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柔性环状分子中旋转运动与拟旋转运动的相互作用

Interplay of Rotational and Pseudorotational Motions in Flexible Cyclic Molecules.

作者信息

Paoloni Lorenzo, Maris Assimo

机构信息

Dipartimento di Fisica e Astronomia, Università di Padova, via Marzolo 8, I-35131 Padova, Italy.

Dipartimento di Chimica G. Ciamician, Università di Bologna, via Selmi 2, I-40126 Bologna, Italy.

出版信息

J Phys Chem A. 2021 May 20;125(19):4098-4113. doi: 10.1021/acs.jpca.1c01472. Epub 2021 May 11.

DOI:10.1021/acs.jpca.1c01472
PMID:33973473
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8279653/
Abstract

Solutions to the time-independent nuclear Schrödinger equation associated with the pseudorotational motion of three flexible cyclic molecules are presented and discussed. Structural relaxations related to the pseudorotational motion are described as functions of a pseudorotation angle ϕ which is formulated according to the definition of ring-puckering coordinates originally proposed by Cremer and Pople ( 1975, 97 (6), 1354-1358). In order to take into account the interplay between pseudorotational and rotational motions, the rovibrational Hamiltonian matrices are formulated for the rotational quantum numbers = 0 and = 1. The rovibrational Hamiltonian matrices are constructed and diagonalized using a Python program developed by the authors. Suitable algorithms for (i) the construction of one-dimensional cuts of potential energy surfaces along the pseudorotation angle ϕ and (ii) the assignment of the vibrorotational wave functions (which are needed for the automatic calculation of rotational transition energies = 0 → = 1) are described and discussed.

摘要

本文给出并讨论了与三个柔性环状分子的赝旋转运动相关的与时间无关的核薛定谔方程的解。与赝旋转运动相关的结构弛豫被描述为赝旋转角ϕ的函数，该赝旋转角ϕ是根据Cremer和Pople最初提出的环皱坐标定义（1975年，97(6)，1354 - 1358）来制定的。为了考虑赝旋转和旋转运动之间的相互作用，针对转动量子数J = 0和J = 1制定了振转哈密顿矩阵。使用作者开发的Python程序构建并对角化振转哈密顿矩阵。描述并讨论了用于（i）沿赝旋转角ϕ构建势能面的一维截面以及（ii）分配振转波函数（这是自动计算转动跃迁能量J = 0 → J = 1所必需的）的合适算法。

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本文引用的文献

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Accuracy Meets Interpretability for Computational Spectroscopy by Means of Hybrid and Double-Hybrid Functionals.通过混合和双混合泛函实现计算光谱学的准确性与可解释性
Front Chem. 2020 Oct 23;8:584203. doi: 10.3389/fchem.2020.584203. eCollection 2020.
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Theoretical Calculations, Microwave Spectroscopy, and Ring-Puckering Vibrations of 1,1-Dihalosilacyclopent-2-enes.
1,1 - 二卤硅杂环戊 - 2 - 烯的理论计算、微波光谱及环扭曲振动
J Phys Chem A. 2020 Oct 8;124(40):8254-8262. doi: 10.1021/acs.jpca.0c07250. Epub 2020 Sep 29.
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Systematic description of molecular deformations with Cremer-Pople puckering and deformation coordinates utilizing analytic derivatives: Applied to cycloheptane, cyclooctane, and cyclo[18]carbon.利用解析导数对 Cremer-Pople 扭转和变形坐标进行分子变形的系统描述：应用于环庚烷、环辛烷和环[18]碳。
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