INFRARED SPECTRUM OF MATRIX-ISOLATED METHYLHYDROXYCARBENE INFRARED SPECTRUM OF MATRIX-ISOLATED...
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![Page 1: INFRARED SPECTRUM OF MATRIX-ISOLATED METHYLHYDROXYCARBENE INFRARED SPECTRUM OF MATRIX-ISOLATED METHYLHYDROXYCARBENE C. A. BAUMANN Department of Chemistry.](https://reader036.fdocuments.net/reader036/viewer/2022081503/56649e8a5503460f94b8f8e7/html5/thumbnails/1.jpg)
INFRARED SPECTRUM OF INFRARED SPECTRUM OF MATRIX-ISOLATED MATRIX-ISOLATED
METHYLHYDROXYCARBENE METHYLHYDROXYCARBENE
C. A. BAUMANN C. A. BAUMANN
Department of ChemistryDepartment of Chemistry
The University of ScrantonThe University of Scranton
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Methylhydroxycarbene
trans cis triplet
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Gas phase photochemistry of biacetyl
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< 450 nm
Gas phase photochemistry of biacetyl
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Difference spectra- 405 nm irradiation
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Computational Details Computational Details
Gaussian 03WGaussian 03W
UB3LYP, UMP2, UMPW1KUB3LYP, UMP2, UMPW1K
6-311++G(2d,p)6-311++G(2d,p)
Scale factors: 0.963, 0.961, 0.943Scale factors: 0.963, 0.961, 0.943
aaGaussian 03, Revision C.02, Frisch, M. J. Gaussian 03, Revision C.02, Frisch, M. J. et al.et al. Gaussian, Inc., Wallingford CT, 2004; Gaussian, Inc., Wallingford CT, 2004; Becke, A. D. Becke, A. D. J. Chem. Phys.J. Chem. Phys. 19931993, , 9898, 5648; , 5648; Lee, C.; Yang, W.; Parr, R. G. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. BPhys. Rev. B 19881988, , 3737, 785;, 785;
Møller, C.; Plesset, M. S. Møller, C.; Plesset, M. S. Phys. Rev.Phys. Rev. 19341934, , 4646, 618;, 618; Lynch, B. J.; Fast, P. L.; Harris, M.; Truhlar, D. G. Lynch, B. J.; Fast, P. L.; Harris, M.; Truhlar, D. G. J. Phys.J. Phys.Chem. A Chem. A 20002000, , 104104, 4811-4815., 4811-4815.
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trans-CH3COH*CH2CO
cis-CH3COH*CH2CO
triplet-CH3COH*CH2CO
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cis-CH3COH*CH2CO
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CH3COH*CH2CO Vibrations
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CD3COD*CD2CO Vibrations
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-100
100
300
500E
ner
gy
(kJ/
mo
l)
= 405 nm
= 436 nm
Intramolecular Hydrogen Transfer
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Acetyl-Acetyl Hydrogen Transfer
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Apparent efficiencies for the production of ketene and MCA.
(nm) matrix CH2CO CD2CO H/D MCA MCA-d6 H/D
N2 3(2)×10-3 1.4(5)×10-4 21 3 (2) ×10-3 5(3)×10-4 6
O2 4(2) ×10-3 4(2) ×10-4 11 6(3) ×10-3 2.5(5) ×10-3 2
405 Ar 2(2) ×10-3 4(1) ×10-5 54 2(2) ×10-3 1.7(3) ×10-4 79
Kr 1.2(7)×10-3 7(3) ×10-6 176 2(1)×10-3 2(1)×10-5 82
Xe 9(5)×10-4 3(3) ×10-6 300 1.2(7) ×10-3 6(6) ×10-6 195
O2 4(2) ×10-4
436 N2 3(2) ×10-3 8(3) ×10-4
Ar 4(4) ×10-4 2(2) ×10-5 25 6(6)×10-5 7(7)×10-5 0.8
254N2 3(2) ×10-3 < 10-5
Ar 0.02(3) 0.006(6) 2 < 10-5 < 10-5
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CH2CO
0.00010
0.00100
0.01000
100 1000 10000 100000
dilution factor
nitrogen
krypton
oxygen
argon
xenon
Concentration Dependence
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CD2O
0.000001
0.000010
0.000100
0.001000
100 1000 10000
dilution factor
nitrogen
krypton
oxygen
argon
xenon
Concentration Dependence
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Pulsed vs. Continuous Irradiation
70
pulsed
cw
405 nm337 nm
20
pulsed
cw
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Pulsed plus Continuous Irradiation
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Triplet-Triplet Absorption
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Triplet-Triplet Absorption
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Triplet-Triplet Absorption
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Triplet-Triplet Absorption
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ConclusionsConclusions
ciscis conformation, complexed with conformation, complexed with keteneketene
H/D isotope effectH/D isotope effect
Acetyl-acetyl H abstractionAcetyl-acetyl H abstraction
Triplet-triplet absorption-TTriplet-triplet absorption-T44
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AcknowledgmentsAcknowledgments
Petroleum Research Fund of the Petroleum Research Fund of the American Chemical SocietyAmerican Chemical Society
National Science FoundationNational Science Foundation
Research CommitteeResearch Committee
Faculty Development BoardFaculty Development Board