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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Nonlinear Free Energy Relations for Adiabatic Proton Transfer Reactions in Polar Environment. I. Fixed Proton Donor-Acceptor Separation
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Nonlinear Free Energy Relations for Adiabatic Proton Transfer Reactions in Polar Environment. I. Fixed Proton Donor-Acceptor Separation

机译：极性环境中绝热质子转移反应的非线性自由能关系。一，固定的质子供体-受体分离

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摘要

A quadratic free energy relationship (FER) between the kinetic activation free energy ΔG~(++) and the thermodynamic reaction asymmetry ΔG_(RXN) is derived for acid-base ionization proton-transfer reactions AH…B→HB~+ in a polar environment in the proton adiabatic regime, in which the proton is treated quantum mechanically, but does not tunnel. The description differs from traditional treatments in both the proton quantization and the identification of a solvent coordinate as the reaction coordinate. The key coefficients in the FER are analyzed analytically for the simplified case, where the proton donor-acceptor distance is held fixed (a restriction removed in the following paper). In particular, the intrinsic barrier is shown to be the sum of an intrinsic solvent barrier, largely determined by solvent reorganization, and the zero point energy difference of the proton between the reactant and the transition state in a solvent coordinate. The Bronsted coefficient is related to the quantum proton-averaged solute electronic structure at, and the position of, this transition state along this reaction coordinate. Similarities and differences of the FER with the well-known Marcus relation are discussed.
机译：推导了极性中酸碱电离质子转移反应AH…B→HB〜+的动活化自由能ΔG〜（++）与热力学反应不对称性ΔG_（RXN）之间的二次自由能关系（FER）。在质子绝热状态下的环境，其中质子被量子力学处理，但不会隧穿。该描述在质子量化和溶剂坐标作为反应坐标的识别方面与传统处理不同。对于简化的情况，需要分析FER中的关键系数，在这种情况下，质子供体-受体的距离保持固定（以下论文中取消了限制）。特别地，本征壁垒显示为本征溶剂壁垒的总和，该壁垒主要由溶剂重组决定，并且在溶剂坐标中反应物和过渡态之间质子的零点能量差。布朗斯台德系数与沿该反应坐标的该过渡态处的量子质子平均溶质电子结构及其位置有关。讨论了FER与众所周知的Marcus关系的异同。

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