Electron spin echo modulation studies of silver atom solvation and desolvation in ice matrices

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Abstract
Electron spin echo modulation patterns have been obtained at 4.2 K and analyzed for desolvated silver atoms produced at 4.2 K by radiolysis of deuterated ice matrices containing AgF and for solvated silver atoms produced by brief warming to 77 K. The analysis shows that desolvated Ag0 is surrounded by eight equivalent deuterons at 3.1±0.1 Å which suggests a tetrahedral model of four waters with their dipoles pointed away from Ag0 (i.e., a solvated Ag+ geometry). Solvated Ag0 appears to be formed by rotation of one or two waters around one of their OD bonds to put one or two deuterons at ∼1.8 Å from Ag0. These close deuterons do not contribute to the echo modulation pattern because the nuclear splitting is larger than the microwave magnetic field, and the remaining six or seven deuterons at 3.1 Å produce the modulation pattern.

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