time-resolved ftir emission spectroscopy of the (v 1 )-ch stretch of the ketenyl (hcco) radical...
TRANSCRIPT
Time-Resolved FTIR Emission Time-Resolved FTIR Emission Spectroscopy of the (vSpectroscopy of the (v11)-CH Stretch )-CH Stretch
of the Ketenyl (HCCO) Radicalof the Ketenyl (HCCO) Radical
Michael J. Wilhelm, William McNavage, and Raymond GrollerDepartment of Chemistry, University of Pennsylvania
Hai-Lung DaiDepartment of Chemistry, Temple University
6262ndnd International Symposium on Molecular International Symposium on Molecular SpectroscopySpectroscopy
[RF03] : Thursday, June 21, 2007[RF03] : Thursday, June 21, 2007
All Roads Lead to Ketenyl…
HCCH + …
NO2 + UV NO + O(3P)
HCCH + O(3P) HCCO + H
HCCO + O2 H + CO + CO2
combustioncombustion
atmosphericatmospheric
Past Spectroscopic Studies of Ketenyl:
K.G. Unfried, G.P. Glass, and R.F. Curl, Chem. Phys. Lett., 117, 33 (1991)
Vibrational SpectroscopyVibrational Spectroscopy Infrared Flask Kinetic Spectroscopy Infrared Flask Kinetic Spectroscopy (v(v22) Asymmetric CCO Stretch:) Asymmetric CCO Stretch:
Pure Rotational SpectrumPure Rotational Spectrum of HCCO with Sub-millimeter Wave Spectroscopy: of HCCO with Sub-millimeter Wave Spectroscopy:Large (Ka)-dependency Large (Ka)-dependency Renner-Teller Interaction Renner-Teller InteractionNear-Prolate Symmetric TopNear-Prolate Symmetric Top
Y. Endo and E. Hirota, J. Chem. Phys., 8, 4319 (1991)
Electronic SpectroscopyElectronic Spectroscopy of the B of the BX System of HCCO:X System of HCCO:LIF - Origin of the (B)-StateLIF - Origin of the (B)-StatePFY – (vPFY – (v66) CCH Bend) CCH BendSmall fluorescence quantum yield.. LIF not advisable!Small fluorescence quantum yield.. LIF not advisable!
Osborn, Mordaunt, Choi, Bise, Neumark and Rohlfing, J. Chem. Phys., 106, 10087 (1997)Brock, Mischler, and Rohlfing, J. Chem. Phys., 110, 6773 (1999)
%0;
%37;~
%63;~/
~
32
324
3222
3.19332
CHCHOHCC
CHCHAaHCCO
CHCHAAXHCCOCHCHOHCC nm
M.J. Krish, J.L. Miller, and L.J. Butler, M.J. Krish, J.L. Miller, and L.J. Butler, J. Chem. PhysJ. Chem. Phys., ., 119119, 176 (2003), 176 (2003)
Generation of Ketenyl..Generation of Ketenyl..
AX 2~
Collider Gas Input
[2-10 Torr]
Sample Input[10 – 100
mTorr]
Oscilloscope
Bruker Transient Recorder
BoardPad82a
MM
IFS 66sIFS 66s
Time-Resolved Fourier Transform Infrared Emission Spectroscopy (TR FTIRES):Time-Resolved Fourier Transform Infrared Emission Spectroscopy (TR FTIRES):
ArF Excimer : LPX 200{l = 193 nm, 20 Hz, ≤ 100 mJ/pulse}
Pre-Amp +
Amplifier
Win2K PC / OPUS
f1 f2
Photodiodetrigger
Gas
Cell
To Glass Manifold / Mechanical Pump(i.e. Continuous Flow..)
Capacitance Manometer[0-10 Torr]
Step-Scan
RA + h193.3 nm R‡ + A‡
R‡(v’=k) + M R‡(v’=k-1) + M*
:
R‡(v’=1) + M R (v’=0) + M*
HCC-O-CH2CH3 + (193 nm) HCCO + CH2CH3
220
200
180
160
140
120
100
80
60
40
20
0
Nor
maliz
ed E
miss
ion
Inte
nsity
/ a
.u.
3800360034003200300028002600240022002000Frequency / cm-1
Time-Resolved FTIR Emission Spectra:
AX 2~HCCO(v2) CO
HCC[XA]CH2CH3 (?) {HCC(v1) HCCO(v1)}
-- Early-- Late
2D Cross-Spectral Correlation Analysis:
AX 2~
(A)
(B)
Frequency / cm-1
Inte
nsi
ty /
a.u
.
Time / s
16
15
14
13
12
11
10
9
8
7
6
5
4
3
2
1
0
Inte
nsity
/ a
.u.
10.09.08.07.06.05.04.03.02.01.00.0
Time / s
(A)
Time / Time / ss
Inte
nsi
ty /
a.u
.
FrequencyFrequency
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
Inte
nsity
/ a
.u.
10.09.08.07.06.05.04.03.02.01.0
Time / s
(B)
Time / Time / ss
Inte
nsi
ty /
a.u
.
FrequencyFrequency
niSignalSignal eII 0 ki
NoiseNoise eII
212121 ,,, iX
synchronoussynchronous asynchronous asynchronous
2D Cross-Spectral Synchronous Correlation Analysis:
AX 2~
16.2 16.2 ss
Tim
e-R
eso
lved D
ata
Tim
e-R
eso
lved D
ata
Set(
1)
Set(
1)
Time-Resolved Data Time-Resolved Data Set(2)Set(2)
212121 ,,, iX
2D Cross-Spectral Synchronous Correlation Analysis:
0.05-1.75 0.05-1.75 ss((0.9 0.9 ss))
5.15-6.85 5.15-6.85 ss((6.0 6.0 ss))
AX 2~
10.25-11.95 10.25-11.95 ss((11.1 11.1 ss))
15.35-17.05 15.35-17.05 ss((16.2 16.2 ss))
Extracted (time-resolved) Synchronous Diagonals:
40
36
32
28
24
20
16
12
8
4
0
Em
issi
on I
nten
sity
/ a
.u.
3800360034003200300028002600240022002000
Frequency / cm-1
1.2
1.1
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0E
mis
sion
Inte
nsity
/ a.
u.
360035003400330032003100300029002800
16.2 s
0.9 s
16.2 s
AX 2~
HCCO(v1)
HCCH(v3)HCC(v1)
PTS + Vibronic
MS-TOF
2D Cross-Spectral Asynchronous Correlation Analysis:
AX 2~ 212121 ,,, iX
Tim
e-R
eso
lved D
ata
Set(
1)
Time-Resolved Data Time-Resolved Data Set(2)Set(2)
2D Cross-Spectral Asynchronous Correlation Analysis:
12 33003200 cmHCCO
AX 2~
CO(01)
HCCO(v2)
1.2
1.1
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
Em
issi
on
In
ten
sity
/ a
.u.
34003360332032803240320031603120308030403000Frequency / cm
-1
Rotational Contour Simulation:
AX 2~
1.2
1.1
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
Em
issi
on I
nten
sity
/ a.
u.
34003360332032803240320031603120308030403000
Frequency / cm-1
8
6
4
2
0
1,,1,;,1,;, 1111 aakak KKJJKJ
HCCH (v3)
HCC (v1)
HCCO[v1] ~ 3232 cm-1
Near-Prolate Symmetric Top..Near-Prolate Symmetric Top..
IR Spectral Assignments:
AX 2~
[X1] – Gaussian03 Calculation[X1] – Gaussian03 Calculation[X2] – Peter Szalay (Private Communication)[X2] – Peter Szalay (Private Communication)
Acknowledgments:
U.S. Department of EnergyU.S. Department of Energy, , Basic Energy Sciences Basic Energy Sciences
NASA Earth System Science Fellowship (WM) NASA Earth System Science Fellowship (WM)
Financial Support:
People:
Hai-Lung Dai (Advisor)Hai-Lung Dai (Advisor)
Matt NikowMatt NikowMin ZhangMin ZhangGrazia GonellaGrazia GonellaJia ZengJia Zeng
Jianqiang MaJianqiang MaJun HanJun HanMichelle WangMichelle WangShi-Hui Jen Shi-Hui Jen
William McNavageWilliam McNavageRay GrollerRay Groller