Laser Spectroscopy of Gadolinium Monofluoride: Ligand Field Assignments of States in the 0–3 eV Range

The Electronic Structure of the Lanthanide Monohalides: A Ligand Field Approach

“…LnX center-of-gravity values were determined by shifting (8,10,12,13), taking into account the Sections 1.3 to 1.5 ) , and all of the Rydberg states are computed dependence on the internuclear distance (22) de-ignored. fined in Eq.…”

“…0 (6p, 6p) EuF (9), GdF (10), TbF (11,12), DyF (13), HoF (14, ú 0; the availability of empirically adjustable shifts of orbital 15), YbF (16)(17)(18), LuF (19,20), LaCl (21), and YbCl energies for several LnF (5,8,10,13) and LnO (37, 38) (17). In recent years, ligand field theory (LFT) models molecules now makes it possible to carry out similar calculathat provide valuable qualitative and quantitative predictions tions for all of the lanthanide monohalides; (iii) the concerning the electronic, vibrational, and rotational states B k 0 (nl, nl) parameters, the anisotropic part of the ligand of diatomic lanthanide oxides and fluorides have been develfield that lifts the m l å l degeneracy of an nl orbital and oped (22)(23)(24)(25) 2 To whom correspondence should be addressed.…”

Low‐Lying Excited States of Lanthanide Diatomics Studied by Four‐Component Relativistic Configuration Interaction Methods

“…The basis function for F is (12s8p2d), which is composed of (12s8p) [38] and 2×d correlating functions of Huzinaga et al [55] The HFR/DC calculations for GdF 2+ and GdF + were first performed at the calculated internuclear distance (R e ) of 3.7599 au, [26] whereas the experimental distance is 3.71 au. [8] We initially assumed the configuration [Gd 10+ (5s 2 5p 6 )F − (2s 2 2p 6 )] 9+ (4f 7 ) and [Gd 10+ (5s 2 5p 6 )F − (2s 2 2p 6 )] 9+ (4f 7 6s 1 ) for HFR/DC. We then performed GOSCI calculations for GdF 2+ , GdF + , and GdF.…”

“…Kaledin et al [8] made a detailed investigation of the GdF molecule, and characterized most of its excited states up to about 3.0 eV above the ground state. They also performed LFT calculations, which gave results consistent with experiment, although some uncertainties remained.…”

“…The electronic structure of these molecules has previously been studied by methods such as ligand field theory, [6][7][8] molecular orbital theory with/without spin-orbit configuration interaction (SOCI), [9][10][11][12][13] and four-component relativistic theory. [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29] Although theory and computer programs have developed rapidly in recent decades, the behavior of f electrons in lanthanide compounds remains a challenging subject.…”