Acta Chimica Sinica ›› 2005, Vol. 63 ›› Issue (6): 465-472. Previous Articles     Next Articles

Original Articles

过渡金属体系非线性光学性质计算的ECP基组研究

刘彩萍,吴克琛*,洪涛,莽朝永,张明昕,韦永勤,周张锋,庄伯涛   

  1. (中国科学院福建物质结构研究所结构化学国家重点实验室 福州 350002)
  • 投稿日期:2004-06-07 修回日期:2004-11-29 发布日期:2010-12-10
  • 通讯作者: 吴克琛

Study on ECP Basis Sets for Calculating Nonlinear Optical Properties of Transition Metal Systems

LIU Cai-Ping, WU Ke-Chen*, HONG Tao, MANG Chao-Yong, ZHANG Ming-Xin, WEI Yong-Qin, ZHOU Zhang-Feng, ZHUANG Bo-Tao   

  1. (State Key Laboratory of Structural Chemistry, Fujian Institute of the Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002)
  • Received:2004-06-07 Revised:2004-11-29 Published:2010-12-10
  • Contact: WU Ke-Chen

The effective core potential (ECP) approach provides a successful way to calculate the electronic structures of transition metal systems. The performance of several typical ECP basis sets on calculating the nonlinear optical properties of transition metal systems has been evaluated. The static first hyperpolarizabilities β0 of some typical organometallic compounds have been studied at the HF, MP2 and DFT levels by using different ECP basis sets for metallic atoms. To calculate properties of transition metal systems accurately, the electrons of ns and np orbitals should act as valence electrons as well as those of nd. Alternatively speaking, the effect of spin-orbit-coupling is uppermost in relativistic effects. By comparison, the ECP basis set, MHF, was good for computing the first hyperpolarizabilities of organometallic systems, and the Stuttgart RSC 1997 and the SBKJC VDZ were relatively good. The Lanl2dz, the Hay-Wadt MB (n+1) and the Hay-Wadt VDZ (n+1) did not apply the spin-orbit-coupling, so their calculating accuracy was a little poorish. Whereas the CRENBL and the CRENBS provided larger deviations between the computed and experimental values than other ECP basis sets.

Key words: ab initio, ECP basis set, transition metal organometallic compound, the static first hyperpolarizability