Energetics of activation of tetracarbonylferrate(1-) and pentacarbonylchromate(1-) in gaseous collisions
Energetics of activation of tetracarbonylferrate(1-) and pentacarbonylchromate(1-) in gaseous collisions
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四羰基铁酸盐(1-)和五羰基铬酸盐(1-)在气体碰撞中的活化能量学
DOI：
10.1021/j100333a055
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发表时间：
1988
期刊：
影响因子：
--
通讯作者：
R. Cooks
中科院分区：
文献类型：
--
作者：
V. Wysocki;H. Kenttämaa;R. Cooks
根据已知的热化学和测定的Fe(CO)4“和Cr(CO)5~+的脱碳产物丰度，估算了Fe(CO)4”和Cr(CO)5~的低能(EV)和高能(KeV)碰撞激活解离的内能分布，并与阳离子自由基Fe(CO)5+、Fe(CO)4+、Cr(CO)6+和Cr(CO)5+的分布进行了比较。结果表明，对于负离子和正离子，碰撞活化所沉积的平均内能是相似的。然而，对负离子的计算结果表明，在两个碰撞能区中，碰撞激活的电子脱离可能与碰撞激活的解离竞争或跟随碰撞激活解离。电荷反转实验记录了Fe(CO)4“和Cr(CO)5”产生的带正电荷的碎片离子，进一步支持了高能碰撞中的电子脱离。
Internal energy distributions associated with low-energy (eV) and high-energy (keV) collision-activated dissociation of Fe (CO) 4" and Cr (CO) 5~ have been estimated from the known thermochemistry and the measured abundances of decarbonylation products of these ions and are compared with the distributions estimated for the cation radicals Fe (CO) 5+, Fe (CO) 4+, Cr (CO) 6+, and Cr (CO) 5+. It is shown that the average amount of internal energy deposited by collisional activation is of similarmagnitude for the negative and positive ions. However, the results obtained for the negative ions indicate that collision-activated electron detachment may compete with or follow collision-activated dissociation in both collision energyregimes. Further support for electron detachment in high-energy collisions is obtained from charge inversion experiments which record the positively charged fragment ions arisingfrom Fe (CO) 4" and Cr (CO) 5".