Issue 14, 2018

Spin–orbit effects in optical spectra of gold–silver trimers


Cationic gold–silver trimers are ideal model systems for the evaluation of relativistic electronic structure theories. The closed-shell triangles allow one to test density functional and wavefunction-based methods in their prediction of optical properties, as dependent on composition and symmetry. Here we present the gas-phase optical spectra of AgNAu3−N+ (N = 0–3) clusters recorded by longitudinal photodissociation spectroscopy in the photon energy range 1.9–4.4 eV. The experimental data are compared to excited electronic state calculations in the framework of all-electron range-separated time-dependent density functional and equation-of-motion coupled cluster theory using two-component as well as the spin-free scalar relativistic theories. In particular, it is shown that for mixed trimers scalar-relativistic corrections are insufficient and a two-component approach becomes obligatory for a correct description of optical response properties including both spin–orbit coupling and charge-transfer effects.

Graphical abstract: Spin–orbit effects in optical spectra of gold–silver trimers

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Article information

Article type
30 Jan 2018
06 Mar 2018
First published
07 Mar 2018
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2018,20, 9108-9114

Spin–orbit effects in optical spectra of gold–silver trimers

A. Shayeghi, L. F. Pašteka, D. A. Götz, P. Schwerdtfeger and R. Schäfer, Phys. Chem. Chem. Phys., 2018, 20, 9108 DOI: 10.1039/C8CP00672E

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