Threshold Ionization and Spin-Orbit Coupling of CeO

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Presentation transcript:

Threshold Ionization and Spin-Orbit Coupling of CeO Wenjin Cao, Yuchen Zhang, Lu Wu, and Dong-Sheng Yang Department of Chemistry University of Kentucky

Motivations CeO vs. LaO Ce 6s14f1 vs. La 6s1 CeO+ vs. LaO+ Metal oxides are widely used as catalysts or catalyst supports. Small metal oxides are the building blocks of nanoparticles and show size- dependent properties. Our group has recently studied several small LanOm clusters. 42300 874 812 CeO vs. LaO Ce 6s14f1 vs. La 6s1 CeO+ vs. LaO+ Ce 6s04f1 vs. La 6s0 L. Wu, et al., J. Chem. Phys. 137, 084312 (2012) L. Wu, et al., J. Chem. Phys. 140, 224307 (2014)

Previous Measurements In the 1970s, CeO was identified in the absorption spectra of S-type stars and attentions started to be drawn on the studies of CeO molecule. Most comprehensive measurements by Linton, Field and coworkers using LIF: Accurate energies of low-lying excited states in the ranges of 0-4500 and 12500-28600 cm-1. Vibrational and rotational constants for different electronic states. Systematic nomenclature for the excited states based on total angular momentum quantum number J and the projections Ω. R. F. Barrow, et al., Astrophys. J. 229, 439 (1979) C. Linton, et al., J. Chem. Phys. 74, 189 (1981) C. Linton, et al., J. Mol. Spectrosc. 102, 441 (1983)

Previous Calculations Dolg and co-workers quasirelativistic pseudopotential CI methods. Tatewaki and co-workers restricted active space CI (RASCI) calculations with four-component relativistic effect. M. Dolg, et al., J. Mol. Struct. 231, 243 (1991) H. Moriyama, et al., J. Chem. Phys.,138, 224310 (2013)

Experimental Setup Detector TOF Tube Extraction Can PV GV HV He/Ar UV 320 V/cm 532 nm Diffusion Pump Turbo pump Reaction Chamber Spectroscopy Chamber

Computational Details Software: GAMESS 2016 R1 Geometry optimization and frequency analysis: completely renormalized (CR)-CCSD(T) Locating spin-orbit states: Reference states (7 singlet states and 7 triplet states for neutral CeO, and 7 doublet states for corresponding cation) calculated by CI. State energies located by spin-orbit coupled multiconfiguration quasi-degenerate perturbation theory (SO-MCQDPT) calculations. Relativistic Effect: local unitary transformation approximation for the infinite order two component transformations (LUT-IOTC) Basis Set: Quadruple ζ-quality core-correlating all-electron basis sets of Noro and co-workers

MATI Spectrum & Calculated Structure 43015 E0 (cm-1) R (Å) ωe (cm-1) Neutral 1.822 826 Cation 42897 1.776 890

Possible Transitions A+ X+ X+ v=2 v=2 v=2 v=1 v=1 v=1 A X B X, A, B: Ground state, 1st, and 2nd excited states of the neutral X+, A+: Ground state and 1st excited state of the cation A+ X+ X+ v=2 v=2 v=2 v=1 v=1 v=1 A X B

43015 817 890 85 1672 1860 Transitions from 2 lowest neutral states to 1st ionic excited state. 1920 2148 2050 2627 665 2775

Measured and Calculated Energies Neutral Cation Expt. SO-MCQDPT 85 86 665 663 817* 828 - 1609 902* 935 2099 1672 1834 1860 2009 1920 2072 2050 2075 2148 2193 2627 2662 2775 2819

Comparisons a C. Linton, et al., J. Mol. Spectrosc. 102, 441 (1983) MATI Linton, et al.a RASCIb SO-MCQDPT Cation [43.7]3/2 43680 - 43562 [43.0]5/2 43015 42900 Neutral W42 2775 2771.7 2527 2819 W33 2627 2617.3 2381 2662 X43 2148 2140.6 2145 2193 X34 2050 2039.8 2025 2075 U10+ 1920 1931.8 1100 2072 V21 1860 1869.7 959 2009 V10- 1672 1679.4 742 1834 W22 902* 912.2 615 935 W11 817* 811.6 493 828 X23 85 80.3 110 86 X12 a C. Linton, et al., J. Mol. Spectrosc. 102, 441 (1983) b H. Moriyama, et al., J. Chem. Phys.,138, 224310 (2013)

Summary 11 low-lying electronic states for CeO neutral molecule due to spin-orbit effect and 2 for the corresponding cation. Vibrational frequencies for both neutral and cation, but intensities do not follow FC principle. Bond lengths predicted to be 1.822 Å for the neutral and 1.776 Å for the cation. Valence electron configurations are Ce 4f16s1,for neutral CeO and Ce 4f1 for the cation. MATI experiment combining with SO-MCQDPT calculation is a powerful method in identifying the energy splitting due to spin-orbit effect. Thank You