Formation and photodestruction of dual dipole-bound anion (H(2)O)(6){e(-)}CH(3)NO(2).
Formation and photodestruction of dual dipole-bound anion (H(2)O)(6){e(-)}CH(3)NO(2).
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双偶极结合阴离子 (H(2)O)(6){e(-)}CH(3)NO(2) 的形成和光破坏。
DOI：
10.1063/1.3152636
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发表时间：
2009
期刊：
影响因子：
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通讯作者：
T. Nagata
中科院分区：
文献类型：
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作者：
Ryuzo Nakanishi;T. Nagata
通过将CH(3)NO(2)引入到Ar-溶剂化的水六面体阴离子(H(2)O)(6)(-)Ar(M)中，形成了一种由水和硝基甲烷组成的新型偶极结合阴离子(CH(3)NO(2))。反应是以Ar为中介的过程，通过连续的Ar蒸发产生有效的能量耗散，形成[CH(3)NO(2)(H(2)O)(6)](-)。用光电子能谱研究了[CH(3)NO(2)(H(2)O)(6)](-)阴离子的电子性质，发现产物阴离子中(H(2)O)(6)(-)的偶极束缚性质基本保持不变，[CH(3)NO(2)(H(2)O)(6)](-)的垂直剥离能为0.65+/-0.02 eV。这一光谱发现，连同其他有提示意义的证据，允许我们将[CH(3)NO(2)(H(2)O)(6)](-)称为(H(2)O)(6){e(-)}CH(3)NO(2)，其中扩散过剩电子通过电子-偶极相互作用与(H(2)O)(6)和CH(3)NO(2)部分相互作用。(H(2O)O)(6){e(-)}CH(3)NO(2)在2134 nm(0.58 eV)处发生光破坏，电子剥离和碎裂发生竞争。后者只导致CH(3)NO(2)(-)(H(2)O)(3)的形成，表明双偶极结合阴离子是CH(3)NO(2)水合价阴离子的前体。
A new type of dipole-bound anion composed of water and nitromethane (CH(3)NO(2)) is formed via the incorporation of CH(3)NO(2) into argon-solvated water hexamer anions, (H(2)O)(6) (-)Ar(m). The reaction proceeds as an Ar-mediated process such that an effective energy dissipation through sequential Ar evaporation gives rise to the formation of [CH(3)NO(2)(H(2)O)(6)](-). Photoelectron spectroscopy is employed to probe the electronic properties of the [CH(3)NO(2)(H(2)O)(6)](-) anion, which reveals that the dipole-bound nature of (H(2)O)(6) (-) remains almost intact in the product anion; the vertical detachment energy of [CH(3)NO(2)(H(2)O)(6)](-) is determined to be 0.65+/-0.02 eV. This spectroscopic finding, together with other suggestive evidences, allows us to refer to [CH(3)NO(2)(H(2)O)(6)](-) as a dual dipole-bound anion described as (H(2)O)(6){e(-)}CH(3)NO(2), where the diffuse excess electron interacts with both the (H(2)O)(6) and CH(3)NO(2) moieties via the electron-dipole interactions. The photodestruction of (H(2)O)(6){e(-)}CH(3)NO(2) at 2134 nm (0.58 eV) occurs with a competition between electron detachment and fragmentation. The latter leads exclusively to the formation of CH(3)NO(2) (-)(H(2)O)(3), indicating that the dual dipole-bound anion serves as a precursor to the hydrated valence anion of CH(3)NO(2).
丙酮簇阴离子的光电子能谱。
DOI：
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发表时间：
2006
期刊：
影响因子：
--
作者：
R. Nakanishi;A. Muraoka;T. Nagata
通讯作者：
T. Nagata