The reaction between phenol and hydroxyl radical, leading to the formation of phenoxy radicals, is analyzed using DFT calculations at the multi-component M06-2X level that accounts for the nuclear quantum effects (NQEs) of hydrogen nuclei. The NQEs affect not only the relative energy diagram of the reaction but also the geometric parameters of the stationary point structures. In the energy minimum structures, the OH covalent bonds have lengthened, while the OHO hydrogen bonds have shortened due to the NQEs. Furthermore, the NQEs also affect the transition state structure, where the distance between carbon and oxygen atoms is strongly influenced by the NQEs of hydrogen nuclei through a hydrogen bond network formed by surrounding water molecules. Different NQEs of hydrogen nuclei have been observed in the / and the stepwise reaction pathways due to differences in the driving force of the reaction.

中文翻译：

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苯酚与羟基自由基反应中质子的显着核量子效应

使用多组分 M06-2X 级别的 DFT 计算分析了苯酚和羟基自由基之间的反应，该反应导致苯氧基自由基的形成，该计算解释了氢核的核量子效应 (NQE)。 NQE 不仅影响反应的相对能量图，还影响驻点结构的几何参数。在能量最小结构中，OH 共价键延长，而 OHO 氢键由于 NQE 缩短。此外，NQE 还影响过渡态结构，其中碳原子和氧原子之间的距离通过周围水分子形成的氢键网络受到氢核 NQE 的强烈影响。由于反应驱动力的差异，在 / 和逐步反应路径中观察到氢核的 NQE 不同。