding to the
CT states. Another transition S0 - 21B1u of DPY possess
large oscillator strengths and more complicated transition
components, where the HOMO  1 and LUMO + 1 of
17278 Phys. Chem. Chem. Phys., 2011, 13, 1727317283
View Article Online
DPY are p and p*-type orbitals that only localized
on conjugated bridge. In this transition, the amounts of
transferred charges for this transition are very small.
In the S0 - 11Bu transition of DPE, the transition component
is domminated by the CT transition (HOMO - LUMO),
which are independent with the dierent conjugated length
and substituted mode. However, unlike the DPE, besides the
HOMO and LUMO, other p and p* orbitals also have to be
considered for the S0 - 11B1u transitions in DPY. The longer
the conjugated chain is, the more important is the participation
of other more orbitals, which normally diminishes the CT
process and cause the decrease of the oscillator strength.6971
On the other hand, the dierent behaviors of the oscillator
strengths of DPY relative to that of DPE also correlated with
the conguration interaction between the 11B1u and 21B1u states
in long chain DPY, which lowers the 11B1u state.60
3.3. Intramolecular charge transfer
The orbital contour plots for the frontier orbitals of donor/
acceptor substituted DPE and DPY are shown in Fig. 4. We
found that the conjugated bridge in substituted DPE and DPY
makes signicant contribution for all the frontier molecular
orbitals, i.e. the electron is transferred via the conjugated
bridge, which indicates the conjugated bridge dependence of
CT process from donor to acceptor and the strong coupling
between donor (acceptor) and the bridge. Therefore, here we
tentatively suggest the CT process in substituted DPE and
DPY follows a through-bond mechanism.
The CIS-GMH approach was further applied to substituted
DPE and DPY compounds to compute the CT coupling HDA
involving the CT state and LE state. The detail information of
CT and LE state identify is shown in ESI S3.w For simplication
without any loss of generality, only the lowest lying LE and
CT states are considered in this work. The CT coupling
squared (with the unit of eV2) is plotted in Fig. 5, the CT
coupling and the corresponding DA distance values are also
summarized in ESI S4.w It is found that the magnitude of the
CT coupling is sensitive to the dierent substituted positions in
both DPE and DPY series, indicating the signicant inuence
of the dierent substituted mode to the ICT process.
Especially, for both of DPE and DPY, the magnitude of the
CT coupling follows the same order of MM 4 PM/MP 4 PP,
which is consistent with the degree of CT character deduced
by HOMOLUMO energy gap and with the ECL values
estimated by the red shifted absorption with the conjugated
extension mentioned in previous sections. In this order, the
DPE and DPY species with meta substituted donor/acceptor
show relative higher CT coupling values than para isomers, which
agrees with the so-called meta-eect in many stilbene-like
molecules.7274 In donoracceptor substituted DPE systems, the
CT state of the meta isomers are more twisted about the aniline-
styrene bond than that of the para isomers,72 which result in
stronger charge localization and account for the larger CT
character of meta isomers. The meta-eect in DPY systems
can be attributed to the more intense cumulenic character of
conjugated bridge in relaxed excited state of meta isomers.75
In our calculations the relative higher CT coupling in meta
isomers of substituted DPE and DPY can be interpretated by
This journal is c the Owner Societies 2011
 View Article Online

Table 4 The calculated vertical excitation energies, oscillator strengths of the important transitions of typical substituted DPE and DPY, together
with the corresponding transition components

MM PP
DPE S0 - 1 Bu 1
DPY S0 - 1 B1u
1
DPY S0 - 2 B1u
1
DPE S0 - 11Bu DPY S0 - 11B1u DPY S0 - 21B1u
n=2 3.0988 eV/0.1674a 3.2720 eV/0.1602 5.9127 eV/1.3913 2.9919 eV/1.6104 3.0825 eV/1.2683 5.2893 eV/0.8875
H - L,b 0.89 H - L, 0.96 H2 - L + 2, 0.25 H - L, 1.00 H - L, 0.95 H5 - L, 0.62
H1 - L, 0.11 H1 - L, 0.04 H4 - L + 1, 0.22 H1 - L, 0.05 H2 - L + 3, 0.27
H1 - L + 4, 0.18 H1 - L, 0.05
H3 - L, 0.08 H1 - L + 1, 0.04
n=4 2.8062 eV/0.9648 2.7688 eV/0.2293 4.3626 eV/1.8665 2.5669 eV/2.3560 2.5663 eV/1.0512 4.1542 eV/3.7302
Published on 30 August 2011. Downloaded by FAC DE QUIMICA on 18/08/2016 19:44:56.

H - L, 0.92 H - L, 0.31 H3 - L, 0.23 H - L, 0.98 H - L, 0.80 H1 - L + 1, 0.37

H1 - L, 0.08 H2 - L, 0.20 H2 - L + 1, 0.21 H1 - L, 0.02 H1 - L + 1, 0.18 H2 - L, 0.21
H1 - L + 1, 0.17 H1 - L + 3, 0.20 H3 - L, 0.18
H1 - L, 0.13 H1 - L + 2, 0.11 H2 - L + 2, 0.11
H2 - L + 1, 0.10 H1 - L, 0.08 H - L + 2, 0.07
n=6 2.5154 eV/2.8622 2.3268 eV/0.1948 3.7240 eV/2.1215 2.2678 eV/3.0507 2.1860 eV/0.6953 3.5518 eV/4.8548
H - L, 0.94 H - L, 0.22 H - L + 2, 0.48 H - L, 0.97 H - L, 0.67 H - L + 2, 0.28
H  1 - L, 0.06 H  2 - L + 1, 0.31 H  1 - L + 2, 0.13 H  1 - L, 0.03 H  1 - L + 1, 0.28 H  1 - L + 1, 0.25
H  1 - L, 0.23 H  2 - L + 1, 0.11 H  3 - L, 0.22
H  1 - L + 1, 0.15 H  1 - L, 0.09 H  2 - L, 0.17
n=8 2.2552 eV/3.9264 2.0308 eV/0.1056 3.1999 eV/3.3297 2.0483 eV/3.6949 1.9343 eV/0.4840 3.1563 eV/5.3355
H - L, 0.96 H - L, 0.19 H - L + 2, 0.20 H - L, 0.97 H - L, 0.59 H - L + 2, 0.41
H  1 - L, 0.04 H  2 - L + 1, 0.31 H  1 - L, 0.17 H  1 - L, 0.03 H  1 - L + 1, 0.33 H  1 - L + 1, 0.20
H  1 - L, 0.20 H  2 - L + 1, 0.17 H  3 - L, 0.18
H  1 - L + 1, 0.15 H  3 - L, 0.16 H  2 - L, 0.14
H  2 - L, 0.09 H  1 - L + 2, 0.15
n = 10 2.0536 eV/4.7349 1.8410 eV/0.0558 2.9295 eV/5.5259 1.8821 eV/4.2979 1.7475 eV/0.3517 2.9431 eV/5.5157
H - L, 1.00 H - L, 0.19 H - L + 2, 0.12 H - L, 0.97 H - L, 0.53 H - L + 2, 0.50
H  2 - L + 1, 0.35 H  1 - L, 0.24 H  1 - L, 0.03 H  1 - L + 1, 0.37 H  1 - L + 1, 0.18
H  1 - L, 0.18 H  2 - L + 1, 0.20 H  3 - L, 0.14
H  1 - L + 1, 0.14 H  3 - L, 0.12 H  2 - L, 0.13
H  2 - L, 0.10 H  1 - L + 2, 0.18
a b
The vertical excitation energy and corresponding oscillator strength. H = HOMO, L = LUMO.

Fig. 4 Schematic diagram with the calculated absolute energies and the orbital contour plots of the frontier orbitals around the gap of donor/
acceptor substituted DPE and DPY.

the dierent electronic structure feature and conguration
interaction properties of corresponding transitions. As shown
in Fig. 4, we found that meta-substitution blocks charge
delocalization in the HOMO, where the wavefunction is higher
localized relative to that in para isomers. As a consequence,
the local excitation of donor is somewhat limited in the para
isomers due to the lower degree of localization, and the CT
coupling is restricted, whereas the singlet states of the meta
derivatives show greater CT character. Moreover, the HOMO
energy in meta isomer of DPE increases around 0.006 eV, while
the LUMO decreases about 0.287 eV relative to that in non-
substituted species. However, substitution of donor/acceptor

This journal is c the Owner Societies 2011 Phys. Chem. Chem. Phys., 2011, 13, 1727317283 17279
Published on 30 August 2011. Downloaded by FAC DE QUIMICA on 18/08/2016 19:44:56.
Fig. 5 Length dependence of squared electronic coupling of DPE/DPY series and its exponential decay tting.
in the para position leads to a more symmetric increase
(0.307 eV)/decrease (0.297 eV) of the HOMO/LUMO, which
would induce a weaker electron interaction than in the meta
isomer (also suitable for the DPY system).76 On ther other
hand, as shown in Table 4 and mentioned above, TDDFT
calculation indicates that the meta isomers show more complex
contributed components of S0 - 11Bu (DPE) and S0 - 11B1u
(DPY) transitions than para isomers, while the contribution of
HOMO - LUMO component accordingly turns lower. As
shown in Fig. 4, many other frontier molecular orbitals beside
HOMO and LUMO (such as HOMO  2, HOMO  1,
LUMO + 1, LUMO + 2) are mainly contributed by the
conjugated bridge, while HOMO locate on donor and con-
jugated bridge, and LUMO is contributed by the acceptor and
conjugated bridge. Therefore, the complex transition compo-
nents involved plenty of frontier molecular orbitals in meta
isomers promote the interaction between donor/acceptor and
conjugated bridge, then accordingly induces the relative high
CT coupling values.
For bridge-assisted CT systems, the squared CT coupling is
usually expected to decrease approximately with distance and
is characterized by an exponential decay formula with an
exponent parameter b:7779
|HDA|2 = |H0DA|2exp[b(r  r0)] (7)
where H0DA is the coupling element at a reference donor
acceptor distance r0, and the parameter b represents the
donoracceptor distance dependence of the squared CT
coupling. In this work, the DA distance is dened as the
nitrogen atom in dimethylamine to carbon in cyano. The
exponential tting of the CT coupling squared (with the unit
of eV2) is also shown in Fig. 5, which is dependent with the
donoracceptor distance (with the unit of angstrom), and the
tted b values are also listed in Fig. 5. The decay parameter
b suggests the coupling mechanism in some extent. Experimental
studies suggested that typical values for b range from 2.8 to
3.0 A1 may be for through-space coupling, and from 0.8 to
17280 Phys. Chem. Chem. Phys., 2011, 13, 1727317283
View Article Online
1.1 A1 for through-bond coupling in saturated hydrocarbon
bridges.30,8082 It is found that most of the tted b values of the
CT coupling in DPE and DPY series are around 0.20.5 A1,
the b value suggests that the through-bond mechanism rather
than the through-space mechanism makes the dominant
contribution to the CT coupling. The through-bond character
of the CT process in DPE/DPY is agreement to the signicant
contribution of conjugated bridge for the HOMO/LUMO
representation as mentioned in the beginning of this section.
Moreover, the overall coupling value is composed of two
contributions as shown below:83,84
HDA = HSpace Bond
DA + HDA (8)
where the rst term HDASpace is the direct through-space
coupling contribution, and the second term HDABond is the
through-bond contribution mediated by the presence of a
conjugated bridge. To further study the through-space/bond charge
transfer mechanism in DPE and DPY, the through-space coupling
is calculated in partial structures containing disconnected donor
and acceptor fragments with two extra lling hydrogen
atoms.37 The calculated coupling values are listed in Table 5.
Compared to the full molecule including the conjugated bridge
connecting donor and acceptor, it is found that the through-space
coupling values are much smaller and decay very fast along with
the donoracceptor distance. Therefore, we conrm that the CT
process in these molecules is predominated by the through-bond
mechanism, which is consistent with the prediction from the
frontier molecular orbital representation and the values of
tted decay parameter b.
On the other hand, the squared CT coupling of DPE and
DPY series shows dierent decay pattern with the extension of
conjugation. For DPE series, the squared CT coupling follows
regular exponential decay monotonously with the increase of
conjugated length, which is consistent with the calculated result
in literature.85 However, the conjugation length dependence of
the squared CT coupling of DPY is obviously dierent from
that of DPE, where the coupling values obeys the exponential
This journal is c the Owner Societies 2011
 View Article Online

Table 5 Calculated CT coupling of the disconnected fragment exponential decay when the repeat units (n) is less than 4. The
without mediated bridge impact of the substituents is pronounced only in the shortest
Through space coupling  102/eV in DPE oligomers, where the donor and acceptor not only inuence
the orbital energies, they also alter the electron correlation as
MM PM MP PP discussed above.
n=1 0.42 0.60 1.57 0.43
n=2 5.46  104 5.08  104 2.08  103 4.84  104
n42 0 0 0 0 4. Conclusions
2
Through space coupling  10 /eV in DPY We have performed a series of quantum chemical calculations
MM PM MP PP
to study the conjugated length and terminal donor/acceptor
Published on 30 August 2011. Downloaded by FAC DE QUIMICA on 18/08/2016 19:44:56.

n=1 0.53 1.09 1.21 0.14

n=2 5.70  104 0 2.03  103 0 substitution dependences of the absorption apectra and CT
n42 0 0 0 0
decay with the number of repeat units (n) larger than 4,
whereas the CT coupling doesnt increase signicantly but
turns into a platform-like stage when n is less than 3, similar to
the behavior of oscillator strength as shown in Fig. 3. In
donorbridgeacceptor system, bridge energetic plays an
important role in controlling coupling and CT rates.38,86 The
stage of CT coupling in short chain DPY is remarkably
correlated to the energetic matching of the donor/acceptor
relative to the conjugated bridge. The DFT calculated
HOMO/LUMO energy levels of the donor, acceptor and
conjugated bridge fragments with dierent length in DPE
and DPY series is showed in Fig. 6. For DPE, it is found that
the LUMO of donor and HOMO of acceptor shows the
perfect matching energetically with that of polyene bridge
with dierent conjugated length, suggesting that the donor
excited state and acceptor CT involved active orbitals are close
in energy to the HOMO/LUMO of the polyene bridge.
However for DPY, those species with short polyyne bridge
show evidently unmatched energy level between donor, bridge
and acceptor. The twisting the cylindrical triple bond in DPY,
which breaks the conjugation of a single DPY chain, could be
the main reason leading to the high bridge energy in the short
chain. Therefore, we believe that the energetic unmatching in
DPY series induced by the torsional motion of bridge may be
the main reason for the CT coupling which doesnt obey the
properties of two model conjugated a,o-diphenylpolyenes and
a,o-diphenylpolyynes. The DFT calculation indicates that the
average bond length alternation between unsaturated multiple
(CRC and CQC) and saturated single bonds (CC), and
HOMOLUMO energy gap decrease regularly with the
extension of conjugation. The TDDFT calculated absorption
spectra of DPE and DPY show typical red shift with the
conjugated length increases and the eective conjugated length
(ECL) shows the same order MM 4 MP/PM 4 PP, resulting
from the dierent p-electron delocalization and conjugation
eciency, which is also reected by the dierent magnitude of
the electronic coupling with the same orders. The GMH
analysis indicates that the CT process in both DPE and
DPY is predominated by the through-bond mechanism.
Specially, for DPE series, the squared CT coupling shows
regular exponential decay monotonously with the increase of
conjugated length, but DPY series show unexpected relative
low coupling values in species with conjugated bridge less than
n = 4, which is the result of low energetic matching degree of
the frontier molecular orbitals between donor/acceptor and
conjugated bridge. We believe that these results provide a well
description about the absorption spectra and CT properties of
DPE and DPY species, and the relationship between the
relative position of the donor and acceptor group, as well as
the inuence of conjugated bridging units. Meanwhile, it is
nessesary to note that for both TDDFT and CIS methods
empolyed in this work, the calculated accuracy are limited, where
the presented calculation are qualitative or semi-quantitative
results. The more accurate result relies on the future application
of highly accurate methods (such as CASPT2 and MRCI) on
such complex systems, which are applicable only to small
molecules up to 20 atoms nowadays.

Acknowledgements
This work was nancially supported by NSFC, 973 Programs
and Chinese Academy of Sciences.

References
1 R. A. Marcus and N. Sutin N, Biochim. Biophys. Acta, 1985, 811,
265322.
2 M. R. Wasielewski, Chem. Rev., 1992, 92, 435461.
3 D. Gust, T. A. Moore and L. Moore, Acc. Chem. Res., 2001, 34,
4048.
4 M. Glasbeek and H. Zhang, Chem. Rev., 2004, 104, 19291954.
5 G. J. Zhao, R. K. Chen, M. T. Sun, J. Y. Liu, G. Y. Li, Y. L. Gao,
Fig. 6 The energy level of the HOMOLUMO of the donor, K. L. Han, X. C. Yang and L. Sun, Chem.Eur. J., 2008, 14,
acceptor and conjugated bridge fragments. 69356947.

This journal is c the Owner Societies 2011 Phys. Chem. Chem. Phys., 2011, 13, 1727317283 17281

6 H. Wang, H. Zhang, W. Rettig, A. I. Tolmachev and M. Glasbeek,
Phys. Chem. Chem. Phys., 2004, 6, 34373446.
7 S. I. Druzhinin, N. P. Ernsting, S. A. Kovalenko, L. P. Lustres,
T. A. Senyushkina and K. A. Zachariasse, J. Phys. Chem. A, 2006,
110, 29552969.
8 V. A. Galievsky, S. I. Druzhinin, A. Demeter, Y. B. Jiang,
S. A. Kovalenko, L. P. Lustres, K. Venugopal, N. P. Ernsting,
X. Allonas, M. Noltemeyer, R. Machinek and K. A. Zachariasse,
Chem. Phys. Chem, 2005, 6, 23072323.
9 Y. Luo, P. Norman, P. Macak and H. Agren, J. Phys. Chem. A,
2000, 104, 47184722.
10 S. Pan, Q. Fu, T. Huang, A. Zhao, B. Wang, Y. Luo, J. Yang and
Published on 30 August 2011. Downloaded by FAC DE QUIMICA on 18/08/2016 19:44:56.
J. Hou, Proc. Natl. Acad. Sci. U. S. A., 2009, 106, 1525915263.
11 P. Brocorens, E. Zojer, J. Cornil, Z. Shuai, G. Leising, K. Mullen
and J. L. Bredas, Synth. Met., 1999, 100, 141162.
12 E. Zojer, P. Buchacher, F. Wudl, J. Cornil, J. P. Calbert,
J. L. Bredas and G. Leising, J. Chem. Phys., 2000, 113,
1000210012.
13 W. He, Z. Li, J. Yang and J. G. Hou, J. Chem. Phys., 2008,
128, 164701.
14 M. Kula, J. Jiang and Y. Luo, J. Comput. Theor. Nanosci., 2008, 5,
401421.
15 L. L. Lin, J. C. Leng, X. N. Song, Z. L. Li, Y. Luo and
C. K. Wang, J. Phys. Chem. C, 2009, 113, 1447414477.
16 S. A. Kovalenko, N. P. Ernsting and J. Ruthmann J, Chem. Phys.
Lett., 1996, 258, 445454.
17 R. Chen, G. Zhao, X. Yang, X. Jiang, J. Liu, H. Tian, Y. Gao,
X. Liu, K. Han, M. Sun and L. Sun, J. Mol. Struct., 2008, 876,
102109.
18 B. C. Lin, C. P. Cheng, Z. Q. You and C. P. Hsu, J. Am. Chem.
Soc., 2005, 127, 6667.
19 B. E. Bowler, T. J. Meade, S. L. Mayo, J. H. Richards and
H. B. Gray, J. Am. Chem. Soc., 1989, 111, 87578759.
20 Y. A. Berlin, A. L. Burin and M. A. Ratner, J. Phys. Chem. A,
2000, 104, 443445.
21 M. M. Toutounji and M. A. Ratner, J. Phys. Chem. A, 2000, 104,
85668569.
22 K. Pettersson, J. Wiberg, T. Ljungdahl, J. Martensson and
B. Albinsson, J. Phys. Chem. A, 2006, 110, 319326.
23 J. Wiberg, L. Guo, K. Pettersson, D. Nilsson, T. Ljungdahl,
J. Martensson and B. Albinsson, J. Am. Chem. Soc., 2007, 129,
155163.
24 R. A. Marcus, J. Chem. Phys., 1965, 43, 679701.
25 J. L. Bredas, D. Beljonne, V. Coropceanu and J. Cornil, Chem.
Rev., 2004, 104, 49715003.
26 R. J. Cave and M. D. Newton, Chem. Phys. Lett., 1996, 249,
1519.
27 R. J. Cave and M. D. Newton, J. Chem. Phys., 1997, 106,
92139226.
28 R. S. Mulliken and W. B. Person, Molecular Complexes, Wiley,
New York, 1969.
29 J. R. Reimers and N. S. Hush, J. Phys. Chem., 1991, 95, 97739781.
30 H. C. Chen and C. P. Hsu, J. Phys. Chem. A, 2005, 109,
1198911995.
31 J. Zheng, Y. K. Kang, M. J. Therien and D. N. Beratan, J. Am.
Chem. Soc., 2005, 127, 1130311310.
32 K. Kumar, I. V. Kurnikov, D. N. Beratan, D. H. Waldeck and
M. B. Zimmt, J. Phys. Chem. A, 1998, 102, 55295541.
33 W. P. Anderson, T. R. Cundari and M. C. Zerner, Int. J. Quantum
Chem., 1991, 39, 3145.
34 (a) A. Dreuw and M. Head-Gordon, J. Am. Chem. Soc., 2004, 126,
40074016; (b) A. Dreuw and M. Head-Gordon, Chem. Rev., 2005,
105, 40094037; (c) A. Dreuw, J. L. Weisman and M. Head-
Gordon, J. Chem. Phys., 2003, 119, 29432946.
35 C. P. Hsu, Acc. Chem. Res., 2009, 42, 509518.
36 J. Gierschner, J. Cornil and H. J. Egelhaaf, Adv. Mater., 2007, 19,
173191.
37 (a) H. C. Chen, Z. Q. You and C. P. Hsu, J. Chem. Phys., 2008,
129, 084708; (b) C. P. Hsu, Z. Q. You and H. C. Chen, J. Phys.
Chem. C, 2008, 112, 12041212.
38 (a) Z. Q. You, C. P. Hsu and G. R. Fleming, J. Chem. Phys., 2006,
124, 044506; (b) Z. Q. You and C. P. Hsu, J. Chem. Phys., 2010,
133, 074105.
39 A. Pogantsch, G. Heimel and E. Zojer, J. Chem. Phys., 2002, 117,
59215928.
17282 Phys. Chem. Chem. Phys., 2011, 13, 1727317283
View Article Online
40 E. Zojer, J. Cornil, G. Leising and J. L. Bredas, Phys. Rev. B:
Condens. Matter, 1999, 59, 79577968.
41 W. Su, J. Jiang and Y. Luo, Chem. Phys. Lett., 2005, 412, 406410.
42 X. Y. Feng, Z. Li and J. Yang, J. Phys. Chem. C, 2009, 113,
2191121914.
43 X. Wu, Q. Li, J. Huang and J. Yang, J. Chem. Phys., 2005,
123, 184712.
44 R. Kiebooms, E. Zojer, P. Markart, R. Resel, L. De Schepper,
D. Vanderzande, J. Gelan, L. Stals, S. Tasch and G. Leising,
Synth. Met., 1999, 102, 997.
45 C. P. Hsu, P. J. Walla, M. Head-Gordon and G. R. Fleming,
J. Phys. Chem. B, 2001, 105, 1101611025.
46 W. Mizukami, Y. Kurashige, M. Ehara, T. Yanai and T. Itoh,
J. Chem. Phys., 2009, 131, 174313.
47 Y. Sonoda, M. Goto, M. Tsuzuki and N. Tamaoki, J. Phys. Chem.
A, 2006, 110, 1337913387.
48 H. El-Gezawy and W. Rettig, Chem. Phys., 2006, 327, 385394.
49 H. El-Gezawy, W. Rettig and R. Lapouyade, J. Phys. Chem. A,
2006, 110, 6775.
50 Y. Luo, H. Agren and S. Stafstrom, J. Phys. Chem., 1994, 98,
77827789.
51 Y. Luo, P. Norman, D. Jonsson and H. Agren, Mol. Phys., 1996,
89, 14091421.
52 M. Wahadoszamen, T. Hamada, T. Iimori, T. Nakabayashi and
N. Ohta N, J. Phys. Chem. A, 2007, 111, 95449552.
53 Y. Nagano, T. Ikoma, K. Akiyama and S. Tero-Kubota, J. Chem.
Phys., 2001, 114, 17751784.
54 I. Ledoux, I. D. W. Samuel, J. Zyss, S. N. Yaliraki,
F. J. Schattenmann, R. R. Schrock and R. J. Silbey, Chem. Phys.,
1999, 245, 116.
55 A. Osuka, N. Tanabe, S. Kawabata, I. Yamazaki and
Y. Nishimura, J. Org. Chem., 1995, 60, 71777185.
56 C. Wu, S. Tretiak and V. Y. Chernyak, Chem. Phys. Lett., 2007,
433, 305311.
57 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, J. A. Montgomery Jr., T. Vreven,
K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi,
V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega,
G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota,
R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda,
O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox,
H. P. Hratchian, 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, P. Y. Ayala, K. Morokuma,
G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski,
S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick,
A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz,
Q. Cui, A. G. Baboul, S. Cliord, J. Cioslowski, B. B. Stefanov,
G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin,
D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara,
M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen,
M. W. Wong, C. Gonzalez and J. A. Pople, GAUSSIAN 03 (Revision
E.01), Gaussian, Inc., Wallingford, CT, 2004.
58 M. Bruschi, M. G. Giureda and H. P. Luthi, Chem. Phys. Chem,
2005, 6, 511519.
59 M. Bruschi, P. A. Limacher, J. Hutter and H. P. Luthi, J. Chem.
Theory Comput., 2009, 5, 506514.
60 Y. Nagano, T. Ikoma, K. Akiyama and S. Tero-Kubota, J. Am.
Chem. Soc., 2003, 125, 1410314112.
61 J. Rissler, Chem. Phys. Lett., 2004, 395, 9296.
62 N. Li, K. Jia, S. Wang and A. Xia, J. Phys. Chem. A, 2007, 111,
93939398.
63 R. J. Magyar, S. Tretiak, Y. Gao, H. L. Wang and A. P. Shreve,
Chem. Phys. Lett., 2005, 401, 149156.
64 T. Itoh, J. Chem. Phys., 2005, 123, 064302.
65 T. Hoshi, J. Okubo, M. Kobayashi and Y. Tanizaki, J. Am. Chem.
Soc., 1986, 108, 38673872.
66 M. Kobayashi, T. Hoshi, J. Okubo, H. Hiratsuka, T. Harazono,
M. Nakagawa and Y. Tanizaki, Bull. Chem. Soc. Jpn., 1984, 57,
29052909.
67 H. Meier, U. Stalmach and H. Kolshorn, Acta Polym., 1997, 48,
379384.
68 J. He, J. L. Crase, S. H. Wadumethrige, K. Thakur, L. Dai, S. Zou,
R. Rathore and C. S. Hartley, J. Am. Chem. Soc., 2010, 132,
1384813857.
This journal is c the Owner Societies 2011

69 H. Meier, Angew. Chem., Int. Ed., 2005, 44, 24822506.
70 H. Meier, J. Gerold, H. Kolshorn, W. Baumann and M. Bletz,
Angew. Chem., Int. Ed., 2002, 41, 292295.
71 H. Meier, B. Muhling, A. Oehlhof, S. Theisinger and E. Kirsten,
Eur. J. Org. Chem., 2006, 405413.
72 F. D. Lewis and J. S. Yang, J. Am. Chem. Soc., 1997, 119,
38343835.
73 F. D. Lewis and W. Weigel, J. Phys. Chem. A, 2000, 104,
81468153.
74 E. M. Crompton and F. D. Lewis, Photochem. Photobiol. Sci.,
2004, 3, 660668.
75 K. M. Gaab, A. L. Thompson, J. Xu, T. J. Martinez and
Published on 30 August 2011. Downloaded by FAC DE QUIMICA on 18/08/2016 19:44:56.
C. J. Bardeen, J. Am. Chem. Soc., 2003, 125, 92889289.
76 M. M. Oliva, J. Casado, G. Hennrich and J. T. L. Navarrete,
J. Phys. Chem. B, 2006, 110, 1919819206.
77 C. P. Hsu and R. A. Marcus, J. Chem. Phys., 1997, 106, 584598.
This journal is c the Owner Societies 2011
View Article Online
78 B. Albinsson and J. Martensson, J. Photochem. Photobiol., C,
2008, 9, 138155.
79 B. Albinsson, M. P. Eng, K. Pettersson and M. U. Winters, Phys.
Chem. Chem. Phys., 2007, 9, 58475864.
80 G. L. Closs, L. T. Calcaterra, N. J. Green, K. W. Peneld and
J. R. Miller, J. Phys. Chem., 1986, 90, 36733683.
81 G. L. Closs and J. R. Miller, Science, 1988, 240, 440447.
82 M. J. Shephard, M. N. Paddon-Row and K. D. Jordan, J. Am.
Chem. Soc., 1994, 116, 53285333.
83 S. Larsson, J. Am. Chem. Soc., 1981, 103, 40344040.
84 V. C. Felicissimo, A. Cesar, Y. Luo, F. Gelmukhanov and
H. Agren, J. Phys. Chem. A, 2005, 109, 73857395.
85 A. V. Vooren, V. Lemaur, A. Ye, D. Beljonne and J. Cornil, Chem.
Phys. Chem, 2007, 8, 12401249.
86 F. D. Lewis, J. Liu, W. Weigei, W. Rettig, I. V. Kurnikov and
D. N. Beratan, Proc. Natl. Acad. Sci. U. S. A., 2002, 99, 1253612541.
Phys. Chem. Chem. Phys., 2011, 13, 1727317283 17283