Accurate double many-body expansion potential energy surface of HS_2(A^2A') by scaling the external correlation  

作　　者：张路路 宋玉志 高守宝 张媛 孟庆田 

机构地区：[1]School of Physics and Electronics, Shandong Normal University

出　　处：《Chinese Physics B》2016年第5期119-125,共7页中国物理B（英文版）

基　　金：Project supported by the National Natural Science Foundation of China(Grant No.11304185);the Taishan Scholar Project of Shandong Province,China;the Shandong Provincial Natural Science Foundation,China(Grant No.ZR2014AM022);the Shandong Province Higher Educational Science and Technology Program,China(Grant No.J15LJ03);the China Postdoctoral Science Foundation(Grant No.2014M561957);the Post-doctoral Innovation Project of Shandong Province,China(Grant No.201402013)

摘　　要：A globally accurate single-sheeted double many-body expansion potential energy surface is reported for the first excited state of HS_2 by fitting the accurate ab initio energies, which are calculated at the multireference configuration interaction level with the aug-cc-pVQZ basis set. By using the double many-body expansion-scaled external correlation method,such calculated ab initio energies are then slightly corrected by scaling their dynamical correlation. A grid of 2767 ab initio energies is used in the least-square fitting procedure with the total root-mean square deviation being 1.406 kcal · mol^（-1）.The topographical features of the HS_2（A_2A＇） global potential energy surface are examined in detail. The attributes of the stationary points are presented and compared with the corresponding ab initio results as well as experimental and other theoretical data, showing good agreement. The resulting potential energy surface of HS_2（A_2A＇） can be used as a building block for constructing the global potential energy surfaces of larger S/H molecular systems and recommended for dynamic studies on the title molecular system.A globally accurate single-sheeted double many-body expansion potential energy surface is reported for the first excited state of HS_2 by fitting the accurate ab initio energies, which are calculated at the multireference configuration interaction level with the aug-cc-pVQZ basis set. By using the double many-body expansion-scaled external correlation method,such calculated ab initio energies are then slightly corrected by scaling their dynamical correlation. A grid of 2767 ab initio energies is used in the least-square fitting procedure with the total root-mean square deviation being 1.406 kcal · mol^（-1）.The topographical features of the HS_2（A_2A＇） global potential energy surface are examined in detail. The attributes of the stationary points are presented and compared with the corresponding ab initio results as well as experimental and other theoretical data, showing good agreement. The resulting potential energy surface of HS_2（A_2A＇） can be used as a building block for constructing the global potential energy surfaces of larger S/H molecular systems and recommended for dynamic studies on the title molecular system.

关 键 词：potential energy surface ab initio calculation HS2 transition state 

分 类 号：TQ125.12[化学工程—无机化工]