synchrotron-based study of the far infrared spectrum of silacyclobutane: the ν 29 and ν 30 bands...
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![Page 1: Synchrotron-based study of the far infrared spectrum of silacyclobutane: the ν 29 and ν 30 bands Ziqiu Chen, Cody W. van Dijk, Samantha Harder and Jennifer](https://reader038.vdocuments.pub/reader038/viewer/2022110207/56649d835503460f94a68f3c/html5/thumbnails/1.jpg)
Synchrotron-based study of the far infrared spectrum of silacyclobutane: the ν29 and ν30 bands
Ziqiu Chen, Cody W. van Dijk, Samantha Harder and Jennifer van Wijngaarden
Department of Chemistry, University of Manitoba, Winnipeg, Canada
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Ring puckering potential of silacyclobutane (SCB)
2
0+0-
1+1-
Ring puckering angle θ
440
cm-1
2+2-
E
Si
C
C
C
a
b
β
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Previous low resolution work
3
W.C. Pringle, J. Chem. Phys. 54,4979 (1971)
MW
J. Laane and R. C. Lord, J. Chem. Phys. 48, 1508 (1968)A.A. Al-Saadi and J. Laane, Organometallics, 27, 3435 (2008)
IR
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Previous high resolution MW work
0-0+
J. van Wijngaarden, Z. Chen, C.W. van Dijk and J.L. Sorensen, J. Phys. Chem. A 115, 8650 (2011)
0+0-
1+1-
Ring puckering angle θ
440
cm-12+
2-E
FTMW spectrum
a-type
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Canadian Light Source, CLS
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NH
D. W. Tokaryk and J. van Wijngaarden, Can J. Phys. 87, 443-448 (2009).
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Far-infrared experiments at CLS
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LiAlH4
110 ˚C
Exp. Parameter FIR set up
Spectrometer Bruker IFS 125 HR FTIR
Aperture 1.3 mm
Resolution
(instrumental)
0.000959 cm-1 (360-500
cm-1)
0.001920 cm-1 (100-200
cm-1)
Absorption pathlength 72 m
Cell temperature 298 K
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380 400 420
cm-1
440
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The ν29 SiH2 rocking mode
6 μm Mylar BS/GeCu Detector
528 interferograms, ~53 h
448 mTorr
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392.9 391.1 391.3
cm-1
391.4391.2391.0
How can we assign them?
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Loomis-Wood plot of the ν29 band: c-type progressions
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oeoo
eoee
A2A1
B2B1
oeoo
eoee
A2A1
B2B1
oeoo
eoee
B2B1
A2A1
oeoo
eoee
B2B1
A2A1
Ring inversion (B1)
ν29 SiH
2 rocking mode (B
1)
ν29 SiH
2 rocking mode (B
1)
0-(B1) 0+ (A1)
ν29+ (B1)
c-type transitions
c-type transitionsν29
- (A1)
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392.9 391.1 391.3
cm-1
391.4391.2391.0
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29 27 2 30 28 2
30 26 4 31 27 4
30 25 5 31 26 5
28 28 0 29 29 031 24 7 32 25 8
29 27 2 30 28 2
31 23 8 32 24 829 26 3 30 27 3
30 25 5 31 26 5
28 28 0 29 29 0
30 24 6 31 25 6
28 27 1 29 28 1
31 23 8 32 24 829 26 3 30 27 3
29 25 4 30 26 4
30 24 6 31 25 6
28 27 1 29 28 1
30 23 7 31 24 7
0- → ν29 -0+ → ν29 +
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Loomis-Wood plot of the ν29 band: c-type progressions
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0- → ν29 -0+ → ν29 +
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Loomis-Wood plot of the ν29 band: a-type progressions 0- → ν29 +
0+ → ν29 -
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oeoo
eoee
A2A1
B2B1
oeoo
eoee
A2A1
B2B1
oeoo
eoee
B2B1
A2A1
oeoo
eoee
B2B1
A2A1
Ring inversion (B1)
ν29 SiH
2 rocking mode (B
1)
ν29 SiH
2 rocking mode (B
1)
0-(B1) 0+ (A1)
ν29+ (B1)
c-type transitions
c-type transitions
a-type transitions
a-ty
pe tr
ansit
ions
ν29- (A1)
~ 6500 transitions assigned
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Loomis-Wood plot of the ν29 band: a- and c-type progressions
cm-1
0.20.10.0-0.1-0.2
0- → ν29 -0+ → ν29 +
0- → ν29 +0+ → ν29 -
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The Q branch of the ν29 band
cm-1
Exp.
Sim.
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The ν30 ring puckering mode
130 140 160cm-1
180150 170
75 μm Mylar BSSi bolometer
844 interferograms, ~42 h
1060 mTorr, 0.00192 cm-1
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0.0
cm-1
-0.2 -0.1 0.1 0.2
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Loomis-Wood plot of the ν29 band: c-type progressions 0- → ν30 -
0+ → ν30 +
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Spectroscopic parameters for the ν29 and ν30 modes of SCB• Global fit of the ν29 and ν30 modes
• ~8,000 transitions• Ground state constants held fixed to values determined from GSCDs
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0 -0 +
ν29 -
0.00254798(7)
158.38466115(11)
158.1218438(2)
410.20889633(7)
410.03760177(14)
ν29 +
ν30 -
ν30 +
Energy differences in cm-1 and not to scale
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Future work : ring puckering manifold
W.C. Pringle, J. Chem. Phys. 54,4979 (1971)cm-1
90 120 180
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Acknowledgement
Dr. van Wijngaardens group:Cody van DijkSamantha Harder
Dr. Wallace Pringle (Wesleyan University) Dr. Brant Billinghurst (Canadian Light Source)