摘要
采用密度泛函(DFT)方法B3LYP/Gen,在Pu为相对论有效原子实势(RECP)基组水平上计算优化得到了分子轴方向不同电偶极场(-0.002～0.002 a.u.)作用下,Pu_2分子的基态D。。(X^(13)∑_g^+)几何结构、偶极矩和分子总能量.在优化构型下,用同样的基组采用含时密度泛函(TDDFT)方法(TD-B3LYP),研究了同样外电场条件下,Pu_2的激发能和振子强度的影响.计算结果表明,在外场作用下,Pu_2的前5个激发态电子跃迁光谱属于可见-红外光谱,波长为642.49～943.77 nm,这是钚原子的奇异特征;激发能与外电场的关系近似满足Grozema等人提出的关系;电场对振子强度的影响比较复杂,但仍满足跃迁选择定则.
The ground states of Pu2 under different electric fields ranging from --0. 002 to 0. 002 a. u. have been optimized using density functional theory DFT/B3LYP with Gen for Pu. The excitation ener- gies have been calculated under the same electric fields employing the time-dependent DFT method. The results show that the electronic state, total energy, molecular geometry, dipole moment, excitation en- ergy and oscillator strengths are strongly dependent on the field strength of applied electric field. The dependence of the calculated excitation energies on the applied electric field strength is fitting well to the relationship proposed by Grozema. The spectra of the first five excited electron of Pu2 are in the region of visible - infrared. The wavelength is in 642.49-943.77nm.
出处
《原子与分子物理学报》
CAS
CSCD
北大核心
2010年第5期833-838,共6页
Journal of Atomic and Molecular Physics
基金
国家自然科学基金项目(10965002)
江西省教育厅科技项目(GJJ10540)
关键词
Pu2
激发态
电偶极场
TD-DFT
Pu2, excited state, dipole electric field, Time-Dependent DFT
