Effects of the System’s-Bath Coupling and Temperature on Electronic

Transport of Dicyanorhodanine + 2-formyltetratiafulvalene

Duvalier Madrid-Usuga, Carlos Melo-Luna, John H. Reina
Universidad del Valle, Departamento de Fisica, A.A 22350, Cali-Colombia
Centre for Bioinformatics and Photonics-CiBioFi, Cali-Colombia

Abstract
Single molecule bonds have been extensively studied in recent years, mainly due to their potential applications in non-electronic devices. However, the successful
implementation of organic molecules in solar cells, for example, the understanding for energy conversion and nanoscale energy transfer, propose the intriguing
challenge of designing particular molecular structures function as efficient energy conversion units and maintain a well-defined geometry. This motivates us to explore
the effects of the environment in this type of systems in order to identify the contributing to the charge transfer process (CT) in molecular systems, since the
environment and quantum correlations in thisprocesso play an important role the CT dinamic. In this work we study the coupling effect between the molecular
system Dicyanorhodanine + 2-formyltetratiafulvalene and the solvent Methanol (enviromente), including changes in the temperature. Here, both in the weak and
strong coupling regime, we found that coherent oscillations are maintained for longer times than in the case of populations even at room temperature. The current
analisis increeses the few physical systems reported in literature in which this behavior is observed.

Molecular System Hierarchy Equation of Motion Results

We consider a study of dicyanorhodanine + 2- The time evolution operator of the time deriva- Electron Transfer Rate
formyltetratiafulvalene (Fig.1) a new push-pull tive of the averaged bath allows the introduction of The electron transfer rate kXT →CT is given by the
chromophores derive of the rhodanine, the complex auxiliary density matrices that considert the non- expression [5]:
consist of 2-formyltetratiafulvalene (TTF) as donor Markovian behavior of the system [3,4] ṖA − ṖD
and dicyanorhodanine (DR) linked by a propylene kXT →CT = (7)
2PD
small bridge, exhibiting interesting photo- and elec- N X M 40
trochemical properties [1]. db
ρn i b 0.2
h i X
= − HS , ρbn − nm νm,i ρb (5) 30
dt ~ m=1 i=0
20 0.1
N
XX M   XN X M
(6)

ET(ps-1)
−i |ϕn ihϕn |, ρbn+ − nm,i 10
0
m,i 1.5 2 2.5
m=1 i=0 m=1 i=0 0
 
|mihm|c∗j,k
-10
cj,k |mihm|b
ρn− + ρbn− η=0.01
m,i m,i η=0.02
-20
η=0.04
η=0.10
Where νaκ is the infinite number of Matsubara -30
0 0.5 1 1.5 2 2.5
terms, cak are the coefficients of the correlation func- t (ps)

Figure 1. Molecular structure of chromophore used tion. Figure 3. Electron transfer rate for different
for the study, this is the synthesis of dicyanorhoda- system-bath couplings as a function of time.
nine + 2-formyltetratiafulvalene
50000
Results
40000
Effects of system-bath coupling and temperature.
Strong Coupling Regime
Absortion

30000

1 0.5 0.5
20000 η=0.10 T=50K
η=0.20 T=100K
0.8 0.4 η=0.30 0.4 T=200K
10000 η=0.40 T=300K
Populations

Coherence

Coherence

0.6 η=0.10 0.3 0.3

0 η=0.20
200 400 600 800 1000 η=0.30
Wavelenght (nm) 0.4 η=0.40 0.2 0.2
Figure 2. Absorption spectrum of the study system
0.2 0.1 0.1

0 0 0
Hamiltonian of the Molecular System 0 0.05 0.1 0.15 0.2 0 0.05 0.1 0.15 0.2 0 0.05 0.1 0.15 0.2
The total Hamiltonian of the XT to CT transfer in t (ps) t (ps) t (ps)
the complex molecular is given by [2]: Figure 4. Time evolution of the density matrix elements for different system-bath coupling. With the
parameters set as ED = −4323.13 cm−1 , EA = −5290.99 cm−1 , γa = 10 ps−1 , T = 300 K. In the figures
H
b =H
bS + H
bB + H
b SB (1) (a), (b) Dynamics for strong coupling regime and (c) Dynamic different temperatures with η = 0.2.
which consists of a two-level system coupled to a Weak Coupling Regime
bath of harmonic oscillators, 1 0.5 0.5
η=0.005 T=050K
T=100K
X1 2 η=0.010 T=200K
2 2
(2)


H
bB = pbj + ωj x
bj 0.8 0.4 η=0.020 0.4 T=300K
2 η=0.040
Populations

Coherence

j
Coherence

0.6 η=0.005 0.3 0.3

where pbj and x
bj are the momenta and position of the η=0.010
η=0.020
jth bath harmonic oscillator with frequency ωj . The 0.4 η=0.040 0.2 0.2

two-level system part consists of the charge transfer 0.2 0.1 0.1
state and the exciton state, and is given by
0 0 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0 0.1 0.2 0.3 0.4 0.5 0.6 0 0.2 0.4 0.6 0.8 1
b S = −∆|1ih1| + V (|2ih1| + |1ih2|)
H (3) t (ps) t (ps) t (ps)

The system-bath coupling is given by Figure 5. Time evolution of the density matrix elements for different system-bath coupling. With the
X parameters set as ED = −4323.13 cm , EA = −5290.99 cm , γa = 10 ps , T = 300 K. In the figures
−1 −1 −1
Hb SB = |1ih1| cj x
bj (4)
(a), (b) Dynamics for weak coupling regime and (c) Dynamic different temperatures with η = 0.02.
j

References
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Conclusion
• In each regime, the quantum coherences persists during a longer time than the populations at both
room and low temperature in the picosecond time scale.
• Due to the electronic dissipation can be associated to the coupling of the system to a bath of nuclear
modes, as bonds to a surface. It is possible to suggest that the system-bath coupling plays an important
role in the control of the electronic transport within molecules.
• For weak η values, the electron transfer rates show an oscillation characteristic, due to the transitional
interference between the discrete energy states at different potentials.