AI 中文总结
该研究针对氢隧穿系统，提出 V-SHAKE 方法，结合 NEO-MSDFT 动力学采样 diabatic seam 空间，揭示振动耦合变化规律，为速率理论假设提供验证。
AI 中文摘要
氢隧穿是众多化学和生物过程的核心。本文介绍 vibronic-SHAKE（V-SHAKE）方法，用于全面采样支持氢隧穿的能量守恒分子构型。采用核-电子轨道多态密度泛函理论（NEO-MSDFT）动力学的约束形式，其中隧穿氢核被量子化，用于采样对应反应物与产物 NEO-DFT diabatic 振动表面交集的 diabatic seam 空间中的几何结构。将 V-SHAKE 应用于 4-氰基丁醇盐和 Z-4-羟基丁-3-烯-2-酮中的氢和氘隧穿。研究发现，diabatic seam 空间中的振动耦合变化显著，主要源于给体-受体距离的改变。在最小能量交叉点，反应坐标与振动耦合梯度近乎正交，分别由稳定产物相对于反应物的运动或缩短给体-受体距离的运动主导。V-SHAKE 为速率理论所基于的假设提供了基础见解与验证。
英文摘要
Hydrogen tunneling is central to many chemical and biological processes. Herein, we introduce the vibronic-SHAKE (V-SHAKE) approach to comprehensively sample energy-conserving molecular configurations enabling hydrogen tunneling. A constrained form of nuclear-electronic orbital multistate density functional theory (NEO-MSDFT) dynamics, where the tunneling hydrogen nucleus is quantized, is used to sample geometries in the diabatic seam space corresponding to the intersection of the reactant and product NEO-DFT diabatic vibronic surfaces. V-SHAKE is applied to hydrogen and deuterium tunneling in 4-cyanobutanolate and Z-4-hydroxybut-3-en-2-one. The vibronic coupling is found to vary significantly in the diabatic seam space, mainly due to changes in the donor-acceptor distance. The reaction coordinate and gradient of the vibronic coupling at the minimum energy crossing point are nearly orthogonal and are dominated by motions stabilizing the product relative to the reactant or decreasing the donor-acceptor distance, respectively. V-SHAKE provides fundamental insights and validation for assumptions underlying rate theories.
