CAJ | 학술논문

【目的】过渡族金属与铝之间的化学成键特性是化学与材料等领域的基础，对铝-4d过渡族金属二聚体的物理性能进行研究。【方法】用密度泛函B3 LYP方法计算铝-4d过渡族金属二聚体的键长、振动频率、解离能、电离势、能隙和二极矩。【结果】对中性和荷电的二聚体，除 AlMo、AlNb＋和 AlMo＋外其键长从 AlY到 AlPd先减少后增加，解离能和振动频率的变化趋势与之相反。电离势随原子序数的递增先增加，在 AlRh处达到极大值后减少。除 AlTc的振动频率外，计算结果与已有的实验结果和其他的理论计算结果相符。计算结果还显示除 AlCd外，前过渡族金属与铝的结合强度比后过渡族金属的结合要强。荷电二聚体的自旋多重度比相应的中性二聚体差±1。带正电的二聚体的键长比中性和带负电的二聚体的键长要长，荷电二聚体的解离能大于中性二聚体的解离能，解离方式为 AlX＋→X ＋ Al＋和 AlX-→Al ＋ X-。
【목적】과도족금속여려지간적화학성건특성시화학여재료등영역적기출，대려-4d과도족금속이취체적물이성능진행연구。【방법】용밀도범함B3 LYP방법계산려-4d과도족금속이취체적건장、진동빈솔、해리능、전리세、능극화이겁구。【결과】대중성화하전적이취체，제 AlMo、AlNb＋화 AlMo＋외기건장종 AlY도 AlPd선감소후증가，해리능화진동빈솔적변화추세여지상반。전리세수원자서수적체증선증가，재 AlRh처체도겁대치후감소。제 AlTc적진동빈솔외，계산결과여이유적실험결과화기타적이론계산결과상부。계산결과환현시제 AlCd외，전과도족금속여려적결합강도비후과도족금속적결합요강。하전이취체적자선다중도비상응적중성이취체차±1。대정전적이취체적건장비중성화대부전적이취체적건장요장，하전이취체적해리능대우중성이취체적해리능，해리방식위 AlX＋→X ＋ Al＋화 AlX-→Al ＋ X-。
Objective]The nature of chemical bond between a transition metal and aluminium is a base of chemistry and materials science.The physical properties of AlX (X=4d elements)Di-mer were studied.[Methods]Bond length,vibrational frequency,dissociation energy,ionization potential,energy gap and dipole moment of the title molecules in neutral and charged ions were studied by density functional method B3LYP.[Results]For neutral and charged molecules,the bond length decreases from AlY (AlY+ and AlY-)to AlPd (AlPd+ and AlPd-)except AlMo, AlNb+ and AlMo+,and then increases.Opposite trends are observed for dissociation energy and vibrational frequency.The ionization energy through the series increases and reaches the maximum at AlRh and then decreases.The present results are in good agreement with the a-vailable experimental and other theoretical values except the vibrational frequency of AlTc.The present calculations show that the late transition metal can combine strongly with aluminum compared with the former transition metal (except AlCd).For cationic dimer,the dissociation procedure of channel AlX+→X+ Al+ is easier than that of channel AlX+→Al+ X+.Howev-er,for anionic dimer,the channel AlX-→Al + X- is favorable except AlY-,AlPd- and Al-Cd-.The ground state spin multiplicity of the charged ions differs by ± 1 from that of the cor-responding neutral parent.The bond length of AlX+ is larger than that of AlX (except AlPd) and that of AlX-(except AlRu- and AlPd-).The dissociation energy of charged dimer is big-ger than that of neutral counterpart.