Spectroscopy of 142NdO: New results

Electronic structure of NdO via slow photoelectron velocity-map imaging spectroscopy of NdO¯

“…Prior experimental work is consistent with our measurements -fluorescence work by Linton 27 and Effantin 28 as well as emission spectra from hot 142 NdO by Shenyavskaya 26 have collectively found states at term energies in the 10500-16500 cm -1 range that reside near features observed in the cryo-SEVI spectrum, though state assignments are limited to the value of Ω based on relative intensities of P, Q, and R branches in each transition. These values are reported in the rightmost column of Table 2.…”

“…2 are reported in Table 2 alongside available literature values. 28,32 In these tables, electronic states are labelled using Hund's case c notation with the (N)Ω convention common in the literature on NdO; 20,27,28,62 (N)Ω represents the N th state with each value of Ω, the summed projections of the electronic orbital and spin angular momenta onto the internuclear axis. Assignments listed in Table 1 for the peaks with upper case letters originate from the anion ground state (see below) and refer to the neutral states.…”

“…24,25 A large number of bands at higher resolution were measured lying between 7500 and 12600 cm -1 , 26 and laser induced fluorescence (LIF) identified low lying states in agreement with ligand field theory. 27,28 Complete active space self-consistent-field (CASSCF) and multireference configuration interaction (MRCI) calculations detail 54 states below 8000 cm -1 , 29 amongst a number of theoretical efforts. [30][31][32] Here, we utilize slow photoelectron velocity-map imaging spectroscopy of cryogenically cooled NdO¯ anions (cryo-SEVI) in tandem with high-level quantum chemical calculations to investigate the electronic and vibrational structure of neutral NdO.…”

“…The values of adiabatic ionization energy (IE) and adiabatic electron affinity (EA) have included SO-CASSCF/NEVPT2 spinorbit coupling corrections of -28 cm -1 for IE and 315 cm -1 for EA. The experimental values for NdO + are taken from the work of Heaven and coworkers,18 the experimental bond length of NdO is the R 0 value from Effantin and coworkers,28 and the ω e and ω e χ e values are derived using the vibrational energy spacings determined by Linton and coworkers 27. Computed levels of NdO from both CASSCF and NEVPT2, both using QZVP-PP basis sets with perturbative inclusion of spin-orbit coupling, along with state assignments, a comparison to experimental fluorescence measurements from Linton and co-workers,27 and compositions in terms of the spin-free wave functions.…”

Electronic structure of NdO via slow photoelectron velocity-map imaging spectroscopy of NdO¯

“…The values of adiabatic ionization energy (IE) and adiabatic electron affinity (EA) have included SO-CASSCF/NEVPT2 spinorbit coupling corrections of -28 cm -1 for IE and 315 cm -1 for EA. The experimental values for NdO + are taken from the work of Heaven and coworkers,18 the experimental bond length of NdO is the R 0 value from Effantin and coworkers,28 and the ω e and ω e χ e values are derived using the vibrational energy spacings determined by Linton and coworkers 27.…”