摘要
In this study,six-dimensional(6D)time-dependent wave packet calcula-tions were employed to investigate the dissociation of HCl molecules on two bimetallic surfaces,Cu/Ag(111)and Cu/Au(111).These calculations were based on two accurate potential energy surfaces(PESs)constructed using neu-ral network methodology.Density functional theory(DFT)calculations revealed that the static barrier heights for HCl on Cu/Ag(111)and Cu/Au(111)were 0.32 eV and 0.28 eV,respectively.These values are significantly lower than the barrier height on pure Cu(111)(0.52 eV),primarily due to surface strain effects.However,it was found that the 6D dissociation probability of HCl in(v=0,1,j=0)states on Cu/Au(111)was considerably lower,despite its barrier height being 0.04 eV lower than that for Cu/Ag(111).The underlying mechanism for this observation was attributed to the non-monotonic dependence of the minimum energy path(MEP)on the molecular orientation,which was induced by charge transfer effect for HCl+Cu/Au(111).In contrast,HCl+Cu/Ag(111)exhibited a monotonic dependence.These contrasting behaviors led to dis-tinct differences in rotational alignment and excitation effects for the two reactions.
本文采用六维含时波包计算方法,研究了HCl分子在Cu/Ag(111)和Cu/Au(111)两种双金属表面的解离过程.计算基于通过神经网络方法构建的两个精确势能面.密度泛函理论计算表明:HCI在Cu/Ag(111)和Cu/Au(111)表面的静态势垒高度分别为0.32和0.28eV,较纯Cu(111)表面的静态势垒高度0.52eV显著降低,这主要归因于表面应变效应.尽管Cu/Au(111)的势垒高度比Cu/Ag(111)低0.04 eV,但HCl在(v=0,1;j=0)量子态下的六维解离概率却明显更低,这一反常现象的机理源于最低能量路径对HCI分子取向的非单调依赖性(由电荷转移效应诱导产生);而HCl+Cu/Ag(111)体系则表现为单调依赖.这种差异导致两个反应体系的转动取向和转动激发效应表现出显著不同.
作者
Tianhui Liu
Bina Fu
Dong HZhang
刘天辉;傅碧娜;张东辉(大湾区大学理学院,东莞523000;大湾区高等研究院,东莞523000;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,北京100049;合肥国家实验室,合肥230088)
基金
supported by the National Key R&D Program of China(No.2018YFE0203003)
the National Natural Science Foundation of China(Nos.22173101,22173099,22288201,21703242)
the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0970203)
the Innovation Program for Quantum Science and Technology(No.2021ZD0303305)
Dalian Talents Innovation Support Program(No.2021RD05)
the Open Fund(SKLMRD-K202508)of the State Key Laboratory of Molecular Reaction Dynamics in Dalian Institute of Chemical Physics,Chinese Academy of Sciences.The computational resources are supported by SongShan Lake HPC Center(SSL-HPC)in Great Bay University.
