mrci理论分析oh分子的光谱性质-spectral properties of oh molecules analyzed by mrci theory.docxVIP

摘 要本文运用多参考组态相互作用(MRCI)方法，在不同的基组水平下，计算了 OH 分子 基态和激发电子态的势能曲线。利用计算所得的势能曲线，通过 Level 程序数值求解分子 核运动的径向薛定谔方程，得到分子各电子态的振动能级、转动常数，继而通过数值拟合 得到各个电子态的光谱常数。本文共分五部分：第一部分概述分子光谱和分子势能函数的研究意义与研究现状。第 二部分对有关原子、分子的理论研究内容进行了介绍。第三部分主要介绍了量化计算的一 些理论基础和计算方法。第四部分是用含 Davidson 修正的多参考组态相互作用方法，考虑 核价相互作用和相对论效应，在基组 aug-cc-pv5z，aug-cc-pcv5z，和 cc-pv5z-DK 等水平下 分别对 OH 分子的六个双重态(2?????,2??,2????,2?,)以及两个四重态(4???和 4?)的性质进行 了研究。计算了核间距在 0.05nm~0.80nm 之间的各电子态的势能曲线以及偶极矩函数，通 过 Level 程序数值求解径向薛定谔方程，得到 OH 分子束缚态 X2??和 A2?+所有可能的振 动能级与转动常数，并且所得光谱常数与实验结果符合较好。用 MRCI 方法计算了基态 X2?与其他激发态之间的跃迁偶极矩，对 A2?+-X2?跃迁的跃迁概率，能级寿命，F-C 因子 进行了讨论并与现有的实验数据进行了比较。第五部分对所进行的研究工作以及最后结果 的总结。本文对于 OH 分子势能曲线的高精度计算，以及计算得到的 OH 分子的相关的振动能 级与光谱常数，为 OH 分子激发态的实验研究提供了有益的参考。关键词：OH 分子；势能曲线；多参考组态相互作用；激发态；光谱常数；F-C 因子AbstractIn this paper, the potential curves for the ground state and excited state of OH molecule were calculated by using multi-reference configuration interaction approach in different levels of basis set. Based on the PECS, the radial Schrodinger equations of nuclear motion were numerically treated by Level program , vibrational levels and rotational constants were deduced for various electronic states, then the obtained spectroscopic date of various electronic states are found significant after comparing with the experimental values.This paper is divided into five parts. In the first part, we will present the significance and research status of molecular spectroscopy and potential energy functions. In the second part, we introduce the theoretical research of atoms and molecules. In the third part, we introduce the theory and calculation methods of the quantum mechanical calculation. In the fourth part, the six doublet and two quartet electronic states(2?????,2??,2????,2?,4??,and 4?) of OH radical have been studied with multi-reference configuration interaction(MRCI) method where the Davidson correction, core-valence interaction and relativistic effect are considered with large basis sets aug-cc-pv5z, aug-cc-pcv5z, and cc-pv5z-DK, respectively.