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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Reactivity of first-row transition metal monocations (Sc~+, Ti~+, V~+, Zn~+) with methyl fluoride: A computational study
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Reactivity of first-row transition metal monocations (Sc~+, Ti~+, V~+, Zn~+) with methyl fluoride: A computational study

机译：第一行过渡金属单阳离子（Sc〜+，Ti〜+，V〜+，Zn〜+）与甲基氟的反应性：计算研究

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The gas-phase reactivity of methyl fluoride with selected first-row transition metal monocations (Sc~+, Ti~+, V~+, and Zn~+) has been theoretically investigated. Our thermochemical and kinetics study shows that early transition-metal cations exhibit a much more active chemistry than the latest transition metal monocation Zn~+. The strong C-F bond in methyl fluorine can be activated by scandium, titanium, and vanadium monocations yielding the metal fluorine cation, MF~+. However, the rate efficiencies vary dramatically along the period 0.73 (Sc), 0.91 (Ti), and 0.028 (V) in agreement with the experimental observation. The kinetics results show the relative importance of the entrance and exit channels, apart from the "inner" bottleneck, to control the global rate constant of these reactions. At the mPW1K/QZVPP level our computed k _(global) (at 295 K), 1.99 × 10~(-9) cm~3 molecule~(-1) s~(-1) (Sc~+), 1.29 × 10 ~(-9) cm~3 molecule~(-1) s~(-1) (Ti ~+), and 3.46 × 10~(-10) cm~3 molecule ~(-1) s~(-1) (V~+) are in good agreement with the experimental data at the same temperature. For the reaction of Zn~+ and CH_3F our predicted value for k_(outer), at 295 K, 3.79 × 10~(-9) cm~3 molecule~(-1) s~(-1), is in accordance with the capture rate constant. Our study suggests that consideration of the lowest excited states for Ti~+ and V~+ is mandatory to reach agreement between calculations and experimental measurements.
机译：从理论上研究了氟与所选的第一行过渡金属单阳离子（Sc〜+，Ti〜+，V〜+和Zn〜+）的气相反应性。我们的热化学和动力学研究表明，与最新的过渡金属单阳离子Zn〜+相比，早期过渡金属阳离子的化学活性更高。甲基氟中的强C-F键可以被scan，钛和钒的单阳离子活化，生成金属氟阳离子MF〜+。但是，速率效率沿0.73（Sc），0.91（Ti）和0.028（V）的周期变化很大，与实验观察结果一致。动力学结果表明，除了“内部”瓶颈外，入口通道和出口通道对于控制这些反应的总体速率常数具有相对重要性。在mPW1K / QZVPP水平，我们计算的k _（global）（在295 K时）为1.99×10〜（-9）cm〜3分子〜（-1）s〜（-1）（Sc〜+）为1.29× 10〜（-9）cm〜3分子〜（-1）s〜（-1）（Ti〜+）和3.46×10〜（-10）cm〜3分子〜（-1）s〜（-1 ）（V〜+）与相同温度下的实验数据吻合良好。对于Zn〜+和CH_3F的反应，我们在295 K时的k_（外）预测值为3.79×10〜（-9）cm〜3分子〜（-1）s〜（-1）与捕获率常数。我们的研究表明，必须考虑Ti〜+和V〜+的最低激发态，才能在计算和实验测量之间达成一致。

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