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Ce-Promoted Bond Activation of Ethylene Probed by Mass-Analyzed Threshold Ionization Spectroscopy Department of Chemistry University of Kentucky, Lexington,

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Presentation on theme: "Ce-Promoted Bond Activation of Ethylene Probed by Mass-Analyzed Threshold Ionization Spectroscopy Department of Chemistry University of Kentucky, Lexington,"— Presentation transcript:

1 Ce-Promoted Bond Activation of Ethylene Probed by Mass-Analyzed Threshold Ionization Spectroscopy Department of Chemistry University of Kentucky, Lexington, KY YUCHEN ZHANG, SUDESH KUMARI, WENJIN CAO, DONG-SHENG YANG 1

2 Previous Studies on Metal + Ethylene Reactions Crossed-molecular beam study Flow reactor-photoionization mass spectrometry No spectral information Willis, P. A.; Stauffer, H. U.; Hinrichs, R. Z.; Davis, H. F. J. Phys. Chem. A 1999, 103, 3706-3720 Porembski, M.; Weisshaar, J. C. J. Phys. Chem. A 2001, 105, 6655-6667 2

3 La + Ethylene Reaction TOF-MS of La + Ethylene LaC 2 H 2 LaO La LaC 4 H 6 3

4 Ce versus. La [Xe] 4f 1 5d 1 6s 2 58 Ce [Xe] 5d 1 6s 2 57 La Ground state 4

5 Experiment Setup Extraction Cans TOF Tube MCP Detector Source Chamber Metal Rod Nozzle Ablation Laser Carrier Gas & Gaseous Hydrocarbon Spectroscopy Chamber Liquid Hydrocarbon 5

6 TOF-MS of Ce + Ethylene CeO CeC 2 H 2 CeC 4 H 6 6 Ce

7 MATI of CeC 2 H 2 Hot band? 41722 526 128 7

8 MATI Spectrum of CeC 2 H 2 8 Wavenumber (cm -1 )

9 Comparison of CeC 2 H 2 and LaC 2 H 2 Wavenumber (cm -1 ) Ce(C 2 H 2 ) LaC 2 H 2 Wavenumber (cm -1 ) CeC 2 H 2 9

10 Spectral Analysis 3A23A2 3B13B1 2A22A2 2A12A1 2B12B1 0 cm -1 1181 cm -1 42456 cm -1 42654 cm -1 43762 cm -1 2 A 2 ← 3 A 2 42456 cm -1 2 A 1 ← 3 A 2 42654 cm -1 2 B 1 ← 3 B 1 42581 cm -1 10 B3LYP/(SDD, 6-311+g(d,p))

11 ν4ν4 ν3ν3 Experimental and Simulated Spectra 2.27 Å CeC 2 H 2 Wavenumber (cm -1 ) (ν4)(ν4) Intensity not matching. Why? 11 525/534(ν 4 ) 795/826(ν 3 ) 525/532(ν 4 ) (ν3)(ν3) 2 A 2 3 A 2 2 A 1 3 A 2 41594/42456 41722/42654 795/828(ν 3 )

12 [Xe] 4f 1 5d 1 6s 2 [Xe] 5d 1 6s 2 M Ce La M-C 2 H 2 [Xe] 4f 1 6s 1 [Xe] 6s 1 [Xe] 4f 1 6s 0 [Xe] 6s 0 (M-C 2 H 2 ) + Electron configurations on metal atom 12

13 Spin-Orbit Effect on CeC 2 H 2 Electron configuration [Xe] 4f 1 6s 1 Orbital function/ 3A23A2 CeC 2 H 2 (CeC 2 H 2 ) + [Xe] 4f 1 2A22A2 Spin function/ (C 2v ) * From Herzberg’s Molecular Spectra and Molecular Structures A 2 + B 1 + B 2 3 A 1 + 3 B 2 + 3 B 1 13

14 3X3X 3A3A 2 E 1/2 E 3B3B Spin-Orbit Effect on CeC 2 H 2 14 Complete Active Space SCF (CASSCF) Complete Active Space Second Order Perturbation Theory (CASPT2)

15 Conclusions * Similar structure and MATI spectra to LaC 2 H 2, but with one more transition * Ab initio calculations (CASSCF or CASPT2) involving spin- orbit effect 15 +

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