Ab initio phonon‐coupled nonadiabatic relaxation dynamics of [Au ₂₅ (SH) ₁₈ ] ⁻ clusters

Journal Article · Mon Oct 26 00:00:00 EDT 2015 · Physica Status Solidi B. Basic Solid State Physics

DOI:https://doi.org/10.1002/pssb.201552405· OSTI ID:1401163

Chen, Xue ^[1]; Prezhdo, Oleg V. ^[2]; Ma, Zeyao ^[1]; Hou, Tingjun ^[1]; Guo, Zhenyu ^[1]; Li, Youyong ^[1]

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1. Institute of Functional Nano and Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon‐Based Functional Materials and Devices Soochow University Suzhou Jiangsu 215123 P.R. China
2. Department of Chemistry University of Southern California Los Angeles CA 90089 USA

Nanoscale gold clusters exhibit unique electronic and optical properties. Here, we study the excited state dynamics and electron–phonon coupling of [Au ₂₅ (SH) ₁₈ ] ^– nanoclusters by using quantum‐classical molecular dynamics combined with time‐dependent density‐functional theory. Our result reproduces the experimental measurements and provides further insights into the relaxation dynamics of ligand protected gold clusters. We examine the ultrafast electronic dynamics induced by specific phonon modes. The roles of the Au ₁₃ core and Au ₁₂ ring in the optical process are investigated. We find that the LUMO–HOMO transition is dominated by AuAu stretching of the Au ₁₃ core, whereas the LUMO + 1 − HOMO transition is induced by breathing vibrations of the Au core as well as AuS stretching. We clarify the interplay between electron–phonon couplings and specific energy‐transfer processes in [Au ₂₅ (SH) ₁₈ ] ^– nanoclusters.

• Sponsoring Organization: USDOE
• Grant/Contract Number: DE‐SC0014429
• OSTI ID: 1401163
• Journal Information: Physica Status Solidi B. Basic Solid State Physics, Journal Name: Physica Status Solidi B. Basic Solid State Physics Vol. 253 Journal Issue: 3; ISSN 0370-1972
• Publisher: Wiley Blackwell (John Wiley & Sons)
• Country of Publication: Germany
• Language: English