Luminescence spectroscopy of matrix-isolated atomic manganese: Site size and orbital occupancy dependence of crystal field splitting

Abstract

Narrow linewidth emission features observed in the near-UV following y 6 P state excitation of atomic manganese isolated in the solid rare gases are assigned to b 4 D and a 4 P states. These states arise from the 3d 5 4s 2 electronic configuration, identical to that of the 6 S ground state, and the origin of the narrow linewidths. Two thermally stable sites, labeled blue and red on the basis of their position in absorption spectra, are occupied by atomic Mn in Ar and Kr while a single site is present in Xe. The red site produces a single, narrow line emission for the b 4 D state at 329 nm. In contrast, a lineshape analysis of the complex blue site b 4 D state emission between 331 and 332 nm reveals the occurrence of three zero phonon lines ͑ZPLs͒. Millisecond emission decay curves recorded for these features are found to be complex, requiring double and triple exponential fit functions. The origins of the complex decays and multiple ZPLs are shown to arise from weak crystal field splitting ͑CFS͒ of the J = 7 / 2 spin-orbit level of the b 4 D state of atomic Mn isolated in the blue site of the solid rare gases. Fields of cubic symmetry are capable of inducing splitting for J Ͼ 3 / 2 so atoms isolated in both single vacancy and tetravacancy sites in the fcc lattices of the solid rare gases are prone to this effect. b 4 D state emission is also produced following y 6 P excitation for Mn atoms occupying the red sites in Ar and Kr. However, Mn atoms isolated in the larger tetravacancy sites have small matrix shifts and do not exhibit any CFS. The magnitudes of the weak CF splittings are shown to depend on both the excited state electronic configurations 3d 5 4s 2 b 4 D and 3d 6 4s 1 a 4 D states and the size of the matrix site occupied by atomic Mn.

In situ formation and characterisation of singly ionised atomic europium in rare gas matrices—Luminescence spectroscopy and MP2 calculations

“…A pulsed dye laser 12,13 (Quantel TDL90) pumped by the second (532 nm) or third (355 nm) harmonics of a Nd:YAG laser (Quantel YG980E) was used as the excitation source for both time-resolved measurements and laser photolysis. The temporal profile of the Nd:YAG laser pulse is about 4 ns (fwhm) and was operated at a repetition rate of 10 Hz.…”

Spectroscopy of Mn atoms isolated in solid 4He

“…The a 6 D 9/2 -a 6 S 5/2 transition is thus perturbed stronger than the a 4 D 7/2 -a 6 S 5/2 transition and the perturbation is larger in Ar than in Kr. It was also found 12 that the crystal field splitting leads to multiple zero-phonon lines.…”

“…Excitation and luminescence spectra of manganese atoms in the heavier solid rare-gas matrices Ar, Kr, and Xe were recently investigated in detail. [9][10][11][12] …”

Eu/RG absorption and excitation spectroscopy in the solid rare gases: State dependence of crystal field splitting and Jahn–Teller coupling

“…These systems possess spherically symmetric ns 1 or ns 2 S ground states and involve np 1 or ns 1 np 1 excited states which can be reached in fully allowed absorptions in the UV-visible (Vis) spectral region. Mn, the most recent metal studied, 7 is located in the centre of the transition metal series and with a halffull d-orbital, yields a 6 S ground state from the [Ar]3d 5 4s 2 configuration. Spherically symmetric metal atoms have been selected for study because of the isotropic interactions the ground states of these atoms have with their surroundings in the fcc solid rare gases.…”

“…Previous work by the Maynooth group has focused on the luminescence of the metal atoms cadmium, 1 zinc, 2 mercury, 3 and magnesium, 4 and, more recently, sodium, 5 and manganese [6][7][8] isolated in the solid rare gases (RG's). These systems possess spherically symmetric ns 1 or ns 2 S ground states and involve np 1 or ns 1 np 1 excited states which can be reached in fully allowed absorptions in the UV-visible (Vis) spectral region.…”