OCS binding to and reactivity with isolated gold cluster cations, Au_n⁺ (n = 1–10), has been studied by infrared multiple photon dissociation (IR-MPD) spectroscopy in conjunction with quantum chemical calculations. The distribution of complexes Au_nS_x(OCS)_m⁺ formed reflects the relative reactivity of different cluster sizes with OCS, under the multiple collision conditions of our ablation source. The IR-MPD spectra of Au_n(OCS)⁺ (n = 3–10) clusters are interpreted in terms of either μ¹ or μ² S binding motifs. Analysis of the fragmentation products following infrared excitation of parent Au_n(OCS)⁺ clusters reveals strongly size-selective (odd–even) branching ratios for OCS and CO loss, respectively. CO loss signifies infrared-driven OCS decomposition on the cluster surface and is observed to occur predominantly on even n clusters (i.e., those with odd electron counts). The experimental data, including fragmentation branching ratios, are consistent with calculated potential energy landscapes, in which the initial species trapped are molecularly bound entrance channel complexes, rather than global minimum inserted structures. Attempts to generate Rh_n(OCS)⁺ and Pt_n(OCS)⁺ equivalents failed; only sulfide reaction products were observed in the mass spectrum, even after cooling the cluster source to −100 °C.

中文翻译：

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OCS结合和与金簇的大小选择反应性的红外研究，Aun +（n = 1-10）。

OCS与孤立的金簇阳离子Au _n ⁺（n = 1-10）结合并与之反应，已通过红外多光子离解（IR-MPD）光谱结合量子化学计算进行了研究。在我们的消融源的多种碰撞条件下，形成的配合物Au _n S _x（OCS）_m ⁺的分布反映了不同簇尺寸与OCS的相对反应性。Au构成的IR-MPD光谱_Ñ（OCS）⁺（Ñ = 3-10）簇中来解释任一μ的¹或μ ²S绑定图案。以下父Au构成红外激发的碎裂产物的分析_Ñ（OCS）⁺簇揭示强烈大小选择性（奇偶）分别分支为OCS和CO损失率。CO损耗表示红外驱动的OCS在团簇表面分解，并且观察到主要发生在偶数个团簇（即那些具有奇数电子数的团簇）上。实验数据，包括碎片支化比率，与计算得到的势能图一致，其中捕获的初始物种是分子结合的入口通道复合物，而不是整体最小插入结构。尝试生成Rh _n（OCS）⁺和Pt _n（OCS）⁺等值项目失败；即使在将簇源冷却至-100°C后，在质谱图中也仅观察到硫化物反应产物。