Global Diabatic Potential Energy Surfaces for the Two Lowest States of Li_(3)  

Li_(3)最低两个电子态的全维透热势能面

作　　者：Yingyue Hong Jiayu Huang Dong H.Zhang 洪樱月;黄嘉宇;张东辉(中国科学院大连化学物理研究所分子反应动力学国家重点实验室,大连116023;中国科学院大学,大连116024;大连理工大学物理学院,北京100049)

机构地区：[1]State Key Laboratory of Molecular Reaction Dynamics,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,China [2]Department of Physics,Dalian University of Technology,Dalian 116024,China [3]University of Chinese Academy of Sciences,Beijing 100049,China

出　　处：《Chinese Journal of Chemical Physics》2025年第2期172-180,I0039,共10页化学物理学报(英文)

基　　金：supported by the National Natural Science Foundation of China(Nos.22103084 and 22233003 to Jiayu Huang,and No.22288201 to Dong H.Zhang);the Innovation Program for Quantum Science and Technology(No.2021ZD0303305)to Dong H.Zhang;the Dalian Innovation Support Program(No.2021RD05)to Dong H.Zhang.

摘　　要：We constructed a new set of diabatic poten-tial energy surfaces(PESs)for the two low-est states involved in Li+Li_(2)reaction by us-ing the fundamental-invariant neural net-work method.The Li_(3)system exhibits a coni-cal intersection(CI)at the geometric D_(3)h symmetries with the energy of the CI point significantly lower than the ground-state en-ab initio ergy of the diatomic molecule.The diabaitc PESs accurately reproduce adiabatic en-ergies,derivative coupling,and energy gradient information,thereby providing a high-fideli-ty description of the CI between the two lowest electronic states.Quantum dynamical calcu-lations have revealed significant non-adiabatic effects in the Li+Li_(2)reaction.本文采用基本不变量神经网络方法构建了Li+Li_(2)反应中最低两个电子态的新型透热势能面.在D_(3)h对称性构型下,两个电子态之间存在一个锥形交叉,且锥形交叉点的能量显著低于基态双原子分子的能量.本文构建的新透热势能面精确复现了量子化学从头算得到的绝热能量、导数耦合及能量梯度,为两个最低电子态之间的锥形交叉提供了一种高精度的表达方法.量子动力学计算显示Li+Li_(2)反应中存在显著的非绝热效应.

关 键 词：Diabatic potential energy matrix Conical intersection Fundamental invariant neural network Non-adiabatic effect 

分 类 号：O561[理学—原子与分子物理]