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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
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)
Sobolewski & Domcke, Chem. Phys. 184 (1994) 115
CASSCF CASPT2
S0
1nπ
1ππ*
S0
1nπ
1ππ*
PT
Photophysical scheme of o-benzaldehyde
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
UV light
VIS light or heat
Photophysics of azobenzene
UV VIS
S0
S1
NH
N
N
NH
Sobolewski & Domcke, J. Phys. Chem. A 111 (2007) 11725
Photophysics of 7-(2’-pyridyl)indole
CI
CC2
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)
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
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
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’
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
Photophysics of 7-hydroxy-(8-oxazine-2-one)-quinoline
PCCP, 10 (2008) 1243
CI
carbon
nitrogen
oxygen
hydrogen
CC2
Photophysics of a molecular switch
S0
S1 S1
„gre
en
” p
ho
ton
„blu
e”
photo
n
OH NH CO
IR IR
„enol” „keto”
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
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
X,Y=N,O
X-H...Y
Intra-molecular hydrogen bonds
Inter-molecular hydrogen bonds
X,Y=N,O
X-H...Y
Photophysics of an acidic chromophore
X,Y=N,O
X-H
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)
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
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
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
Hydrated electrons(?)
Abel, Buck, Sobolewski, Domcke,
On the nature and signatures of the solvated electron in water,
PCCP, 14 (2012) 22
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
Inter-molecular hydrogen bonds
X,Y=N,O
X-H...Y
„non-saturated” chromophores?
guanine
X-H...Y
cytosine
Photophysics of the GC base pair
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
Hobza, De Vries, et al., PNAS, 102 (2005) 20
WC type
non-WC type
Photophysics of guanine-cytosine base pairs
REMPI spectra
Photophysics of guanine-cytosine base pairs
Sobolewski, Domcke, Hättig, PNAS., 102 (2005) 17903
CT
CT CT >ps
fs >ps
CC2
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-
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
Hydrogen-bonded bio-structures
DNA proteins
cellulose
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
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
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(?)
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
Photophysics of pyridine-H radical
CC2
abs
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
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
+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
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
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
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!
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
Photosynthesis
Photosystem II
Chlorophyll absorption spectrum
Qy
Qx
Soret
UV OH-/H+
adsorbed H2O H2O@TiO2
TiO
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
Photophysics of TiOP:H2O complex
OH
photogeneration
of OH radicals
from water
Theoretical
prediction:
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
IC
abs
TiPOH TD/DFT/cc-pVDZ(TZVP) MEP Photophysics of TiPOH radical
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
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
Photophysics of pyridine-ammonia complex
CC2
ET
J. Phys. Chem. A, 111 (2007) 11725
ET