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双金属AuAg(SCH)单层保护簇揭示的金属域的成分依赖性电子能量弛豫动力学

Composition-dependent electronic energy relaxation dynamics of metal domains as revealed by bimetallic AuAg(SCH) monolayer-protected clusters.

作者信息

Zheng Hongjun, Tofanelli Marcus A, Ackerson Christopher J, Knappenberger Kenneth L

机构信息

Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306-4390, USA.

出版信息

Phys Chem Chem Phys. 2017 Jun 7;19(22):14471-14477. doi: 10.1039/c7cp00884h.

Abstract

We examined the electronic relaxation dynamics for mono and bimetallic AuAg(SCH) monolayer-protected clusters (MPCs) using femtosecond time-resolved transient extinction spectroscopy. MPCs provide compositionally well-defined model systems for structure-specific determination of nanoscale electronic properties. Based on pulse-energy-dependent transient extinction data, we quantified electron-phonon coupling constants for three distinct AuAg(SCH) MPC samples, where x = 0, 0 < x < 30, and x ∼ 30, as G = (1.61 ± 0.1) × 10 W m K, G = (1.74 ± 0.1) × 10 W m K and G = (2.07 ± 0.15) × 10 W m K, respectively. These results reflect a trend of greater electron-phonon coupling efficiency with increasing silver content. Based on these data, we conclude that gold-atom replacement by silver occurs at surface sites of the 114-atom metal core of the MPC. Definitive determinations of functional response to nanoscale "alloy" formation and dopant inclusion are critical to establishing predictive models for the development of materials that feature nanoparticles as active components.

摘要

我们使用飞秒时间分辨瞬态消光光谱法研究了单金属和双金属AuAg(SCH)单层保护簇(MPC)的电子弛豫动力学。MPC为纳米级电子性质的结构特异性测定提供了成分明确的模型系统。基于与脉冲能量相关的瞬态消光数据,我们对三个不同的AuAg(SCH) MPC样品(其中x = 0、0 < x < 30和x ∼ 30)的电子-声子耦合常数进行了量化,其值分别为G = (1.61 ± 0.1) × 10 W m K、G = (1.74 ± 0.1) × 10 W m K和G = (2.07 ± 0.15) × 10 W m K。这些结果反映出随着银含量增加电子-声子耦合效率更高的趋势。基于这些数据,我们得出结论,银对金原子的取代发生在MPC的114原子金属核的表面位点。确定对纳米级“合金”形成和掺杂剂掺入的功能响应对于建立以纳米颗粒为活性成分的材料开发预测模型至关重要。

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