Observation of electron transfer mediated decay in aqueous solution

Photoionization is at the heart of X ray photoelectron spectroscopy XPS , which gives access to important information on a sample s local chemical environment. Local and non local electronic decay after photoionization in which the refilling of core holes results in electron emission from either the initially ionized species or a neighbour, respectively have been well studied. However, electron transfer mediated decay ETMD , which involves the refilling of a core hole by an electron from a neighbouring species, has not yet been observed in condensed phase. Here we report the experimental observation of ETMD in an aqueous LiCl solution by detecting characteristic secondary low energy electrons using liquid microjet soft XPS. Experimental results are interpreted using molecular dynamics and high level ab initio calculations. We show that both solvent molecules and counterions participate in the ETMD processes, and different ion associations have distinctive spectral fingerprints. Furthermore, ETMD spectra are sensitive to coordination numbers, ion solvent distances and solvent arrangemen

Wave-packet dynamics within the multiconfigurational Hartree framework: General aspects and application to NOCl

Manthe U, Meyer HD, Cederbaum LS. Wave-packet dynamics within the multiconfigurational Hartree framework: General aspects and application to NOCl. JOURNAL OF CHEMICAL PHYSICS. 1992;97(5):3199-3213

The multi-configurational time-dependent Hartree approach

Meyer HD, Manthe U, Cederbaum LS. The multi-configurational time-dependent Hartree approach. CHEMICAL PHYSICS LETTERS. 1990;165(1):73-78

Multiconfigurational time-dependent Hartree study of complex dynamics: Photodissociation of NO2

Manthe U, Meyer HD, Cederbaum LS. Multiconfigurational time-dependent Hartree study of complex dynamics: Photodissociation of NO2. JOURNAL OF CHEMICAL PHYSICS. 1992;97(12):9062-9071