卟啉中双氢转移的多维量子动力学：非谐波振动模式耦合的影响。

IF 4.6 2区化学 Q2 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry Letters Pub Date : 2025-10-01 DOI:10.1021/acs.jpclett.5c02371

Xiaoxi Liu,Wei Liu,Wensheng Bian

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引用次数: 0

摘要

卟啉是研究双氢传递（DHT）隧穿的重要原型，一直受到人们的关注。然而，基于全局从头算势能面（PES）的多维量子动力学（QD）研究仍然是不可缺少的，这对于研究非简谐振动模式耦合是必不可少的。在这里，我们对全球HDNNP-G PES （Litman et al.）进行了第一次多维量子点计算。Faraday discussion . 2020, 221, 526)使用我们小组开发的QD方案来研究卟啉中的DHT隧道。揭示了各种非谐波振动耦合，并系统分析了那些与trans-trans DHT强耦合的模式，包括以前未被识别的Q56模式。我们对隧道分裂的量子力学结果与实验结果吻合较好。此外，我们发现同位素效应对非谐波振动耦合有显著影响。特别是，在单氘化卟啉中，Q2与Q1强烈耦合，而这种耦合对于原始卟啉来说可以忽略不计。

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Multidimensional Quantum Dynamics of Double Hydrogen Transfer in Porphycene: Effects of Anharmonic Vibrational Mode Couplings.

Porphycene is an important prototype for the study of double hydrogen transfer (DHT) tunneling and has attracted great attention. However, a multidimensional quantum dynamics (QD) study based upon a global ab initio potential energy surface (PES) is still unavailable, which is imperative for the study of anharmonic vibrational mode couplings. Here, we perform the first multidimensional QD calculations on the global HDNNP-G PES (Litman et al. Faraday Discuss. 2020, 221, 526) using a QD scheme developed in our group to study DHT tunneling in porphycene. Various anharmonic vibrational couplings are revealed, and a systematic analysis uncovers those modes strongly coupled to trans-trans DHT, including the Q56 mode that was unrecognized before. Our QD results of tunneling splittings agree well with experiment. Moreover, we find that isotope effects have a significant impact on anharmonic vibrational couplings. In particular, in singly deuterated porphycene, Q2 strongly couples with Q1, whereas this coupling is negligible for the original porphycene.

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来源期刊

The Journal of Physical Chemistry Letters CHEMISTRY, PHYSICAL-NANOSCIENCE & NANOTECHNOLOGY

CiteScore

9.60

自引率

7.00%

发文量

1519

审稿时长

1.6 months

期刊介绍： The Journal of Physical Chemistry (JPC) Letters is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, chemical physicists, physicists, material scientists, and engineers. An important criterion for acceptance is that the paper reports a significant scientific advance and/or physical insight such that rapid publication is essential. Two issues of JPC Letters are published each month.