Motivation and Applications

Molecular System
Model
Results
Conclusions

Room Temperature Quantum Coherence vs. Electron Transfer

in a Rhodanine Derivative Chromophore

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina

DOI: 10.1039/c9cp01398a

Tecnologı́a, Información y Complejidad Cuántica–QuanTIC

Universidad del Valle

2019.

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Content

1 Motivation and Applications

2 Molecular System

3 Model

4 Results

5 Conclusions

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Why Organic Molecules?

Organic molecules are important because whole life is composed by carbon.

Photosynthesis, basis of all life on earth Organic solar cells, sustainable energy conversion

Savoie, Ratner et al., Chem. Res. 47, 3385 (2014).

Bioluminescent resonance energy transfer

Biosensor developed by the lab of Professor Kai Johnsson and the startup
Hu et al., Quart. Rev. Biophys. 35 (2002). LUCENTIX.

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Electron Transfer Process

It shows a particular type of spatial distribution of charge It presents tunneling across the barrier or
resonant jump of electron

Y. Omar, G. Engel, M. Plenio, Quantun effect In

Biology, Cambridge University Press (2014)
Y. Omar, G. Engel, M. Plenio, Quantun effect In Biology, Cambridge
University Press (2014)
ET reaction of an excess electron

V. May, O. Kühn, Charge and Energy Transfer

Dynamic in Molecular System (2011)

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Molecular System

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Molecular System

Figure 1: Molecular structure of the chromophore used for the study: Dicyanorodamine+2-
formyltetrathiafulvalene

Courtesy of: Prof. Alejandro Ortiz, Heterocyclic Compounds Research Group-GICH (CIBioFi)

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Molecular System

We can describe the solvation process using the well-known Onsager model. This is a type of
continuum model where the solvent is treated as a homogeneous dielectric.

Figure 2: Onsager model of solvation.

J. Gilmore and R. H. McKenzie, J.Phys.: Cond. Matt. 17, 1735, (2005).

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Molecular System

Figure 3: Absorption spectrum for the molecular system in study

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Transition state π → π ∗ and CT state

Figure 4: Molecular orbitals and charge transfer (CT) states

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Approach to a two-level system

Figure 5: Energy representation of the π −π ∗ and CT states of interest in the D2F complex.  = |ED −EA | is
the energy difference between the EX and CT states, and VDA stands for the D– electronic coupling. Methanol:
ED = −4323cm−1 , EA = 5291cm−1 , VDA = 280cm−1 ; Toluene: ED = −5201cm−1 , EA = −5838cm−1 ,
VDA = 317cm−1 .

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Model

In an environment
Fluctuation
Dissipation

H = Hs + HB + HI (1)
Heat bath model H

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Model

We will calculate the dynamics of a quantum system coupled to a bath with a complete Hamilto-
nian given by:

Hamiltonian of the system

p2j
X b 
X 1
H bs +
b= H gn,j Q xj
b nb + + mj ωj2b
xj2
n,j j
2mj 2

Interaction

Here, j indexes the bath modes, which have coordinates b b n = |ϕn ihϕn | denotes a operator
xj . Q
on the Hilbert space of the system, which couples to the bath modes with strengths gn,j .

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Model

We will calculate the dynamics of a quantum system coupled to a bath with a complete Hamilto-
nian given by:

Hamiltonian of the system

p2j
X b 
X 1
H bs +
b= H gn,j Q xj
b nb + + mj ωj2b
xj2
n,j j
2mj 2

Interaction
Bath

Here, j indexes the bath modes, which have coordinates b b n = |ϕn ihϕn | denotes a operator
xj . Q
on the Hilbert space of the system, which couples to the bath modes with strengths gn,j .

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Model

We will calculate the dynamics of a quantum system coupled to a bath with a complete Hamilto-
nian given by:

Hamiltonian of the system

p2j
X b 
X 1
H bs +
b= H gn,j Q xj
b nb + + mj ωj2b
xj2
n,j j
2mj 2

Interaction
Bath

Here, j indexes the bath modes, which have coordinates b b n = |ϕn ihϕn | denotes a operator
xj . Q
on the Hilbert space of the system, which couples to the bath modes with strengths gn,j .

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Model

The Hamiltonian of the system for N electronic sites is given by:

N
X N
X
bS =
H En |ϕn ihϕn | + Vnm |ϕn ihϕm | (2)
n=1 n6=m=1

Figure 6: Molecular orbitals and charge transfer (CT) states

R. Volkovich and U.P., J. Chem. Phys. (2006).

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Model

In approaching a two level system, the Hamiltonian system can be written as:

2 2 p2j
X b 
X X X 1
b=
H En |ϕn ihϕn | + Vnm |ϕn ihϕm | + xj σ
gjb bz + + mj ωj2b
xj2 . (3)
n=1 n6=m=1 j j
2mj 2

2 2
a†j )b a†j b
X X X X
b=
H En |ϕn ihϕn | + Vnm |ϕn ihϕm | + Cj (b
aj + b σz + ωjb aj . (4)
n=1 n6=m=1 j j

Where E1(2) , and V12 = V21 = V are the energy of donor, acceptor part and electronic coupling
between the two site, the system is coupled with the bath by means of a strength Cj .

J. Strümpfer and K. Schulten, J. Chem. Theory Comput., 8, 2808-2816, (2012)

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Correlation Functions

The effect of the environment on the dynamics of the subsystem of interest can be completely
encapsulated in the called spectral density function J(ω) in the defined as:

Nω
πX
J(ω) = g2 (ω)δ(ω − ωj ), (5)
2 j j

here, δ(ω − ωj ) is the Dirac δ-function, and so J(ω) is effectively the density of states of the
environment, but weighted by the couplings g2j .

U. Weiss, Quantum dissipative systems, 13, World scientific, (2012).

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Correlation Functions
Spectral density function

For the case of a molecular system within a solvent, we can use the spectral density as defined
by Gilmore:

2αωωc2 2λωc ω
J(ω) = = 2 (6)
ω 2 + ωc2 ω + ωc2
with

6(∆µ)2 (s − ∞ )
α= τs (7)
4π0 a30 (2s + 1)(2∞)
1
where τs = is Relaxation time, ∞ is High frequency dielectric constant, s state dielectric
ωc
constant, ∆µ, Difference of dipole moment

J. Gilmore and R. H. McKenzie, J.Phys.: Cond. Matt. 17, 1735, (2005).

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Correlation Functions
Z
2 J(ω)
The reorganization energy associated with each part of the environment is given by λ = dω
π ω
therefore:

(∆µ)2 6(s − ∞ )
λ= (8)
4π0 a30 (2s + 1)(2∞ + 1)

In the case of Ohmic dissipation, we can define a dimensionless coupling:

α λ
η= = (9)
2π~ 2π~ωc
So we have to:

2λωc ω
J(ω) = (10)
ωc2 + ω 2

Hsu, C.-P.; You, Z.-Q.; Chen, H.-C. J. Phys. Chem. C, 112,v1204–1212 (2008).

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Correlation Functions

The bath correlation functions C(t) determines how the environment fluctuations affect the sys-
tem through the couplings Qb n = |ϕn ihϕn |
 
exp(−βHB )
Cab (t) = hu(t)u(0)iB = TrB u(t)u(0) (11)
TrB {exp(−βHB )}

The correlation functions are usually specified through the Fourier-Laplace transform of the spec-
tral density J(ω) as:

1 ∞
Z    
β~ω
C(t) = J(ω) coth cos ωt − i sin ωt dt (12)
π 0 2
with
i
Z ∞
CI (t) = dωJ(ω) sin(ωt) (13)
π 0

1
Z ∞ 
β~ω

CR (t) = dωJ(ω) coth cos(ωt) (14)
π 0 2

Tanimura, Y.; Kubo, R. J. Phys. Soc. Jpn, 58, 1199–1206 (1989).

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Correlation Functions
β~ω
Expanding in Fourier series coth( ) and using the Eq. 10 we have
2
   ∞ 
β~ω 2 1 X 2ω
coth = + . (15)
2 β~ ω k=1
ω 2 + νk2
We have to CI (t) and CR (t), it can be written as:

CI (t) = iλωc e−ω|t| , (16)

  ∞  
β~ωc −ωc |t| X 4λωc νk
CR (t) = λωc cot e + e−ωc |t| (17)
2 k=1
β~ νk2 + ωc2
Therefore,   ∞  
β~ωc −ωc |t| X 4λωc νk
C(t) = iλωc e−ωc |t| + λωc cot e + 2 + ω2
e−ωc |t| (18)
2 k=1
β~ νk c

The correlation function associated with the Drude spectral density is:
∞
X
C(t) = Ck e−νk t (19)
k=0

Caldeira, A.; Leggett, A. J. Annals of physics, 149, 374–456 (1983).

Ishizaki, A.; Tanimura, Y. J. Phys. Soc. Jpn, 74, 3131–3134 (2005).
Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Correlation Functions
The huge computational expense of such arbitrary correlation functions (especially with large
M and K) restricts us to forms with Cab (t) = δab Ca (t) and Ωabk = 0
∞
X
C(t) = Ck e−νk t (20)
k=0
2πk

where ν0 = ωc and νk = k ≥1 are the Matsubara frequencies.
β~

While coefficients, C0 and Ck ≥ 1 are given by

 λω   β~ω  
c c

 cot −i , for k = 0;
 ~

 2
Ck = " #
 4λωc

 νk
, for k ≥ 0.

νk2 − ωc2

β~

Caldeira, A.; Leggett, A. J. Annals of physics, 149, 374–456 (1983).

Ishizaki, A.; Tanimura, Y. J. Phys. Soc. Jpn, 74, 3131–3134 (2005).
Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Hierarchy equations of motion

Dissipative Dynamics
The exponential terms in Eq. 14 lead to a hierarchy of matrices ρn , called auxiliary density
matrices (ADMs), to take into account the non-Markovian evolution of ρ(t). The hierarchy
equations of motion are:

N X K N X K  
ρn
db i hb i X X
= − HS , ρbn − nnk νnk ρbn − i |ϕn ihϕn |, ρbn+
dt ~ n=1 k=0 n=1 k=0
nk

N K
!
X 2λj X cnk   
− 2ω
− |ϕn ihϕn |, |ϕn ihϕn |, ρbn
n=1
β~ c ν
k=0 nk
N X
X K  
− nnk ρn− + ρbn− |ϕn ihϕn |c∗nk
cnk |ϕn ihϕn |b (21)
nk nk
n=1 k=0

Y. Tanimura and R. Kubo, J. Phys. Soc. Jpn. 58, 1199 (1989)

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Results

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Effects of the Oscillator-Bath Coupling Strenght

Weak coupling regime:

Figure 7: Population inversion hσz (t)i (panels (a) and (c)) and real-part coherence <(ρDA ) (panels (b) and
(d)) dynamics as a function of the chromophore-solvent coupling at T = 300 K. Subscripts M and T stand for
methanol and toluene (top and bottom plots). In each figure, turquoise, violet, and black curves correspond to
η = 0.005, η = 0.010, η = 0.025, respectively. Hereafter, populations are considered to be localised on the
donor at t = 0, i.e., hσz (0)i = 1.

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Effects of the Oscillator-Bath Coupling Strenght

Strong Coupling Regime:

Figure 8: Strong coupling regime. Population inversion hσz (t)i (panels (a) and (c)) and real-part coherence
<(ρD A) (panels (b) and (d)) dynamics as functions of the chromophore-solvent coupling at T = 300 K.
Methanol (top) and toluene (bottom), for η = 0.10 (turquoise), η = 0.25 (violet), and η = 0.33 (black)
curves.
Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Effects of the Temperature

Figure 9: Temperature dependence of D2F–solvent dynamics. Population inversion hσz (t)i ((a) and (c)) and
real-part coherence <(ρDA (t)) ((b) and (d)) dynamics as functions of temperature, for methanol (ηM = 0.25)
and toluene (ηT = 0.33). In each panel, turquoise, violet, orange and black curves correspond to T = 10 K,
T = 50 K, T = 100 K and T = 300 K, respectively.

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Electron Transfer Rate

It is possible to relate the ET speed with the time-dependent density matrix elements. In general,
for an N − 2-bridge system, the charge transfer from site m to site n can be described by,

dρD
= −kD2 ρD + k2D ρ2 (22)
dt
..
.
dρN−1
= kN−2N−1 ρN−2 + kAN−1 ρA
dt
−(kN−1N−2 + kN−1A )ρN−1
dρA
= kN−1A ρN−1 − kAN−1 ρA .
dt
In our N = 2-site model, this set reduces to:
dρD
= −kDA ρD + kAD ρA , (23)
dt
Assuming kAD = 0 for the sake of simplicity, according to the D2F chromophore site energies,
the ET rate can be written as:
1 dρD (t)
kDA = − (24)
ρD (t) dt
J. Blumberger, Chem. Rev., 2015, 115, 11191–11238.
Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Electron Transfer Rate

Figure 10: Electron transfer rates as functions of the D2F-solvent coupling strength. Methanol, T = 300 K
(a), T = 50 K (b), and toluene, T = 300 K (c), T = 50 K (d). Turquoise, violet, black, orange and green
curves correspond to η = 0.08, η = 0.25, η = 0.45, η = 0.50 and η = 0.60, respectively.

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Conclusions

we have computed the effects due to the chromophore environment by considering polar
(methanol) and non polar (toluene) solvents, under different temperature conditions. The D2F
chemical structure (and the identification of suitable excited and charge transfer states) allowed
us to evaluate, within the Onsager model of solvation, the complex-solvent coupling strengths η,
which clearly set the dynamics within the strong coupling regime.

Our simulations show that, at room temperature, the steady value of κDA increases with the
coupling strength η, and reaches values almost two orders of magnitude higher in methanol
than in toluene. Furthermore, although prolonged coherence oscillations are observed at lower
temperatures, the ET rate optimises at room temperature for both solvents as it reaches higher
steady values

Finally, we conclude that the non polar solvent enhances the quantum properties of the organic
chromophore dynamics when compared to the polar solvent; yet, and perhaps counterintuitive, it
is the latter that exhibits the higher ET rates.

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De
 Motivation and Applications
Molecular System
Model
Results
Conclusions

Duvalier Madrid-Úsuga; Cristian E. Susa; and John H. Reina Room Temperature Quantum Coherence vs. Electron Transfer in a Rhodanine De