Electronic spectra and excited states of neptunyl and its [NpO2Cl4]2- complex

Inorganic Chemistry
Jing SuJun Li

Abstract

Electronic states and spectra of NpO(2)(2+) and NpO(2)Cl(4)(2-) with a Np 5f(1) ground-state configuration, related to low-lying 5f-5f and ligand-to-metal charge-transfer (CT) transitions, are investigated, using restricted-active-space perturbation theory (RASPT2) with spin-orbit coupling. Restrictions on the antibonding orbital occupations have little influence on the 5f-5f transition energies, but an important impact on the CT states with an open bonding orbital shell. The present calculations provide significant improvement over previous literature results. The assignment of the experimental electronic spectra of Cs(2)NpO(2)Cl(4) is refined, based on our calculations of NpO(2)Cl(4)(2-). Assignments on the basis of bare NpO(2)(2+) are less reliable, since the equatorial Cl ligands perturb the excited-state energies considerably. Calculated changes of the Np-O bond lengths are in agreement with the observed short symmetric-stretching progressions in the f-f spectra and longer progressions in the CT spectra of neptunyl. A possible luminescence spectrum of the lowest quartet CT state is predicted.

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Citations

May 23, 2012·The Journal of Chemical Physics·Phuong Diem DauLai-Sheng Wang
Aug 18, 2012·The Journal of Chemical Physics·Phuong Diem DauLai-Sheng Wang
Oct 22, 2015·The Journal of Physical Chemistry. a·Norman M Edelstein
Aug 25, 2015·The Journal of Chemical Physics·Attila Kovács, Ivan Infante
May 23, 2014·Chemistry : a European Journal·Frédéric GendronJochen Autschbach
Jul 31, 2014·Inorganic Chemistry·Frédéric GendronJochen Autschbach
Dec 23, 2014·Chemical Communications : Chem Comm·Sean D WoodallLouise S Natrajan
Sep 12, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Shu-Xian HuJun Li
Jul 13, 2012·The Journal of Physical Chemistry. a·Guokui LiuMarianne P Wilkerson
Aug 14, 2021·Journal of the American Chemical Society·Fabrizio OrtuLouise S Natrajan
Nov 26, 2020·Inorganic Chemistry·Bonnie E KlammThomas E Albrecht-Schönzart
Mar 23, 2017·The Journal of Physical Chemistry. a·Beau J BarkerMarianne P Wilkerson
Feb 20, 2018·Inorganic Chemistry·Shu-Xian HuJun Li

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