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DNQ
DNQ
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MID-IR Ultrafast Spectroscopy DNQ
Motivation:
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MID-IR Ultrafast Spectroscopy DNQ
? Carbene
Ketene Enol
DNQ
4.0
3.5
After 20 min UV
DNQ in Methanol 100m Before
3.0
13 mmol/L 15
2.5
DNQ
Absorption
Absorption
2.0
10
1.5
1708
Indene C. Ester
1.0
0.5 5
Methanol
0.0
200 250 300 350 400 450 500
Lambda(nm)
0
UV/VIS spectrum of DNQ in methanol
1200 1400 1600 1800 2000 2200
-1
Wavenumber (cm )
Vibrational modes of both Ketene and DNQ fall into the same interval
covered by MID-IR fs laser spectrum
DNQ KETENE
C=N=N Stretching:
C=C=O Stretching:
2084 cm-1
2118 cm-1 2128 cm-1
2168 cm-1
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MID-IR Ultrafast Spectroscopy DNQ
Transient Absorption
Photodiode Array
MID-IR Probe
UV Pump
MID-IR Pump
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MID-IR Ultrafast Spectroscopy DNQ
UV MID-IR
Dynamics of photoproduct Ketene
With quantum yield Q
N1 (t ) QN EXC e t /t1 S1
N 2 (t ) QN EXC e t /t1 C e t /t1 e t /t 2
Very fast
N 3 (t ) QN EXC e t /t1 De t /t1 Ce t /t 2 1
Dynamics of the bleach recovery - DNQ
Q
t /t 0
DNQ(t ) A Be N1(t)
t1
1-Q N2(t)
t2
S0 t0 N3(t)
DNQ(t)
DNQ Ketene
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MID-IR Ultrafast Spectroscopy DNQ
Ketene formation
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MID-IR Ultrafast Spectroscopy DNQ
Ketene formation
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MID-IR Ultrafast Spectroscopy DNQ
0,0
t0=9.8.2 ps
Abs.(mOD)
-6,0
-1,0
-8,0
-10,0
A=0.69 mOD
-12,0
B=0.68 mOD -2,0
-14,0
-16,0
-20 -10 0 10 20 30 -3,0
t(ps) -20 -10 0 10 20 30
t(ps)
4,0 1,0
2,0
0,0
0,0
-2,0 UV & MID-IR Pump
-4,0
Abs.(mOD)
Abs.(mOD)
-6,0 -1,0
-8,0
t0=3.8.2 ps
-10,0 A=1.37 mOD -2,0
-12,0
B=1.41 mOD
-14,0
-16,0 -3,0
-20 -10 0 10 20 30 -20 -10 0 10 20 30
t(ps) t(ps)
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MID-IR Ultrafast Spectroscopy DNQ
Introduction of MID IR pump changes the short time dynamics of the DNQ
bleach but does not change the final yield of photoproduced Ketene
That means that the 2128 stretching mode is not the reactive coordinate
Reactive coordinate must be in FC region.
Next step for achieving VMP is to try with 1600 mode, ring-rearrangement
mode
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MID-IR Ultrafast Spectroscopy DNQ
30
10
14
MID-IR Ultrafast Spectroscopy DNQ
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