13 November 1998

Chemical Physics Letters 296 1998. 483488

Interference effects on through-bond electronic interaction

propagation
A.J. Parnaba-daSilva,
A.A.S. da Gama

Departamento de Qumica
Fundamental, Uniersidade Federal de Pernambuco, 50.670-901, Recife-PE, Brazil

Received 7 July 1998; in final form 10 September 1998

Abstract
The propagation of an electron donoracceptor interaction through a molecular structure is described by using the
Greens function formalism, with orbital decimation to reduce the system to a two-level representation. Analytical
expressions for the effective donorracceptor energy and coupling show the effect of destructive interference of pathways
created by side bonds or lone pairs, respect to the main chain pathway. Application for model systems suggests that
destructive interference will make saturated bridging groups, and particularly with lone pairs, less efficient than unsaturated
groups, for donoracceptor interaction propagation through a s-bond pathway. q 1998 Elsevier Science B.V. All rights
reserved.

1. Introduction
Since the suggestion about the role of a peptide
chain in communicating chemical reactions between
distant sites of a protein w1,2x, several experimental
and theoretical works are reinforcing the belief that
electron transfer interaction is rather through-bond
controlled w3x. Evidences of the special role of
through-bond interactions are known from the interpretation of the splitting of nitrogen lone-pair states
w4,5x measured from photoelectron spectroscopy w6x.
Along the last 20 years, several donoracceptor
bridged systems have been designed w7x to help the
understanding of the role of the intervening media in
propagating electron-transfer interactions. It is in
general believed that a bridge delocalized p orbital
can be more efficient for propagating a donoraccep)

Corresponding author. E-mail: arnobio@npd.ufpe.br

tor interaction. However, in several biological and

model systems, no efficient p pathway is available
and the effectiveness of saturated bridges may be
analysed.
A recently studied donorbridgeacceptor system
is constituted of two metalloporphyrins bridged by
aromatic groups w8x. This system may be helpful to
illustrate the dependence of through-bond interaction
with the relative orientation of the delocalized p
orbitals on the individual molecular blocks. Since the
angle between the porphyrins and its neighbouring
aromatic group was found around 608 and also nearly
408 between two aromatic groups w9x, a p electron
delocalization can be of little effectiveness over the
whole structure. In this condition, a s pathway may
be more reliable in mediating the donoracceptor
interaction.
Portela et al. w10x measured electron transfer rates
in porphyrin bridged systems with a saturated group,

0009-2614r98r$ - see front matter q 1998 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 9 - 2 6 1 4 9 8 . 0 1 0 4 1 - 0

A.J. Parnaba-daSila,
A.A.S. da Gama r Chemical Physics Letters 296 (1998) 483488

484

piperazyl, replacing an aromatic group and found a

slightly larger rate of exited state quenching, assigned to faster electron transfer, at nearly the same
separation distance. Since piperazyl has two nitrogens in an ortho position, the role of the nitrogen
lone pairs may be analysed.
Using the Greens function formalism, as has
been applied to electron-transfer problems w11x, the
contribution of the nitrogen lone pairs, in mediating
donoracceptor interaction through a s pathway,
will be discussed.
2. Electronic interaction
For weakly coupled donor and acceptor, a diabatic electron transfer rate constant k . is assumed to
be given, as a transition probability rate from a
reactant state a s D ) y B y A. to a product state
b s Dqy B y Ay ., by Fermis golden rule:
2p
< V < 2 FC . .
ks
1.
" da
The electronic matrix element Vda is associated
with an effective donoracceptor interaction w12x,
while the FranckCondon FC. term contains the
contribution of the nuclear co-ordinates coupled to
the process. This expression assumes the BornOppenheimer and Condon approximations, and has been
widely used and discussed in the recent literature
w13x.
Vda can be obtained from quantum chemical calculations as half of the splitting D . of the energy
surfaces at a avoid crossing geometry w14x. Another
approach to calculate Vda uses Greens function to
reduce the system to a two-level representation, with
an effective donoracceptor interaction w11,12x given,
for an orthonormal basis set, by:
Vdaeff E . s da q d i Gi j E . ja

2.

ij

where da , the through space interaction, is assumed

to be negligible at large distance, dl and na are,
respectively, the donorbridge and acceptorbridge
interactions, and the Greens function matrix element, Gi j E ., describes the interaction propagation
through a bridging pathway beginning at an orbital i
and ending at an orbital j. A chain of n orbitals of
same energy , with an interaction between first

neighbours, for example, gives the classical McConnells result w15x:

Vdaeff E . s

d l na

Ey

Ey

4.

corresponding to an exponential decay of the electron transfer rate, k s A expy2 j R ., respect to the
donoracceptor separation distance R ., with a decay parameter given by j s yay1 ln r E y ..,
where a is the dimension of the bridge unit.
Simple models may be helpful for the interpretation of experiments. The pathway model, the simplest theoretical approach for the calculation of Vda
in biological system w16x, assumes a parameter
ir E y i . per bond, with different interaction parameters for covalent bond C ., hydrogen bridges
H . and through-space contacts S ., has been succeeded in reproducing and predicting electron transfer rates in modified metalloproteins w3x. Using the
Greens function formalism, the pathway model is
being improved to account for multiple pathways
and interference among them w17x. The identification
of the effect of lone pairs, side groups or chains is an
important contribution for the improvement of the
pathway model w18x.
Without lost of generality, the donor and acceptor
may be assumed to be bonded to single sites of the
bridge, since, by orbital decimation, the whole Fock
matrix can be reduced to two effective orbitals at
these sites w11x, and all pathways may be included in
a single Greens function matrix element. Several
limitations, due to the approximations leading to Eq.
4., can be avoided by the calculation of the Greens
function matrix element.
Although the selected bridging structures were not
so large for more rigorous calculations, they are just
considered as models for the identification of the
details of the bridge electronic structure that controls
the electronic interaction propagation. The effort for
exact calculation may not be compensated since
basic limitations remain, related to the molecular
dynamics and numerical methods: ab initio calculations are sensitive to the choice of base functions
w19x and semi-empirical methods are parametrized, in
general for other properties.
Using the Greens function formalism, with orbital decimation in an atomic orbital representation,
Gi j E . will be calculated for unsaturated and satu-

A.J. Parnaba-daSila,
A.A.S. da Gama r Chemical Physics Letters 296 (1998) 483488

rated bridging systems and compared with piperazyl,

to analyze the possible role of the nitrogen lone pairs
in mediating donoracceptor interaction through a s
pathway.
The use of a non-orthonormal atomic basis set is a
serious approximation w20x. However, the aim of this
work is to show that the effect of interference by
side groups or bonds is consistently described at an
analytical level, based in atomic orbital or bonding
orbital picture of the bridge, and by a simple calculation with a parametric tight-binding hamiltonian.
Several other important approximations are also introduced: the interactions are limited to first neigh-

485

bours, through-space interactions are neglected and

the donor and acceptor are not explicitly considered.
However, the results were observed in a fair agreement with semi-empirical and ab initio calculations
of D for the same structures w9x, and also with
preliminary results of a more rigorous calculation
w21x that uses a generalisation of the strategy of
Coutinho-Neto and da Gama w11x that accounts for
the non-orthonormality of the basis set w20x. An
analysis of the Fock matrix indicate that the interaction beyond first neighbours or through space are
small and that a separation between s and p pathways may be assumed.

Fig. 1. Single units: phenyl, cyclohexyl, piperazyl and carboxyl-acid dimer, and three unit bridges of the kind phenylXphenyl, with
X s phenyl, cyclohexyl, piperazyl and carboxyl-acid dimer.

A.J. Parnaba-daSila,
A.A.S. da Gama r Chemical Physics Letters 296 (1998) 483488

486

3. Results and discussion

The molecular model system considered uses
phenyl, cyclohexyl and piperazyl groups as constituents for the bridges Fig. 1.. All these groups are
cyclic structures six-member rings. and may be
considered as having two parallel pathways. Propagation through these pathways shows constructive
interference effects. However, other pathways must
also be considered, created by the side bonds andror
lone pairs. These later pathways are of special interest, because they are responsible for destructive interference that distinguish the electronic interaction
propagation among the three kind of rings.
The decimation follows a hierarchy strategy that
begins by the side bonds and lone pairs. In a sbondrlone-pair representation of the bridges, the
central CC bond, for example, interact with two CH
bonds in phenyl, but with two pairs of CH bonds in
both saturated rings. Then, the effective energy for
these bonds, after eliminating the CH bonds will be:
M
uns
sq

M
sat
sq

2 2
Ey

unsaturated. and

4 2
Eyy

saturated.

and the effective interactions with the neighbouring

bonds:
M
uns
sq

M
sat
sq

2
Ey

unsaturated. and

2 2
Eyy

saturated. ,

where equal energy . and interaction . parame-

Fig. 2. The Greens function matrix element between two opposite

side bonds of a hexagonal ring, G1,10 E . for the unsaturated ring
continuous., for the saturated cyclohexyl ring points. and for the
saturated ring with lone pairs dash..

Fig. 3. The decay of the Greens function matrix element through

a bridge with one, two and three phenyl B., cyclohexyl m.,
piperazyl '. or carboxyl-acid dimer %..

ters are assumed for the bonding orbitals of the

bridge and the electron tunneling energy E . is
placed above the bonding states and far from antibonding ones. In this condition, the corrections results in destructive interference. The fact that saturated bridges have two CH bonds, for one on the
unsaturated bridge, results in larger destructive contribution across the former.
When piperazyl is compared with cyclohexyl, the
new feature is the presence of two lone pairs replacing CH bonds. Since the energy of a lone pair is
higher than a CH bond, the destructive interference
become even larger.
The qualitative analysis are confirmed from calculations with an atomic orbital representation and are
also consistent with more rigorous calculations w9,21x.
Fig. 2 shows the behaviour of the Greens function
matrix elements between the extreme sites of a bridge
made of one unit of each ring phenyl, cyclohexyl
and piperazyl. around an electron tunnelling energy
arbitrarily set at y11.5 eV, a meddle gap region
where the Greens function matrix element is nearly
independent of the energy, as convenient for description of the interaction between localised states and
for a two state reduction.
When a sequence of rings is calculated, a fair
exponential behaviour is observed, as can be seen in
Fig. 3. These results were obtained by a decimation
strategy, with extended Huckel
parameters at a

tight-binding hamiltonian, for a molecular geometry

A.J. Parnaba-daSila,
A.A.S. da Gama r Chemical Physics Letters 296 (1998) 483488

Table 1
The Greens function matrix elements between the extreme sites
of three unit bridges < G1,26 Esy11.5 eV.<..
Bridge

< G1, n Esy11.5 eV.<

phenyl. 3
cyclohexyl. 3
piperazyl. 3
carboxyl-acid dimer. 3
phenylcyclohexylphenyl.
phenylpiperazylphenyl.
phenylcarboxyl-acid dimerphenyl.

2.1=10y3
3.9=10y5
1.9=10y7
4.5=10y9
3.5=10y4
5.3=10y5
2.2=10y5

optimised by an semi-empirical AM1 calculation.

The behaviour of Fig. 3 were observed to be similar
with CNDOr2 or AM1 parameters, at different
choices of the tunnelling energy.
Finally, the Greens function matrix elements
G 1,26 E .. were calculated for mixed bridges of the
kind phenylXphenyl, with X s cyclohexyl, piperazyl or carboxyl-acid dimer. The later was included
as an example of a bridge that contain hydrogen
bond in the main pathway w22x. The results can be
compared at Table 1. The qualitative results are in
agreement with the expectations and with quantum
chemical ab initio and semi-empirical calculations
w9,21x. The pure aromatic bridge is the more efficient, not because of p-electron delocalization, but
due to the smaller destructive interference of side
bonds. Substitution of unsaturated by saturated units
will decrease the electron transfer interaction propagation. The presence of lone pairs instead of CH side
bonds will make the bridge even less efficient.
The bridge with carboxyl-acid dimer may be the
less efficient due to the hydrogen bonds in the main
pathway. However, there are also two oxygen lone
pairs contributing with destructive interference.
Therefore, a more detailed study of bridges with
hydrogen bonds will be necessary to identify the
conditions where the pathways created by them can
be more efficient w23x. Hydrogen bonds are very
important in providing efficient pathways in biological systems, because avoid pathways with large number of intermediate units.
4. Conclusion
The Greens function formalism offers an understandable picture for the differences in electron

487

transfer interaction propagation through unsaturated

and saturated units, as well as for bridges made of
sequences of unsaturated and saturated units. Also,
gives a simple explanation of the interference effects
of side bonds and lone pairs.
A simple s-bond and lone-pair representation of
the bridging structures allows an analytical interpretation of these interference effects, and the results are
qualitatively consistent with more accurate levels of
calculations.
Both, side bonds and lone pairs, contribute with
destructive interference for the propagation of the
electron transfer interaction through the bridges, the
latter being even more destructive than the former.
Then, the use of groups with nitrogen lone pairs may
be unfavourable to electron transfer propagation, unless the donor and acceptor are bonded to these lone
pairs, what places them inside the main pathway.

Acknowledgements
The authors are grateful to Dr. J.B.P. da Silva for
suggestions on the study of bridges with hydrogen
bonds.

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