Analysis of the Proton Transfer Bands in the Infrared Spectra of Linear N2H+···OC and N2D+···OC Complexes Using Electric Field-Driven Classical Trajectories.,The Journal of Physical Chemistry A

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Analysis of the Proton Transfer Bands in the Infrared Spectra of Linear N2H+···OC and N2D+···OC Complexes Using Electric Field-Driven Classical Trajectories.
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-08-18 , DOI: 10.1021/acs.jpca.0c06756
Dalton Boutwell ₁ , Onyinye Okere ₁ , Oluwaseun Omodemi ₁ , Alexander Toledo ₁ , Antonio Barrios ₁ , Monique Olocha ₁ , Martina Kaledin ₁

Affiliation

In this work, we describe ab initio calculations and assignment of infrared (IR) spectra of hydrogen-bonded ion–molecular complexes that involve a fluxional proton: the linear N₂H⁺···OC and N₂D⁺···OC complexes. Given the challenges of describing fluxional proton dynamics and especially its IR activity, we use electric field-driven classical trajectories, i.e., the driven molecular dynamics (DMD) method that was developed by us in recent years and for similar applications, in conjunction with high-level electronic structure theory. Namely, we present a modified and a numerically efficient implementation of DMD specifically for direct (or “on the fly”) calculations, which we carry out at the MP2-F12/AVDZ level of theory for the potential energy surface (PES) and MP2/AVDZ for the dipole moment surfaces (DMSs). Detailed analysis of the PES, DMS, and the time-dependence of the first derivative of the DMS, referred to as the driving force, for the highly fluxional vibrations involving H⁺/D⁺ revealed that the strongly non-harmonic PES and non-linear DMS yield remarkably complex vibrational spectra. Interestingly, the classical trajectories reveal a doublet in the proton transfer part of the spectrum with the two peaks at 1800 and 1980 cm^–1. We find that their shared intensity is due to a Fermi-like resonance interaction, within the classical limit, of the H⁺ parallel stretch fundamental and an H⁺ perpendicular bending overtone. This doublet is also observed in the deuterated species at 1360 and 1460 cm^–1.

中文翻译：

使用电场驱动的经典轨迹分析线性N2H +··OC和N2D +···OC配合物的红外光谱中的质子传递带。

在这项工作中，我们描述了涉及通量质子的线性键合的N ₂ H ⁺ ···OC和N ₂ D ⁺的氢键结合的离子分子复合物的从头计算和红外（IR）光谱的分配。···OC络合物。鉴于描述质子流变动力学尤其是其IR活性所面临的挑战，我们使用电场驱动的经典轨迹，即近年来我们针对类似应用开发的驱动分子动力学（DMD）方法，级电子结构理论。也就是说，我们提出了一种DMD的修改后的高效数值实现，专门用于直接（或“即时”）计算，我们在MP2-F12 / AVDZ理论水平上对势能面（PES）和MP2进行了计算/ AVDZ用于偶极矩曲面（DMS）。对涉及H ⁺ / D ⁺的高通量振动的PES，DMS以及DMS一阶导数的时间依赖性（称为驱动力）进行详细分析揭示强非谐波PES和非线性DMS产生非常复杂的振动谱。有趣的是，经典轨迹在光谱的质子转移部分显示了一个双峰，两个峰分别位于1800和1980 cm ^–1处。我们发现它们的共同强度是由于H ⁺平行拉伸基波和H ⁺垂直弯曲泛音在经典极限内的费米式共振相互作用。在氘化的物种中，在1360和1460 cm ^–1处也观察到这种双峰。

更新日期：2020-09-18

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