new paradigms in the photophysics of hydrogen- … › on-2 › on21 › tum_2017.pdf · paradigm...
TRANSCRIPT
![Page 1: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/1.jpg)
Andrzej L. Sobolewski Institute of Physics, Polish Academy of Sciences Warsaw, Poland
Kolloquium für Physikalische und Theoretische Chemie, 3.04.2017, Garching
NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN-BONDED MOLECULAR SYSTEMS
![Page 2: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/2.jpg)
VIS
em
issio
n V
IS a
bso
rptio
n
„Old” photophysical scheme of HB system
PT
VIS
em
issio
n
S0
PT coordinate X-H...Y X…H-Y
UV
abso
rption
S1 PT
(Excited-State Intramolecular Proton Transfer - ESIPT)
![Page 3: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/3.jpg)
Sobolewski & Domcke, Chem. Phys. 184 (1994) 115
CASSCF CASPT2
S0
1nπ
1ππ*
S0
1nπ
1ππ*
PT
Photophysical scheme of o-benzaldehyde
![Page 4: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/4.jpg)
En
erg
y
“keto”
“enol”
S0
S1
UV
ab
so
rptio
n
VIS
em
issio
n
VIS
ab
so
rptio
n
O
O
OH
O
OH
O
PT coordinate
Photophysical scheme of ESIntraPT
Inte
rnal c
onvers
ion
coordinate(?)
CI
PT
PT
<1ps
![Page 5: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/5.jpg)
UV light
VIS light or heat
Photophysics of azobenzene
UV VIS
S0
S1
![Page 6: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/6.jpg)
NH
N
N
NH
Sobolewski & Domcke, J. Phys. Chem. A 111 (2007) 11725
Photophysics of 7-(2’-pyridyl)indole
CI
CC2
![Page 7: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/7.jpg)
Photophysics of 7-(2’-pyridyl)indole
τ= 280 fs in jet
τ =1.0 ps in ACN
Waluk et al., Angew.Chem.Int.Ed., 47 (2008) 603
Kochman & Morrison, J. Chem. Theory Comput., 9 (2013) 1182
θ
PT(50fs)
PT+twist(200fs)
![Page 8: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/8.jpg)
Y H
X
Y
H X
Y H
X X
Y H
PD
PA
S0
S0’
S1 S1’
CI
hn
PT Twist
Photophysics of ESIPT process
Sobolewski, Domcke, Hättig, J. Phys. Chem. A 110 (2006) 6301
![Page 9: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/9.jpg)
Paradigm I:
Twisting around double bond associated
with ESIPT process provides a path for
fast radiationless decay of electronic
excitation in intra-HB molecules
J. Phys. Chem. A 111 (2007) 11725 J. Phys. Chem. A 110 (2006) 6301
![Page 10: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/10.jpg)
Y H
X
Y
H X
Y H
X X
Y H
PD
PA
S0
S0’
S1 S1’
CI
l1
l2
PT Twist
Application of the ESIPT process
Z
S0’
![Page 11: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/11.jpg)
PDA
PA Y
H X Z
Y H
X Z X
Y H
Z
Y
H Z X
Y H
X Z
PT PT Twist
S0
S0’
S1 S1’
CI
l1 l2
Molecular switch based on ESIPT phenomenon
A. L. Sobolewski
Reversible molecular switch driven by excited-state hydrogen transfer
PCCP 10 (2008) 1243
ESIPT
![Page 12: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/12.jpg)
Photophysics of 7-hydroxy-(8-oxazine-2-one)-quinoline
PCCP, 10 (2008) 1243
CI
carbon
nitrogen
oxygen
hydrogen
CC2
![Page 13: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/13.jpg)
Photophysics of a molecular switch
S0
S1 S1
„gre
en
” p
ho
ton
„blu
e”
photo
n
OH NH CO
IR IR
„enol” „keto”
![Page 14: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/14.jpg)
0.0
0.4
0.8
1400 1200 1000 800
0.08
0.04
0.00
-0.01
0.00
0.01 a
bsorb
ance
b
c
wavenumbers /cm-1
a
NO
H
CH3
HO
NO
CH3
OHH
Lapinski et al., ChemPhysChem., 10 (2009) 2290
Photophysics of 7-hydroxy-4-methylquinone-8-carbaldehyde
IR spectrum
before irradiation
IR spectrum
after irradiation
l295nm
IR difference
Spectrum
after irradiation
l360nm
l ≤ 295 nm
l ≤ 360 nm
![Page 15: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/15.jpg)
Paradigm II:
Molecular photoswitches or transistors
based on the ESIntraPT phenomenon:
- photostable
- chemically tunable
- fast
hn1 hn1
hn1
hn1
J. Phys. Chem. C, 113 (2009) 10315 J. Mol. Model. 20 (2014) 2163
PCCP, 10 (2008) 1243
![Page 16: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/16.jpg)
X,Y=N,O
X-H...Y
Intra-molecular hydrogen bonds
![Page 17: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/17.jpg)
Inter-molecular hydrogen bonds
X,Y=N,O
X-H...Y
![Page 18: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/18.jpg)
Photophysics of an acidic chromophore
X,Y=N,O
X-H
![Page 19: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/19.jpg)
abs
carbon
nitrogen
oxygen
hydrogen
A”
A’
Sobolewski, et al., 1999-2005
p
p*
s*
πσ* paradigm of photoacids
NH
H diss abs
50fs
IC (exp100fs)
![Page 20: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/20.jpg)
Photofragment velocity map imaging of H atom elimination in the first excited state of pyrrole F. Temps et al., PCCP, 5 (2003) 315
Photophysics of pyrrole
σ* 1sH
Chem. Phys. Lett. 321 (2000) 479
TKER spectroscopy
M.N.R. Ashfold et al., PCCP, 12 (2010) 1218
hν
εk
![Page 21: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/21.jpg)
A. L. Sobolewski and W. Domcke
Photoinduced electron and proton transfer in phenol and its clusters with water and ammonia
J. Phys. Chem. A 105 (2001) 9275
Photophysics of phenol and phenol-H2O complex
3sH2O σ*
1sH
σ*
3sH2O
![Page 22: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/22.jpg)
Hydrated hydronium clusters: SOMO orbital
e¯
H3O+
H3O (H3O)W1
(H3O)W3 (H3O)W6
(H3O)W9
A. L. Sobolewski and W. Domcke
Hydrated hydronium: a cluster model of the solvated electron?
Phys. Chem. Chem. Phys. 4 (2002) 4
![Page 23: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/23.jpg)
Hydrated electrons(?)
Abel, Buck, Sobolewski, Domcke,
On the nature and signatures of the solvated electron in water,
PCCP, 14 (2012) 22
![Page 24: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/24.jpg)
Paradigm III:
Hydrogen (or any of the first column metal) atom injected
into a saturated polar solvent ionizes spontaneously into
proton (cation) and a solvated electron
e¯
H3O+
(H3O)W9
e–
K+
K(H2O)20
![Page 25: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/25.jpg)
Inter-molecular hydrogen bonds
X,Y=N,O
X-H...Y
„non-saturated” chromophores?
![Page 26: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/26.jpg)
guanine
X-H...Y
cytosine
Photophysics of the GC base pair
![Page 27: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/27.jpg)
Sobolewski&Domcke, PCCP 6 (2004) 2763
LE(G) LE(C)
CT(GC)
p(G) p(C)
p*(G) p*(C)
Photophysics of guanine-cytosine base pair
[fs]
IC
CI
CI
abs
CC2
![Page 28: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/28.jpg)
Hobza, De Vries, et al., PNAS, 102 (2005) 20
WC type
non-WC type
Photophysics of guanine-cytosine base pairs
REMPI spectra
![Page 29: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/29.jpg)
Photophysics of guanine-cytosine base pairs
Sobolewski, Domcke, Hättig, PNAS., 102 (2005) 17903
CT
CT CT >ps
fs >ps
CC2
![Page 30: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/30.jpg)
S0
1LE
1CT
PT coordinate
En
erg
y
coupling coordinate
IC
ET [X–...(H-Y)+]hot
X-H...Y
ab
so
rpti
on
(X-H...Y)*
[(X-H)...Y–]hot
Sobolewski & Domcke
ChemPhysChem, 7 (2006) 561
Electron-Driven Proton-Transfer (EDPT) proces
IC
X•...(H-Y)•
e-
e-
ET
e-
![Page 31: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/31.jpg)
Photochemistry of the GC base pair in vacuum.
.
CASSCF NBO dynamics simulations
Michael A. Robb et al., J. Am. Chem. Soc. 2007, 129, 6812-6819
![Page 32: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/32.jpg)
Hydrogen-bonded bio-structures
DNA proteins
cellulose
![Page 33: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/33.jpg)
Paradigm IV:
EDPT process provides an universal mechanism for ultra-fast radiationless decay of electronic
excitation in nucleotides, peptides, and in strands of DNA and RNA.
Hydrogen bonds are a key not only for functionality of biological matter,
but also for its photostability.
AMP Gly-Phe-Ala G-C/A-T J. Phys. Chem. A, 118 (2014) 122 JACS, 131 (2009) 1374 PNAS, 102 (2005) 17903
J. Phys. Chem. A 110 (2006) 9031
![Page 34: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/34.jpg)
S0
1L
E
1CT
PT coordinate
Energ
y
Coupling coordinate
IC
ET [X–...(H-Y)+]hot
X-H...Y
ab
so
rpti
on
(X-H...Y)*
[(X-H)...Y–]hot
Sobolewski & Domcke
ChemPhysChem, 7 (2006) 561
photoreactivity
photostability
IC
X•...(H-Y)•
X-H...Y
Y...H-X
X-H...H
X-H...Y
e-
e-
ET
e-
Electron-Driven Proton-Transfer (EDPT) proces
![Page 35: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/35.jpg)
Photophysics of a single-HB system
X-H...Y X...H-Y hn
X + H-Y
oxidation reduction
if X-H HO-H
photo-oxidation of water!
photo-redox reaction
HO + H-Y
hn(?)
![Page 36: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/36.jpg)
X. Liu, A.L. Sobolewski, R. Borrelli, W. Domcke, PCCP 15 (2013) 5957
Photophysics of pyridine-H2O complex
π*
π
n
2pz(O)
2px(O)
π*
1,3pxπ*
1,3pzπ*
CC2
OH• PyH•
abs
![Page 37: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/37.jpg)
Photophysics of pyridine-H radical
CC2
abs
![Page 38: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/38.jpg)
hν(UV)
electron/proton
transfer
hν(UV) H-detachment
+H2O
∆
hydrogen-bond
breaking
water
splitting
Pyridine-H2O: The photocatalytic cycle
X. Liu, et al.., PCCP 15 (2013) 5957 J. Phys. Chem. A, 118 (2014) 7788
C. Jouvet, et al.., PCCP 18 (2016) 25637 Photoinduced water splitting in pyridine water cluster
theory experiment
![Page 39: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/39.jpg)
N
N
N NH2NH
2
Heterocycles absorption vs. the solar spectrum
Ac
BA
AO
Xiaojun Liu, Tolga N.V. Karsili, Andrzej L. Sobolewski, Wolfgang Domcke
Photocatalytic water splitting with acridine dyes: Guidelines from computational chemistry
Chemical Physics, Volume 464, 2016, 78–85
![Page 40: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/40.jpg)
+H2O
hν(Vis) electron
driven
proton
transfer
-OH
hν(Vis) H-detachement
Theory: Sobolewski&Domcke, PCCP 14 (2012) 12807
Experiment: Morawski et al., PCCP 16 (2014) 15256
Oxotitanium porphyrin-H2O: The photocatalytic cycle
![Page 41: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/41.jpg)
Paradigm V:
Photoreactivity (redox reaction) related to EDPT process provides a template for designing
molecular systems which can catalyse photochemical splitting of water.
pyridine TiO-porphyrin TiO-phthalocyanin
PCCP 14 (2012) 12807 PCCP 16 (2014) 15256
J. Phys. Chem. C, 119 (2015) 14085 PCCP 15 (2013) 5957 J. Phys. Chem. A, 118 (2014) 7788
![Page 42: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/42.jpg)
Photophysics of Hydrogen-Bonded Systems A summary
X-H...Y
X,Y=N,O X-H...Y
Intra-molecular HB Inter-molecular HB
e e
PT vs. HT dilemma
1CT 1LE
S0
PT coordinate
absorp
tion
PT coordinate
En
erg
y
S0
S1 “keto”
“enol”
absorp
tion e
mis
sio
n
carbon
nitrogen
oxygen
hydrogen
PT
HT
HT
PT
HT
![Page 43: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/43.jpg)
Acknowledgements
Theory: Dr. Joanna Jankowska Dr. Michal F. Rode Experiment: Prof. Maciej Nowak Dr. Olaf Morawski Dr. Elena Karpiuk Dr. Leszek Lapinski
Theory: Prof. Wolfgang Domcke Dr. Xiaojun Liu Dr. Deniz Tuna Dr. Tolga N. V. Karsili Dr. Dorit Shemesh
Thank you for your attention!
![Page 44: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/44.jpg)
A”
A’ abs
H-diss IC
e–
H3O+
Solvated electron
abs IC
PT
Photostability
Molecular switch Photocatalytic water splitting
TKER spectroscopy
New paradigms in photophysics of hydrogen-bonded molecular systems
A general overview
![Page 45: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/45.jpg)
Photosynthesis
Photosystem II
Chlorophyll absorption spectrum
Qy
Qx
Soret
UV OH-/H+
adsorbed H2O H2O@TiO2
TiO
![Page 46: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/46.jpg)
Photophysics of TiOP: theory
1,3CT
S0
1Q
1B
LE(Q,B) CT
Ti
Ti(IV)
Ti(III)
O
S0 + H2O
hυ
CT
O ●
+ + _
+ OH ● OH ●
(?)
Sobolewski&Domcke, PCCP 14 (2012) 12807
![Page 47: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/47.jpg)
Photophysics of TiOP:H2O complex
OH
photogeneration
of OH radicals
from water
Theoretical
prediction:
![Page 48: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/48.jpg)
Spectroscopic detection of OH
radicals
340 360 380 400 420 440 460 480 500 520 540 560 580 600
0
500
1000
1500
2000
2500
3000
3500
4000
4500
without illumination
illumination 0.5 h
illumination 1.5 h
illumination 2.5 h
illumination 3.5 h
illumination 4.5 h
illumination 5.5 h
Flu
ore
scen
ce i
nte
nsi
ty, a.
u.
Wavelength, nm
λexc=315nm
HTA fluorescence vs. TiOP illumination
Morawski et al., PCCP 16 (2014) 15256
![Page 49: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/49.jpg)
IC
abs
TiPOH TD/DFT/cc-pVDZ(TZVP) MEP Photophysics of TiPOH radical
![Page 50: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/50.jpg)
ns-s
EVR
Exte
rnal vib
rational bath
S0
S1
IVR
ps
Inte
rnal vib
rational bath
Photostability via EDPT process
UV VIS
EDPT
fs
NH
/OH
str
etc
h
IR
![Page 51: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/51.jpg)
CC2
Photophysics of indole-ammonia complex
Sobolewski & Domcke, Computational studies of the photophysics of hydrogen-bonded molecular systems, J. Phys. Chem. A, 111 (2007) 11725, feature article
3sNH4
3sNH3
![Page 52: NEW PARADIGMS IN THE PHOTOPHYSICS OF HYDROGEN- … › ON-2 › on21 › TUM_2017.pdf · Paradigm II: Molecular photoswitches or transistors based on the ESI ntra PT phenomenon: -](https://reader033.vdocuments.us/reader033/viewer/2022060407/5f0f931c7e708231d444d6c5/html5/thumbnails/52.jpg)
Photophysics of pyridine-ammonia complex
CC2
ET
J. Phys. Chem. A, 111 (2007) 11725
ET