Nonadiabatic Hydrogen Tunneling Dynamics for Multiple Proton Transfer Processes with Generalized Nuclear-Electronic Orbital Multistate Density Functional Theory,Journal of Chemical Theory and Computation

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Nonadiabatic Hydrogen Tunneling Dynamics for Multiple Proton Transfer Processes with Generalized Nuclear-Electronic Orbital Multistate Density Functional Theory
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2024-09-11 , DOI: 10.1021/acs.jctc.4c00737
Joseph A Dickinson ₁ , Sharon Hammes-Schiffer _{1,

2}

Affiliation

Proton transfer and hydrogen tunneling play key roles in many processes of chemical and biological importance. The generalized nuclear-electronic orbital multistate density functional theory (NEO-MSDFT) method was developed in order to capture hydrogen tunneling effects in systems involving the transfer and tunneling of one or more protons. The generalized NEO-MSDFT method treats the transferring protons quantum mechanically on the same level as the electrons and obtains the delocalized vibronic states associated with hydrogen tunneling by mixing localized NEO-DFT states in a nonorthogonal configuration interaction scheme. Herein, we present the derivation and implementation of analytical gradients for the generalized NEO-MSDFT vibronic state energies and the nonadiabatic coupling vectors between these vibronic states. We use this methodology to perform adiabatic and nonadiabatic dynamics simulations of the double proton transfer reactions in the formic acid dimer and the heterodimer of formamidine and formic acid. The generalized NEO-MSDFT method is shown to capture the strongly coupled synchronous or asynchronous tunneling of the two protons in these processes. Inclusion of vibronically nonadiabatic effects is found to significantly impact the double proton transfer dynamics. This work lays the foundation for a variety of nonadiabatic dynamics simulations of multiple proton transfer systems, such as proton relays and hydrogen-bonding networks.

中文翻译：

广义核电子轨道多态密度泛函理论的多质子传递过程的非绝热氢隧道动力学

质子转移和氢隧道效应在许多具有重要化学和生物学意义的过程中发挥着关键作用。广义核电子轨道多态密度泛函理论（NEO-MSDFT）方法的开发是为了捕获涉及一个或多个质子转移和隧道效应的系统中的氢隧道效应。广义 NEO-MSDFT 方法将传输的质子与电子在量子力学上进行相同的处理，并通过在非正交构型相互作用方案中混合局域 NEO-DFT 态来获得与氢隧道相关的离域电子振动态。在这里，我们提出了广义 NEO-MSDFT 振动态能量和这些振动态之间的非绝热耦合矢量的解析梯度的推导和实现。我们使用这种方法对甲酸二聚体以及甲脒和甲酸的异二聚体中的双质子转移反应进行绝热和非绝热动力学模拟。广义的 NEO-MSDFT 方法可以捕获这些过程中两个质子的强耦合同步或异步隧道效应。发现包含振动非绝热效应会显着影响双质子转移动力学。这项工作为多个质子传输系统（例如质子中继和氢键网络）的各种非绝热动力学模拟奠定了基础。

更新日期：2024-09-11

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