Importance of Double-resonance Effects in Two-photon Absorption Properties of Au(SR)

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2017 Jun 20

PMID 28626569

Citations 1

Authors

Zhongwei Hu

Lasse Jensen

Affiliations

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Abstract

The two-photon absorption (TPA) cross-sections of small thiolate-protected gold clusters have been shown to be much larger than typical small organic molecules. In comparison with larger nanoparticles, their TPA cross-sections per gold atom are also found to be larger. Theoretical simulations have suggested that the large enhancement of these TPA cross-sections comes from a one-photon double-resonance mechanism. However, it remains difficult to simulate TPA cross-sections of thiolate-protected gold clusters due to their large system size and a high density of states. In this work, we report a time-dependent density functional theory (TDDFT) study of the TPA spectra of the Au(SR) cluster based on a damped response theory formalism. Damped response theory enables a consistent treatment of on- and off-resonance molecular properties even for molecules with a high density of states, and thus is well-suited for studying the TPA properties of gold clusters. Our results indicate that the one- and two-photon double-resonance effect is much smaller than previously found, and thus is unlikely to be the main cause of the large TPA cross-sections found experimentally. The effect of symmetry breaking of the Au(SR) cluster due to the ligands on the TPA cross-sections has been studied and was found to only slightly increase the cross-section. Furthermore, by comparing with larger nanoparticles we find that the TPA cross-section per gold atom scales linearly with the diameter of the particles, and that the Kerr non-linear response of the Au(SR) cluster is on the same order as that of bulk gold films.

Citing Articles

Observation of a new type of aggregation-induced emission in nanoclusters.

Kang X, Wang S, Zhu M Chem Sci. 2018; 9(11):3062-3068.

PMID: 29732091 PMC: 5916020. DOI: 10.1039/c7sc05317g.

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