Slow Relaxation of Surface Plasmon Excitations in Au55: The Key to Efficient Plasmonic Heating in Au/TiO2

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• 作者：Oshadha Ranasingha ; Hong Wang ; Vladimír Zobač ; Pavel Jelínek ; Gihan Panapitiya ; Amanda J. Neukirch ; Oleg V. Prezhdo ; James P. Lewis
• 刊名：The Journal of Physical Chemistry Letters
• 出版年：2016
• 出版时间：April 21, 2016
• 年：2016
• 卷：7
• 期：8
• 页码：1563-1569
• 全文大小：480K
• 年卷期：0
• ISSN：1948-7185

文摘

Gold nanoparticles distinguish themselves from other nanoparticles due to their unique surface plasmon resonance properties that can be exploited for a multiplicity of applications. The promise of plasmonic heating in systems of Au nanoparticles on transition metal oxide supports, for example, Au/TiO₂, rests with the ability of the surface plasmon in Au nanoparticles to effectively transfer energy into the transition metal oxide. Here, we report a critical observation regarding Au nanoparticle (Au₅₅) surface plasmon excitations, that is, the relaxation of the surface plasmon excitation is very slow, on the order of several picoseconds. Starting from five plasmon states in Au₅₅ nanoparticles using nonadiabatic molecular dynamics simulations, we find that the relaxation time constant resulting from these simulations is ∼6.8 ps, mainly resulting from a long-lived intermediate state found at around −0.8 eV. This long-lived intermediate state aligns with the conduction band edge of TiO₂, thereby facilitating energy transfer injection from the Au₅₅ nanoparticle into the TiO₂. The current results rule out the previously reported molecular-like relaxation dynamics for Au₅₅.