This work was supported at part of the Center for Excitonics, an Energy Frontier Research Center
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Presentation on theme: "This work was supported at part of the Center for Excitonics, an Energy Frontier Research Center"— Presentation transcript:
Slide1
This work was supported at part of the Center for Excitonics, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (BES) under award number: DE-SC0001088
Zhou Lin, Hikari Iwasaki and Troy A. Van VoorhisDepartment of Chemistry, Massachusetts Institute of Technology06/21/2017
Photochemical
Dynamics
for
Intramolecular Singlet Fission I
–
Energy Levels
and
Non-Adiabatic Couplings
Slide2
Singlet fission (SF) converts one singlet into two triplets.[1]1[1] Smith and Michl, Chem. Rev. 110
, 6891 (2010).
Slide3
Singlet fission (SF) converts one singlet into two triplets.[1]2
S
0
S
0
[1] Smith and
Michl
,
Chem. Rev.
110
, 6891 (2010).
S
0
T
1
S
1
Slide4
Singlet fission (SF) converts one singlet into two triplets.[1]incident photon3
S
0
S
0
S
1
S
0
[1] Smith and
Michl
,
Chem. Rev.
110
, 6891 (2010).
S
0
T
1
S
1
S
0
T
1
S
1
Slide5
Singlet fission (SF) converts one singlet into two triplets.[1]incident photon4
S
0
S
0
S
1
S
0
T
1
T
1
[1] Smith and
Michl
,
Chem. Rev.
110
, 6891 (2010).
S
0
T
1
S
1
S
0
T
1
S
1
S
0
T
1
S
1
singlet
fission
Slide6
Singlet fission (SF) converts one singlet into two triplets.[1]incident photon5
S
0
S
0
S
1
S
0
T
1
T
1
[1] Smith and
Michl
,
Chem. Rev.
110
, 6891 (2010).
S
0
T
1
S
1
S
0
T
1
S
1
S
0
T
1
S
1
singlet
fission
Slide7
[2] Tabachnyk, Musser, and Rao, SPIE Nanotechnology, “Beyond the Shockley-Queisser limit with singlet exciton fission.”Singlet fission promotes efficiency of photovoltaics.[2]
6
Slide8
[2] Tabachnyk, Musser, and Rao, SPIE Nanotechnology, “Beyond the Shockley-Queisser limit with singlet exciton fission.”Singlet fission promotes efficiency of photovoltaics.[2]
7direct relaxation to band edge
relaxation
S
1
S
1
'
Slide9
[2] Tabachnyk, Musser, and Rao, SPIE Nanotechnology, “Beyond the Shockley-Queisser limit with singlet exciton fission.”Singlet fission promotes efficiency of photovoltaics.[2]
relaxation
singlet fission
relaxation
8
direct relaxation
to band edge
singlet fission
before relaxation
S
1
S
1
T
1
T
1
T
1
'T
1
'
S
1
'
Slide10
S0T1S1Singlet
fission has two possible mechanisms.[3]9
S
1
S
0
S
0
T
1
S
1
T
1
T
1
[3]
Berkelbach
,
Hybertsen
, and
Reichman
,
J. Chem. Phys.
,
138
, 114103 (2013).
?
Slide11
S0T1S1Singlet
fission has two possible mechanisms.[3]10
S
1
S
0
S
0
T
1
S
1
T
1
T
1
[3]
Berkelbach
,
Hybertsen
, and
Reichman
,
J. Chem. Phys.
,
138
, 114103 (2013).
direct
Slide12
S0T1S1
S0T1S1Singlet fission has two possible mechanisms.[3]11
36We ordered energies and non-adiabatic couplings.
E
(eV)
0.0
1.0
2.0
3.0
0.5
1.5
2.5
3.5
1
(S
1
S
0
)
1
(S
0
S
1
)
1
(S
0
S
0
)
1
(S
0
S
0
)
1
(S
0
S
0
)
1
(
S
1
S
0
+S
0
S
1
)
1
(
S
1
S
0
–
S
0
S
1
)
1
(
S
1
S
0
+S
0
S
1
)
1
(C
+
A
–
)
1
(C
+
A
–
)
1
(C
+
A
–
)
1
(A
–
C
+
)
1
(A
–
C
+
)
1
(A
–
C
+
)
1
(
S
1
S
0
–
S
0
S
1
)
o
−2
m
−2
p
−2
:
m
−2
p
−2
o
−
2
[5]
:
o
−2
m
−2
p
−2
:
m
−2
p
−2
o
−2
Charge-transfer-mediated
mechanism
–
first
step
S
1
S
0
C
+
A
–
[4]
Zirzlmeier
,
Lehnherr
,
Coto
,
Chernick
, Casillas, Basel,
Thoss
,
Tykwinski
, and
Guldi
,
Proc. Natl. Acad. Sci. U.S.A.
112
, 5325 (2015).
Slide38
37We ordered energies and non-adiabatic couplings.
E
(eV)
0.0
1.0
2.0
3.0
0.5
1.5
2.5
3.5
1
(S
1
S
0
)
1
(S
0
S
1
)
1
(S
0
S
0
)
1
(S
0
S
0
)
1
(S
0
S
0
)
1
(
S
1
S
0
+S
0
S
1
)
1
(
S
1
S
0
–
S
0
S
1
)
1
(
S
1
S
0
+S
0
S
1
)
1
(C
+
A
–
)
1
(C
+
A
–
)
1
(C
+
A
–
)
1
(A
–
C
+
)
1
(A
–
C
+
)
1
(A
–
C
+
)
1
(
S
1
S
0
–
S
0
S
1
)
o
−2
m
−2
p
−2
:
m
−2
p
−2
o
−
2
[5]
:
o
−2
m
−2
p
−2
:
m
−2
p
−2
o
−2
Charge-transfer-mediated
mechanism
is
probably
more
important!
[4]
Zirzlmeier
,
Lehnherr
,
Coto
,
Chernick
, Casillas, Basel,
Thoss
,
Tykwinski
, and
Guldi
,
Proc. Natl. Acad. Sci. U.S.A.
112
, 5325 (2015).
Slide39
38We ordered energies and non-adiabatic couplings.
E
(eV)
0.0
1.0
2.0
3.0
0.5
1.5
2.5
3.5
1
(T
1
T
1
)
1
(S
0
S
0
)
1
(S
0
S
0
)
1
(S
0
S
0
)
1
(T
1
T
1
)
1
(T
1
T
1
)
1
(C
+
A
–
)
1
(C
+
A
–
)
1
(C
+
A
–
)
1
(A
–
C
+
)
1
(A
–
C
+
)
1
(A
–
C
+
)
o
−2
m
−2
p
−2
:
m
−2
p
−2
o
−
2
[5]
:
o
−2
p
−2
m
−2
:
m
−2
o
−2
p
−2
Charge-transfer-mediated
mechanism
–
second
step
C
+
A
–
T
1
T
1
[4]
Zirzlmeier
,
Lehnherr
,
Coto
,
Chernick
, Casillas, Basel,
Thoss
,
Tykwinski
, and
Guldi
,
Proc. Natl. Acad. Sci. U.S.A.
112
, 5325 (2015).
Slide40
39We ordered energies and non-adiabatic couplings.
E
(eV)
0.0
1.0
2.0
3.0
0.5
1.5
2.5
3.5
1
(T
1
T
1
)
1
(S
0
S
0
)
1
(S
0
S
0
)
1
(S
0
S
0
)
1
(T
1
T
1
)
1
(T
1
T
1
)
1
(C
+
A
–
)
1
(C
+
A
–
)
1
(C
+
A
–
)
1
(A
–
C
+
)
1
(A
–
C
+
)
1
(A
–
C
+
)
o
−2
m
−2
p
−2
:
m
−2
p
−2
o
−
2
[5]
:
o
−2
p
−2
m
−2
:
m
−2
o
−2
p
−2
Charge-transfer-mediated
mechanism
is
probably
more
important!
[4]
Zirzlmeier
,
Lehnherr
,
Coto
,
Chernick
, Casillas, Basel,
Thoss
,
Tykwinski
, and
Guldi
,
Proc. Natl. Acad. Sci. U.S.A.
112
, 5325 (2015).
Slide41
40We ordered energies and non-adiabatic couplings.
E
(eV)
0.0
1.0
2.0
3.0
0.5
1.5
2.5
3.5
1
(S
1
S
0
)
1
(S
0
S
1
)
1
(T
1
T
1
)
1
(S
0
S
0
)
1
(S
0
S
0
)
1
(S
0
S
0
)
1
(T
1
T
1
)
1
(
S
1
S
0
+S
0
S
1
)
1
(
S
1
S
0
–
S
0
S
1
)
1
(
S
1
S
0
+S
0
S
1
)
1
(T
1
T
1
)
1
(
S
1
S
0
–
S
0
S
1
)
o
−2
m
−2
p
−2
:
m
−2
p
−2
o
−
2
[5]
:
p
−2
m
−2
o
−2
:
m
−2
p
−2
o
−2
Direct
mechanism
–
S
1
S
0
T
1
T
1
[4]
Zirzlmeier
,
Lehnherr
,
Coto
,
Chernick
, Casillas, Basel,
Thoss
,
Tykwinski
, and
Guldi
,
Proc. Natl. Acad. Sci. U.S.A.
112
, 5325 (2015).
Slide42
41We ordered energies and non-adiabatic couplings.
E
(eV)
0.0
1.0
2.0
3.0
0.5
1.5
2.5
3.5
1
(S
1
S
0
)
1
(S
0
S
1
)
1
(T
1
T
1
)
1
(S
0
S
0
)
1
(S
0
S
0
)
1
(S
0
S
0
)
1
(T
1
T
1
)
1
(
S
1
S
0
+S
0
S
1
)
1
(
S
1
S
0
–
S
0
S
1
)
1
(
S
1
S
0
+S
0
S
1
)
1
(T
1
T
1
)
1
(
S
1
S
0
–
S
0
S
1
)
o
−2
m
−2
p
−2
:
m
−2
p
−2
o
−2
[5]
:
p
−2
m
−2
o
−2
:
m
−2
p
−2
o
−2
Direct
mechanism
might
work
for
p
−
2
!
[4]
Zirzlmeier
,
Lehnherr
,
Coto
,
Chernick
, Casillas, Basel,
Thoss
,
Tykwinski
, and
Guldi
,
Proc. Natl. Acad. Sci. U.S.A.
112
, 5325 (2015).
Slide43
We evaluated the energies for relevant states and non-adiabatic couplings between them.42What can
we conclude from the study?[6] Tomasi, Mennucci and Cammi,
Chem.
Rev.
105, 2999 (2005).
[7]
Warshel
and
Levitt,
J.
Mole.
Bio.
103
,
227
(1976).
[8]
Car and
Parrinello
,
Phys.
Rev.
Lett.
55
,
2471
(1985).
[9]
Vaissier
and
Van Voorhis,
J. Chem. Theory Comput
.
12
,
5111
(2016).
[10]
Mavros
,
Hait
and
Van
Voorhis,
J.
Chem.
Phys.
145
,
214105
(2016).
Slide44
We evaluated the energies for relevant states and non-adiabatic couplings between them.Our results support the trend that : m
−2 p−2 o−2. 43What can we conclude
from
the
study?
[6
]
Tomasi
,
Mennucci
and
Cammi
,
Chem.
Rev.
105
, 2999 (2005).
[7]
Warshel
and
Levitt,
J.
Mole.
Bio.
103
,
227
(1976).
[8]
Car and
Parrinello
,
Phys.
Rev.
Lett.
55
,
2471
(1985).
[9]
Vaissier
and
Van Voorhis,
J. Chem. Theory Comput
.
12
,
5111
(2016).
[10]
Mavros
,
Hait
and
Van
Voorhis,
J.
Chem.
Phys.
145
,
214105
(2016).
Slide45
We will obtain more quantitative results for energy
gaps and non-adiabatic couplings.44What should we do next?[6] Tomasi,
Mennucci
and
Cammi,
Chem.
Rev.
105, 2999 (2005).
[7]
Warshel
and
Levitt,
J.
Mole.
Bio.
103
,
227
(1976).
[8]
Car and
Parrinello
,
Phys.
Rev.
Lett.
55
,
2471
(1985).
[9]
Vaissier
and
Van Voorhis,
J. Chem. Theory Comput
.
12
,
5111
(2016).
[10]
Mavros
,
Hait
and
Van
Voorhis,
J.
Chem.
Phys.
145
,
214105
(2016).
Slide46
We will obtain more quantitative results for energy
gaps and non-adiabatic couplings.We will study the solvation effects, using both the polarizable continuum model (PCM)[6] and the quantum mechanical/molecular mechanical (QM/MM)[7] model.45What
should we do next?
[6
]
Tomasi
,
Mennucci
and
Cammi
,
Chem.
Rev.
105
, 2999 (2005).
[7]
Warshel
and
Levitt,
J.
Mole.
Bio.
103
,
227
(1976).
[8]
Car and
Parrinello
,
Phys.
Rev.
Lett.
55
,
2471
(1985).
[9]
Vaissier
and
Van Voorhis,
J. Chem. Theory Comput
.
12
,
5111
(2016).
[10]
Mavros
,
Hait
and
Van
Voorhis,
J.
Chem.
Phys.
145
,
214105
(2016).
Slide47
We will obtain more quantitative results for energy gaps
and non-adiabatic couplings.We will study the solvation effects, using both the polarizable continuum model (PCM)[6] and the quantum mechanical/molecular mechanical (QM/MM)[7] model.We will perform ab initio molecular dynamics
(AIMD)[
8]
or QM/MM dynamics
[9]
for geometries and spectral densities.
46
What
should we do next?
[6
]
Tomasi
,
Mennucci
and
Cammi
,
Chem.
Rev.
105
, 2999 (2005).
[7]
Warshel
and
Levitt,
J.
Mole.
Bio.
103
,
227
(1976).
[8]
Car and
Parrinello
,
Phys.
Rev.
Lett.
55
,
2471
(1985).
[9]
Vaissier
and
Van Voorhis,
J. Chem. Theory Comput
.
12
,
5111
(2016).
[10]
Mavros
,
Hait
and
Van
Voorhis,
J.
Chem.
Phys.
145
,
214105
(2016).
Slide48
We will obtain more quantitative results for energy gaps
and non-adiabatic couplings.We will study the solvation effects, using both the polarizable continuum model (PCM)[6] and the quantum mechanical/molecular mechanical (QM/MM)[7] model.We will perform ab initio molecular dynamics (AIMD
)[8] or QM/MM
dynamics
[9]
for geometries and spectral densities.
We will evaluate Condon/non-Condon dynamics using
spin
−
boson Hamiltonian.
[10]
47
What
should we do next?
[6
]
Tomasi
,
Mennucci
and
Cammi
,
Chem.
Rev.
105
, 2999 (2005).
[7]
Warshel
and
Levitt,
J.
Mole.
Bio.
103
,
227
(1976).
[8]
Car and
Parrinello
,
Phys.
Rev.
Lett.
55
,
2471
(1985).
[9]
Vaissier
and
Van Voorhis,
J. Chem. Theory Comput
.
12
,
5111
(2016).
[10]
Mavros
,
Hait
and
Van
Voorhis,
J.
Chem.
Phys.
145
,
214105
(2016).
Slide49
48AcknowledgementPrincipal Investigator: Troy Van VoorhisPostdoctoral associates: James Shepherd,
Piotr de Silva, Tamar Goldzak.Graduate students: Nadav Geva, Alexander Kohn, Nathan Ricke, Tianyu Zhu, Hongzhou Ye, Lexie McIsaac.
