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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Blackbody Infrared Radiative Dissociation of Partially Solvated Tris(2,2'-bipyridine)ruthenium(II) Complex Ions
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Blackbody Infrared Radiative Dissociation of Partially Solvated Tris(2,2'-bipyridine)ruthenium(II) Complex Ions

机译：部分溶解的三（2,2'-联吡啶）钌（II）络合物离子的黑体红外辐射解离

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摘要

Electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometry has been utilized to study solvers of tris(2,2'-bipyridine)ruthenium(II). Spontaneous dissociation of solvent (acetonitrile, acetone, or methyl ethyl ketone) from the solvation shell occurs when these ions are trapped for extended periods of time in the ICR cell. The pressures employed in these experiments are low enough (10~(-9) to 10~(-8) mbar) to neglect (or partially neglect) collisional activation as a means for dissociation. Therefore, it is suggested that the solvated ruthenium species undergo dissociation following the absorption of blackbody infrared radiation. Solvent-complex dissociation has been studied at several pressures ranging from 10~(-9) to 10~(-8) mbar to provide a range of dissociation data in the low-pressure regime. The results reported here demonstrate the consistency of the dissociation rate constants at pressures that differ by an order of magnitude. Temperature dependence studies were performed to extract zero-pressure activation energies from Arrhenius analyses. Given the number of degrees of freedom and the magnitude of the rate constants at a given temperature of the ruthenium complex ion solvates, the experimental Arrhenius activation energies are likely to be substantially lower than the true bond dissociation energies. ZINDO seiempirical methods, which were calibrated against DFT and experimental values, have been used to determine optimized structures and vibrational frequencies for bipyridine-containing ruthenium(II) solvates. These parameters were then used both for master equation modeling and the truncated Boltzmann/modified Tolman approach, each of which provide calculated binding energies of the solvents to the ruthenium complex ion. Solvation energies in the range 15-20 kcal/mol were found for binding of solvent molecular in the first solvation shell of tris(2,2'-bipyridine) ruthenium(II) ions.
机译：电喷雾电离傅立叶变换离子回旋共振（ESI-FTICR）质谱已用于研究三（2,2'-联吡啶）钌（II）的求解器。当这些离子在ICR池中长时间捕获时，溶剂（乙腈，丙酮或甲乙酮）会自溶剂化壳中自发解离。这些实验中使用的压力足够低（10〜（-9）至10〜（-8）mbar），可以忽略（或部分忽略）碰​​撞激活作为分离手段。因此，建议溶剂化的钌物质在吸收黑体红外辐射后发生离解。已经在10〜（-9）到10〜（-8）mbar的几种压力下研究了溶剂-复合物的解离，以提供低压状态下的一系列解离数据。此处报道的结果证明了在相差一个数量级的压力下，解离速率常数的一致性。进行了温度依赖性研究，从Arrhenius分析中提取零压力活化能。给定自由度的数量和在给定温度下钌络合物离子溶剂化物的速率常数的大小，实验的Arrhenius活化能很可能大大低于真实的键解离能。针对DFT和实验值进行校准的ZINDO经验方法已用于确定含联吡啶的钌（II）溶剂化物的优化结构和振动频率。然后将这些参数用于主方程建模和截断的Boltzmann /改进的Tolman方法，每一个都提供了溶剂与钌络合物离子的计算结合能。发现溶剂分子在三（2,2'-联吡啶）钌（II）离子的第一个溶剂化壳中的结合能为15-20 kcal / mol。

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