Magneto-optical studies of silver atoms in neon matrices

The neon matrix has a profound influence on the silver atom spin-orbit coupling constant, increasing it from 614 cm−1 in the gas phase to 829 cm −1. This large value is in line with the trend previously found for the other rare gas matrices: spin-orbit constant decrease with rare gas atomic mass increase. The trend is: 829 cm−1 (Ag/Ne), 783 cm−1 (Ag/Ar), 638 cm−1 (Ag/Kr), and 583 cm−1 (Ag/Xe). Calculations of the spin-orbit reduction factors using a “supermolecule” model involving the metal atom and the 12 surrounding rare gas atoms mimics the experimental results well, although the predicted value for Ag/Ne is smaller than the observed one by ∼15%. This discrepancy may arise from a slight collapsing of the rare gas cage onto the entrapped silver atom.