Density Functional Theory Study of Reaction Equilibria in Signal Amplification by Reversible Exchange,ChemPhysChem

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Density Functional Theory Study of Reaction Equilibria in Signal Amplification by Reversible Exchange
ChemPhysChem ( IF 2.3 ) Pub Date : 2021-09-22 , DOI: 10.1002/cphc.202100204
Kailai Lin ₁ , Patrick TomHon ₂ , Sören Lehmkuhl ₂ , Raul Laasner ₃ , Thomas Theis _{2,

4,

5} , Volker Blum _{1,

3}

Affiliation

An in-depth theoretical analysis of key chemical equilibria in Signal Amplification by Reversible Exchange (SABRE) is provided, employing density functional theory calculations to characterize the likely reaction network. For all reactions in the network, the potential energy surface is probed to identify minimum energy pathways. Energy barriers and transition states are calculated, and harmonic transition state theory is applied to calculate exchange rates that approximate experimental values. The reaction network energy surface can be modulated by chemical potentials that account for the dependence on concentration, temperature, and partial pressure of molecular constituents (hydrogen, methanol, pyridine) supplied to the experiment under equilibrium conditions. We show that, under typical experimental conditions, the Gibbs free energies of the two key states involved in pyridine-hydrogen exchange at the common Ir-IMes catalyst system in methanol are essentially the same, i. e., nearly optimal for SABRE. We also show that a methanol-containing intermediate is plausible as a transient species in the process.

中文翻译：

可逆交换信号放大反应平衡的密度泛函理论研究

提供了对可逆交换信号放大 (SABRE) 中关键化学平衡的深入理论分析，采用密度泛函理论计算来表征可能的反应网络。对于网络中的所有反应，探测势能面以确定最小能量路径。计算能垒和过渡态，并应用谐波过渡态理论计算接近实验值的汇率。反应网络能面可以通过化学势进行调制，化学势解释了在平衡条件下提供给实验的分子成分（氢气、甲醇、吡啶）对浓度、温度和分压的依赖性。我们表明，在典型的实验条件下，在常见的 Ir-IMes 催化剂体系中，甲醇中涉及吡啶-氢交换的两个关键状态的吉布斯自由能基本相同，即。即，几乎是 SABRE 的最佳选择。我们还表明，含甲醇的中间体作为过程中的瞬态物质似乎是合理的。

更新日期：2021-09-22

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