Ultraviolet Absorption Spectra of Transition Metal Atoms in Rare-Gas Matrices

Abstract

Absorption spectra from 2200 to 4000 Å have been obtained of chromium, manganese, iron, cobalt, copper, nickel, tin, and palladium atoms trapped in argon matrices at 4.2°K and of iron and copper in krypton and xenon matrices at 4.2 and 20°K. Observed transitions were found to correlate with gas phase transitions, under the assumption of a matrix and atomic configuration dependent shift of the atomic transitions. Energy shifts of the transitions were inversely proportional to matrix atom size. Configurations with an odd number of 3d electrons were shifted less than those with an even number. Within a given configuration, the transitions at higher energies were shifted more than those at lower energies. A Lennard-Jones potential was unsuccessful in generating the observed energy shifts caused by the interaction between the trapped atom and the matrix. Atom diffusion and resultant aggregation within the matrix both during the condensation of the solid from the gas phase and during warming was found to be a significant effect. Oscillator strengths, calculated from observed spectra, were from 10 to 100 times less than gas phase values.

Matrix spectroscopy of Ag, Ta, W, and Mo trapped in Ar and Xe using a triode sputtering source

“…Ag has one of the highest sputtering rates [sf (1 + y) = 3.4 atoms/ion at 500 eV incident Xe+], where y is the secondary electron coefficient. 10 The atomic silver spectrum shown in Fig. 1 compares well with data in the literature 5 but also shows additional spectral features around 35000 cm -1.…”

A Matrix Isolation and Computational Study of Molecular Palladium Fluorides: Does PdF6 Exist?

“…Summary of thermochemistry from relativistic DFT calculations a , the spectral features at 40310, 42300, 45410 cm −1 are essentially identical to those of Pd atoms in argon matrices [75][76][77][78][79][80][81][82]. On annealing to 18 K the Pd atomic spectral features were replaced by broader ones at 40210, 45880 and 49010 cm −1 .…”

Photochemistry of Fe:H2O Adducts in Argon Matrixes: A Combined Experimental and Theoretical Study in the Mid-IR and UV–Visible Regions

“… a Experimental reference data for free Fe atom from Nave et al b SO-CASPT2 energy levels for free iron atoms and SO-MS-CASPT2 energy levels for Fe:H 2 O adducts, with relative oscillator strengths in parentheses. c Positions of absorption bands in experimental spectra presented in this work (Fe:Ar ∼ 1:1000), with relative abundance in parentheses. d Experimental reference data for Fe in an argon matrix (Fe:Ar 1:2000) from Mann and Broida, with oscillator strengths in parentheses and poorly resolved bands in italics (with intensities rather than oscillator strengths). Experimental reference data for Fe 2 in an argon matrix from de Vore et al …”