1. C-O and O-H Bond Activation of Methanol by Lanthanum Atom Ruchira Silva, Dilrukshi Hewage and Dong-Sheng Yang Department of Chemistry University of Kentucky Lexington, KY 40506-0055

2. Motivations and Background  C-O and O-H bond activation Catalysts in cross coupling reactions  Decomposition of methanol Alternative fuel  Reaction of M + (M=Sc, Y, Lu) with methanol M(OH) and M(OCH 3 ) are the primary products Undergo subsequent reaction to produce M(OCH 3 ) n [n=1-3] M. Azzaro, S. Breton, M. Decouzon, S. Geribaldi.; lnt. J. Mass Spectrom. Ion Processes 128, 1993, 1-20 Bradley, D.C.; Chem. Rev. 1989, 89, 1317-1322. Kilbourn, B. T. Journal of the Less-Common Metals, 111, 1985, 1-8

3. Experimental Setup Pulsed valve and La rod Repeller and extraction cans MCP DP (2300 l/s) HV TOF TP (400 l/s) 1x10 -6 torr 2x10 -4 torr CH 3 OH

4. TOF of La with CH 3 OH LaO La(OH)(OCH 3 ) La(OH) 2 LaO La(OCH 3 ) 2 La(OH)(OCH 3 ) Increase in CH 3 OH conc. @ 41000 cm -1

5. Wavelength (cm -1 ) MATI Spectrum of La(OH) 2 663 * * 110 0-0 127 Andrews. L, Wang, X.;J. Phys. Chem. A 2006, 110, 4157-4168.  La-O stretching = 624 cm -1  La-O bending (Calc) = 112 cm -1

6. Wavelength (cm -1 ) 1 A 1  2 A 1, B3LYP @ 150 K 663/662 127/126 110/107 Measured and Simulated Spectra of La(OH) 2 Expt. IP = 40145 ± 5 cm -1 Calc. IP= 40388 cm -1 0-0

7. Wavelength (cm -1 ) MATI Spectrum of La(OCH 3 ) 2 ~ 440 52

8. PES of La(OCH 3 ) 2  Single isomer in ionic state  [La, O, C, H]= 128 0 La O C H 1 2 3 4 Dihedral angle[La, O, C, H] (0) Relative energy (cm -1 )

9. Wavelength (cm -1 ) 1 A  2 A, B3LYP @ 150 K Measured and Simulated Spectra of La(OCH 3 ) 2 Expt. IP = 38660 ± 5 cm -1 Calc. IP= 39040 cm -1 0-0 22 229 464 1098

10. Conclusions O-H and C-O bond activation by neutral La atom Structures and electronic states of La(OH) 2 and La(OCH 3 ) 2 IPs & vibrational frequencies of La(OH) 2 and La(OCH3) 2 CH 3 torsion affects on the MATI spectrum

11. Thank you