Ab Initio Study of Vibronic and Magnetic 5f-to-5f and Dipole-Allowed 5f-to-6d and Charge-Transfer Transitions in [UX6] n− (X = Cl, Br; n = 1, 2)

• Published in: Journal of chemical theory and computation Vol. 16; no. 8; pp. 5189 - 5202
• Main Authors: Ganguly, Gaurab, Ludowieg, Herbert D, Autschbach, Jochen
• Format: Journal Article
• Language: English
• Published: Washington American Chemical Society 11.08.2020
• Subjects: Absorption spectra; Charge transfer; Chemistry; Coupling; Density functional theory; Electron states; Ligands; Magnetic dipoles; Mathematical analysis; Oxidation; Perturbation theory; Physics; Relativistic theory; Spectroscopy and Excited States; Valence; Wave functions
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.0c00386

The absorption spectra of the octahedral [UX6] n− (X = Cl, Br; n = 1, 2) complexes in the near-infrared (NIR) and UV–vis spectral regions were studied theoretically, using a relativistic restricted active space second-order perturbation theory (RASPT2) wavefunction framework, with the spin–orbit (SO) coupling treated by state interaction, in conjunction with Kohn–Sham density functional theory calculations for determining the vibrational normal modes. The electric-dipole-allowed ligand-to-metal charge-transfer (LMCT) and 5f-to-6d transitions, and the electric-dipole-forbidden 5f-to-5f ligand field (LF) transitions, are thereby obtained within the same theoretical framework. For the 5f-to-5f LF transitions, the observed absorption intensity is mostly due to vibronic coupling with low-energy electric-dipole-allowed transitions, but in some cases, the magnetic dipole intensity of the purely electronic transition has comparable intensity to the vibronic transitions. Experimental LF spectra of 5f2 open-shell systems have been reported decades back, but ab initio calculations of their vibronic intensity have not yet been reported in the literature. Although the LF spectra for the 5f2 systems can be assigned in detail, based on the calculations, the spectra are very complex and the underlying electronic states are strongly multiconfigurational. Therefore, the usefulness of the LF spectra beyond serving as a “fingerprint” of the LF and the metal oxidation state appears to be limited.