Spectroscopic and Computational Studies of Spin-Orbit Coupling of Lanthanide Oxides

Grants and Contracts Details


Spin-orbit (SO) coupling makes it possible for spin forbidden transitions or reactions within non-relativistic quantum theory feasible. Thus, quantification of such interactions has important implications in photophysics and chemical catalysis. We plan to quantify SO interactions using lanthanide oxides of the form LnxOy (Ln = lanthanide, x, y = 1-4) as target molecular systems. Through these systems, we will examine the impact on the SO coupling by electron configurations and 4f orbital occupancies of Ln elements and sizes of the metal oxides. By examining these factors, we will explore how SO coupling is affected by the number of Ln 4f electrons for a given size of molecules and if the Ln 4f orbitals remain atomic in nature in these small clusters. Because oxides are the most common Ln compounds, a correct description of SO coupling and relativistic effects in these systems shall expand our ability to predict lanthanide chemical and physical behavior. Ln oxides are produced in laser ablation molecular beams, identified with time-of-fight mass spectrometry, and characterized with laser spectroscopy and relativistic quantum chemical computations. Spectroscopic measurements include mass-analyzed threshold ionization, zero electron kinetic energy, infrared-ultraviolet photoionization, and slow electron velocity-map imaging spectroscopies. Relativistic computations involve scalar relativity corrections, electron correlation, and SO interactions. The main results are SO terms and energies of the neutral molecules and singly charged cations, ionization energies of the neutral species, metal-metal and metal-oxygen vibrational frequencies of the ions and, in some cases, neutrals as well, and charge effects on the bonding and structures. The SO term and energy quantify the extent and strength of electron spin and spatial orbital mixing. The ionization energy is a basic thermochemical property of a molecule and is used to obtain the metal-metal or metal-oxygen bond energies of the neutral molecule through a thermodynamic relation. The vibrational frequencies give direct evidence about the metal-metal and metal-oxygen bonding. The degree of the charge effect reveals the nature of the electron bonding in the highest occupied molecular orbital
Effective start/end date8/1/207/31/24


  • Department of Energy: $357,812.00


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