Zappa Fabio, Denifl Stephan, Mähr Ingo, Bacher Arntraud, Echt Olof, Märk Tilmann D, Scheier Paul
Institut für Ionenphysik und Angewandte Physik, Leopold Franzens Universität, Technikerstrasse 25, A-6020 Innsbruck, Austria.
J Am Chem Soc. 2008 Apr 23;130(16):5573-8. doi: 10.1021/ja075421w. Epub 2008 Mar 29.
Attachment of free electrons to water clusters embedded in helium droplets leads to water-cluster anions (H2O)n(-) and (D2O)n(-) of size n > or = 2. Small water-cluster anions bind to up to 10 helium atoms, providing compelling evidence for the low temperature of these complexes, but the most abundant species are bare cluster anions. In contrast to previous experiments on bare water clusters, which showed very pronounced magic and anti-magic anion sizes below n = 12, the presently observed size distributions vary much more smoothly, and all sizes are easily observed. Noticeable differences are also observed in the stoichiometry of fragment anions formed upon dissociative electron attachment and the energy dependence of their yield. Spectroscopic characterization of these ultracold water-cluster anions promises to unravel the relevance of metastable configurations in experiments and the nature of the still controversial bonding sites for the excess electron in small water-cluster anions.
自由电子附着到嵌入氦滴中的水团簇上会产生尺寸为n≥2的水团簇阴离子(H2O)n(-)和(D2O)n(-)。小的水团簇阴离子最多能结合10个氦原子,这为这些复合物的低温提供了有力证据,但最丰富的物种是裸团簇阴离子。与之前对裸水团簇的实验不同,之前的实验表明在n = 12以下有非常明显的幻数和反幻数阴离子尺寸,而目前观察到的尺寸分布变化更为平滑,所有尺寸都很容易观察到。在解离电子附着时形成的碎片阴离子的化学计量以及其产率的能量依赖性方面也观察到了显著差异。对这些超冷水团簇阴离子进行光谱表征有望揭示实验中亚稳态构型的相关性以及小水团簇阴离子中仍存在争议的多余电子结合位点的性质。