物理化学学报 >> 2005, Vol. 21 >> Issue (07): 716-720.doi: 10.3866/PKU.WHXB20050704

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钒氢化物电子结构的量子化学研究

李荣; 周上祺; 陈昌国; 梁国明; 刘守平; 孔纪兰   

  1. 重庆大学材料科学与工程学院，重庆 400044； 重庆师范大学化学学院，重庆 400047
  • 收稿日期:2004-10-13 修回日期:2004-12-30 发布日期:2005-07-15
  • 通讯作者: 李荣 E-mail:Rongli258@163.com

Quantum Chemistry Study on Electronic Structure of Vanadium Hydride

LI Rong; ZHOU Shang-qi; CHEN Chang-guo; LIANG Guo-ming; LIU Shou-ping; KONG Ji-lan   

  1. College of Material Science and Engineering, Chongqing University, Chongqing 400044： College of Chemistry, Chongqing Normal University, Chongqing 400047
  • Received:2004-10-13 Revised:2004-12-30 Published:2005-07-15
  • Contact: LI Rong E-mail:Rongli258@163.com

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摘要： 利用电荷自洽离散变分Xα(SCC-DV-Xα)方法计算了钒基固溶体中钒氢反应前后钒及其氢化物(VHx, x=0, 1, 2)、假定原子簇模型VHx*(x=1, 2)和VHx′(x=0, 1)的电子结构. 结果表明：钒与氢气反应生成VH时, 化学效应和结构效应都使V 3d和H 1s轨道向低能量方向移动, 氢化物VH中V 3d和H 1s轨道重叠最多, V－H之间的相互作用较强。VH再与氢气反应生成VH2时, 结构效应使V 3d和H 1s轨道都向高能量方向移动, 氢化物VH2中V 3d和H 1s轨道重叠最少, V和H之间的相互作用较弱。氢化物VH和VH2中不仅存在离子性相互作用, 而且还存在共价性相互作用. 结构效应导致VH2中V－H键的共价性减弱, 从而导致VH2中V和H之间的相互作用减弱. 氢化物VH的费米能级比VH2的低, 说明VH更稳定.

关键词: 金属材料, 钒氢化物, SCC-DV-Xα方法, 电子结构

Abstract: The electronic structure of V and VHx (x=0, 1, 2) in vanadium-based solid solution was calculated by using self-consistent-charge discrete variational (SCC-DV-Xα) method of quantum chemistry. The results demonstrated that the interaction between V and H in VH and VH2 was not only ionic but also covalent; the V－H bond between V and H bands in hydride VH2 was weaker than that in VH. The bonds were due to interaction between the V 4s and H 1s in hydride VH, and the interaction between V 4s, V 3d and H 1s in VH2. Fermi energy level in VH was lower than in VH2. The results suggested that VH is more stable.

Key words: Metallic materials, Vanadium hydride, SCC-DV-Xα method, Electronic structure