Mass-Analyzed Threshold Ionization of Lu 2 Lu Wu, Mourad Roudjane, Dong-Sheng Yang Department of Chemistry University of Kentucky Lexington, KY, 40504,USA.

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Mass-Analyzed Threshold Ionization of Lu 2 Lu Wu, Mourad Roudjane, Dong-Sheng Yang Department of Chemistry University of Kentucky Lexington, KY, 40504,USA 1

Previous Studies Zero Electron Kinetic Energy (ZEKE) spectrum of Y 2 – Y 2 : – Y 2 + : Mass Analyzed Threshold Ionization (MATI) spectrum of La 2 – La 2 : – La 2 + : Liu et. al., J. Chem. Phys., 135 (2011) Yang et. al., Int. J. Mass Spectrom. Ion Process. 159 (1995) 203 2

39 Y 57 La 71 Lu 21 Sc Y: 4d5s 2 La: 4f 0 5d6s 2 Lu: 4f 14 5d6s 2 Sc: 3d4s 2 3

Previous Studies Experiment – Thermochemistry ： – Matrix-isolated Raman: Calculations – Ground state Fang et. al.,J. Chem. Phys., 22 (2000) K. A. Gingerich, Faraday Symp. Chem. Soc., 14 (1980) 109 Dolg et. al., Theor. Them. Acc., 108 (2002) 143 Ions? No Previous Studies 4

MATI Experimental Setup Pulsed Valve and Rod Source Carrier Gas Mixture He/Ar Extraction Can MCP  -Metal Shielding Turbo pump Diffusion Pump HV GV TOF 320 V/cm Source ChamberDetection Chamber Laser ablation 5

Theoretical Methods Calculations – Multi-configuration methods: CASPT2 CAS (6,18) – Basis set: ANO-RCC – Relativistic effect: Douglas-Kroll-Hess Hamiltonian; spin orbit coupling – Program: MOLPRO

0-0 MATI of La 2 MATI of Lu 2 7

Vibrational Frequencies: Lu 2 : Lu 2 + : 91 MATI of Lu Ionization Energies: cm -1 (UPPER LIMIT) cm cm

Energy Freq. (cm -1 ) cm -1 (UPPER LIMIT) cm cm -1 IONIZATION ENERGYFREQUENCIESTRANSITION

Lu 2 La 2 Y2Y Electron Removed 5dπ u 6sσ g 5dπ u 5sσ u Neutrals Ions R (Å) E-state sσ u 10

Comparison of Y, La and Lu Δ (eV) YLaLu

12