STUDY ON THE VIBRATIONAL DYNAMICS OF PHENOL AND PHENOL-WATER COMPLEX BY PICOSECOND TIME- RESOLVED...
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Transcript of STUDY ON THE VIBRATIONAL DYNAMICS OF PHENOL AND PHENOL-WATER COMPLEX BY PICOSECOND TIME- RESOLVED...
![Page 1: STUDY ON THE VIBRATIONAL DYNAMICS OF PHENOL AND PHENOL-WATER COMPLEX BY PICOSECOND TIME- RESOLVED IR-UV PUMP-PROBE SPECTROSCOPY Yasunori Miyazaki, Yoshiya.](https://reader031.fdocuments.us/reader031/viewer/2022032308/56649f4e5503460f94c70072/html5/thumbnails/1.jpg)
STUDY ON THE VIBRATIONAL DYNAMICS OF STUDY ON THE VIBRATIONAL DYNAMICS OF PHENOL AND PHENOL-WATER COMPLEX BY PHENOL AND PHENOL-WATER COMPLEX BY PICOSECOND TIME-RESOLVED IR-UV PUMP-PROBE PICOSECOND TIME-RESOLVED IR-UV PUMP-PROBE SPECTROSCOPYSPECTROSCOPY
Yasunori Miyazaki, Yoshiya Inokuchi, Takayuki EbataYasunori Miyazaki, Yoshiya Inokuchi, Takayuki Ebata
Department of Chemistry, Graduate school of Science,Department of Chemistry, Graduate school of Science,
Hiroshima UniversityHiroshima University
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Vibrational Energy Vibrational Energy RelaxationRelaxation
Intramolecular Vibrational energy Redistribution (IVR)
ls>
lb>
ρ b
Vsb)(
2 2EVk bsbIVR
Fermi’s Golden Rule
= anharmonic coupling
= density of bath state
sbV
b
![Page 3: STUDY ON THE VIBRATIONAL DYNAMICS OF PHENOL AND PHENOL-WATER COMPLEX BY PICOSECOND TIME- RESOLVED IR-UV PUMP-PROBE SPECTROSCOPY Yasunori Miyazaki, Yoshiya.](https://reader031.fdocuments.us/reader031/viewer/2022032308/56649f4e5503460f94c70072/html5/thumbnails/3.jpg)
Vibrational Energy Vibrational Energy RelaxationRelaxation
Intramolecular Vibrational energy Redistribution (IVR)
Anharmonic coupling (normal mode analysis)
ls>
lb>
ρ b
Vsb
...6
1
2
1)(
,,
3
,
2
0
jis
jis jisji
is is
qqqqqq
Vqq
VVqV
jis vvv ,,00,0,
ls>
li>
li>lj>
lj>
Csij
Anharmonic term
Csij = qsqiqj = anharmonic constantEvaluation of coupling amongvibrational modes: s, i, j
)(2 2
EVk bsbIVR
Fermi’s Golden Rule
![Page 4: STUDY ON THE VIBRATIONAL DYNAMICS OF PHENOL AND PHENOL-WATER COMPLEX BY PICOSECOND TIME- RESOLVED IR-UV PUMP-PROBE SPECTROSCOPY Yasunori Miyazaki, Yoshiya.](https://reader031.fdocuments.us/reader031/viewer/2022032308/56649f4e5503460f94c70072/html5/thumbnails/4.jpg)
IR spectrum of phenolIR spectrum of phenol%
tran
smitt
ance
in solutionLarge red-shift•Reduced force constant of the OH bondSpectral broadening•Vibrational Energy Relaxation•Fermi Resonance with overtone and/or combination band•Inhomogeneous broadening due to random geometries
etc
Free OH stretchHydrogen-bonded
OH stretchOH
![Page 5: STUDY ON THE VIBRATIONAL DYNAMICS OF PHENOL AND PHENOL-WATER COMPLEX BY PICOSECOND TIME- RESOLVED IR-UV PUMP-PROBE SPECTROSCOPY Yasunori Miyazaki, Yoshiya.](https://reader031.fdocuments.us/reader031/viewer/2022032308/56649f4e5503460f94c70072/html5/thumbnails/5.jpg)
IR spectrum of phenolIR spectrum of phenol
*T. Ebata, et. al., International Journal of Mass Spectrometry, Vol. 159, pp. 111 (1996).
in supersonic molecular beam*
OH
% tr
ansm
ittan
ce
in solution
Free OH stretchHydrogen-bonded
OH stretch
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Experimental SetupExperimental Setup
Supersonic Molecular Beam• Directional (minimizing the Doppler effect)
• Population at the lowest vibrational energy level of S0
• Isolated condition
T O F +c hanneltron
mode- loc kedN d: Y A G laser
T H G
1064 nmsample
P G 401S H
P G 401/ D F G
delay- timec ontrol
IR range2300 - 10000 nm
U V range210 - 440 nm
355 nm
Resolution: 14 ps, 5 cm-1
S 0
O H
S 1
IP
IR
UV
UV
doorwaystate
bathstate
U V
U V UV
UVΔ t
τ 1 τ 2
![Page 7: STUDY ON THE VIBRATIONAL DYNAMICS OF PHENOL AND PHENOL-WATER COMPLEX BY PICOSECOND TIME- RESOLVED IR-UV PUMP-PROBE SPECTROSCOPY Yasunori Miyazaki, Yoshiya.](https://reader031.fdocuments.us/reader031/viewer/2022032308/56649f4e5503460f94c70072/html5/thumbnails/7.jpg)
phenol-dphenol-d00
transient 1+1 REMPI*
U V energy
0O H v' - v''
decay
rise
Energy diagram
Y. Yamada, et. al., J. Chem. Phys., Vol. 120, No. 16, pp. 7400 (2004).
a) OH = 32693 cm-1 b) bath = 35461 cm-1
IR
OH
S 0
O H
S 1
IP
IR
UV
UV
doorwaystate
bathstate
U V
U V UV
UVΔ t
τ 1 τ 2
v'
v''
IR wavenumber (cm-1)3620 3660 3700
νOH = 3656 cm-1
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150100500- 50
delaytimeΔ t (ps)
phenol-dphenol-d00
Time Profile
a) OH
b) bath state
U V energy
0O H v' - v''
decay
riseIR
OH
Energy diagram
S 0
O H
S 1
IP
IR
UV
UV
doorwaystate
bathstate
U V
U V UV
UVΔ t
τ 1 τ 2
v'
v''
IR wavenumber (cm-1)3620 3660 3700
νOH = 3656 cm-1
decay τ = 14 ps
rise τ = 14 ps
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Summary 1Summary 1
S 0
O H
IR
doorwaystate
bathstate
τ 1 14ps
τ 2<<14ps
densityof state
110state/cm-1
v’IVR1 IVR2
S 1v"
*Petkovic, M. Journal of Physical Chemistry A, Vol. 116, pp. 364-371 (2012)
doorway stateγCH
* bath stateνCH
*
IR
OH
OH
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phenol-dphenol-d11
Energy diagram transient 1+1 REMPI
a) OD = 33647 cm-1
b) doorway = 34784 cm-1
IR
OD
33500 34000 34500 35000
S 0
O D
S 1
IP
IR
U V
U V
doorwaystate
bathstate
Δ t
U V U V
U V U V
τ 2
IR wavenumber (cm-1)2660 2700 2740
v'
v''νOD = 2700 cm-1
OD106a
U V energy
0O D v' - v''
decay
risedecaydoorwaystate
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phenol-dphenol-d11
Time Profile
U V energy
0O D v' - v''
decay
risedecaydoorwaystate
IROD
IR
OD
Energy diagram
S 0
O D
S 1
IP
IR
U V
U V
doorwaystate
bathstate
Δ t
U V U V
U V U V
τ 2
IR wavenumber (cm-1)2660 2700 2740
v'
v''νOD = 2700 cm-1
O D
doorwaystate
- 100 0 100 200 300delay time Δ t (ps)
![Page 12: STUDY ON THE VIBRATIONAL DYNAMICS OF PHENOL AND PHENOL-WATER COMPLEX BY PICOSECOND TIME- RESOLVED IR-UV PUMP-PROBE SPECTROSCOPY Yasunori Miyazaki, Yoshiya.](https://reader031.fdocuments.us/reader031/viewer/2022032308/56649f4e5503460f94c70072/html5/thumbnails/12.jpg)
Time evolution of existence probability after time t
phenol-dphenol-d11
t
mnmmn
n
t
nn
mnn
eEEt
etOD)
11(2
12
2343
1
2222 cos2)(
t
mnmnmmn
n
t
nn
n
mnn
eEEt
etl)
11(2
1
113
121
23
1
2
2222 cos2)(
OD:
Doorway:
Bath: t
nn
n
etbath 2
123
1
1)(
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Fitting parameters*
α1 = 0.616 β21 = 0.323
α2 = 0.663 β22 = 0.353
α3 = 0.424 β23 = -0.911
Assignment of the doorway state l2
116a112118b1
Summary 2Summary 2
Energy gapE13 = 0.656 cm-1
E23 = 0.489 cm-1
E12 = 0.167 cm-1
ODl2l1
2700 cm-1
33647 cm-1
1137 cm-1
34784 cm-1
S0
S1
IR
OD
OD
IVR lifetimeτ2
1 = 80 psτ2
2 = 90 psτ2
3 = 60 ps
Y. Yamada, et. al., J. Chem. Phys., Vol. 121, No. 23, pp. 11530 (2004).
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Energy diagram
phenol-dphenol-d11▪▪(D(D22O)O)
ODIRODD
H-bonded νOD = 2600 cm-1
a) OD = 33410 cm-1 b) 34965 cm-1
c) 35211 cm-1
d) 35461 cm-1
U V wavenumber (c m- 1)
33500 34000 34500 35000 35500delay t ime
Δ t (ps )
287
53
20
6.7
transient 1+1 REMPI
S 0
H - bondedO D
S 1
IP
IR
U V
U V
intramolec ularV R
intermolec ularV R
phenol- d1- (D 2O )
phenol- d1 + D 2O
dissoc iation
vibrationalpredissoc iation
U V U V
U V U V
Δ t
τ 1
2560 2600 2640
IR wavenumber (c m- 1)
vO D
τ 2 τ 3
U V energy
0
O D intermolecularintramolecular
Vibrational Predissociation
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4003002001000
delay time Δ t (ps)
a)
b)
c )
d)
Time Profile
phenol-dphenol-d11▪▪(D(D22O)O)
ODIRODD
intramolecularVR τ1 = 12 ps intermolecularVR τ2 = 24 ps
VP τ3 = 100 ps
Energy diagramH-bonded νOD = 2600 cm-1
S 0
H - bondedO D
S 1
IP
IR
U V
U V
intramolec ularV R
intermolec ularV R
phenol- d1- (D 2O )
phenol- d1 + D 2O
dissoc iation
vibrationalpredissoc iation
U V U V
U V U V
Δ t
τ 1
2560 2600 2640
IR wavenumber (c m- 1)
vO D
τ 2 τ 3
U V energy
0
O D intermolecularintramolecular
Vibrational Predissociation
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Time Profile
phenol-dphenol-d00▪▪(H(H22O)O)
ODIRODD
U V energy
0
O H intermolecularintramolecular
Vibrational Predissociation
* Doi, A.; Mikami, N. J. Chem. Phys. Vol. 129, pp. 154308. (2008)
intramolecularVR τ1 = 4 ps * intermolecularVR τ2 = 5 ps
VP τ3 = 25 ps
Energy diagram
S 0
H- bondedO H
S 1
IP
IR
U V
U V
intramolec ularV R
intermolec ularV R
phenol- d0- (H 2O )
phenol- d0 + H 2O
dissoc iation
vibrationalpredissoc iation
U V U V
U V U V
Δ t
3480 3520 3560
vOH
IR wavenumber (cm-1)
τ 1 τ 2 τ 3
H-bonded νOH = 3525 cm-1
4003002001000
b)
c )
d)
delaytimeΔ t (ps)
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phenol-water complexphenol-water complex
RRKM theory
)(
)(1)( 0
. E
EEW
hEk D
diss
excess energy~600cm-1
excess energy~1525cm-1
HH
DD
3525cm-1
2600cm-1
HH
DD
E0
EDdiss.energy~2000cm-1
Energy scheme
phenol-d1(D2O):
pskRRKM
RRKM 6.431
phenol-d0(H2O):
RRKM
RRKM k
1
1525
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Summary 3Summary 3
*Petkovic, M. Journal of Physical Chemistry A, Vol. 116, pp. 364-371 (2012)
dominantIntermolecular vibrationalmode for dissociation*
S 0
O D
IR
S 1
intramolecularvibration
intermolecularvibration
Δ v =0,± 1,± 2,.. Δ v =0
vibrationalpredissociation
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Future WorksFuture Works Obtain more data about IVR process of phenol-
derivatives after the OH stretching vibration
Measure the predissociation lifetime of various H-bonded phenol-d1▪(X) complexes
where X = (π-type) acetylene, ethylene, benzene,
(σ-type) dimethyl ether, etc
Effect of intramolecular hydrogen-bonding?Coupling of non-CH related vibrational modes and its IVR rate?
Comparison to the dissociation lifetime of phenol-d0(X) complex