摘要
本文通过系统的使用完全活化空间自洽场(CASSCF)和多组态二阶微扰理论(CASPT2)方法配合augcc-p VTZ基组研究了CCCF自由基及其阴阳离子的低能电子态.计算结果显示,CCCF自由基的基态X2A'的转动常数B=4 500.5 MHz,这与实验值的4 555.804 3 MHz吻合良好.垂直激发过程中,最大振子强度出现在2.893e V和4.180 e V的位置,对应的激发属性分别为X2A'→32A″和X2A'→52A'.另外分析得到CCCF自由基的基态电子态X2A'呈现弯曲结构,且其未成对的单电子出现在C3原子上,而其对应的激发态电子态12A″(12Π)则呈现线性结构,并且其对应的未成对单电子出现在C1原子上.
The low-lying electronic states of the CCCF radical and its ionic states was investigated systematically using the complete active space self-consistent field （CASSCF） and multiconfiguration second-order perturbation theory （ CASPT2 ） methods in conjunction with ANO-RCC-TZP basis set .The CCCF was found to have a X2A′ground state with rotational constant =4 500.5 MHz,which was in good agreement with the experimental values of 4 555.804 3 MHz.The calculations of vertical excitation energies of CCCF at 2.973 and 3.782 eV were attribute to the X2A′→ 32A″and X2A′→52A′,respectively,which had larger oscillator strengths.The CCCF radicals presented the ground state X2A′,which could be described as allenic structures with the unpaired electron on the C3 atom,while the excited state 12 A″（12Π） had the linear acetylenic structures with the unpaired electron on the C1 atom.
出处
《吉林师范大学学报（自然科学版）》
2015年第3期94-97,共4页
Journal of Jilin Normal University:Natural Science Edition
基金
吉林省科技发展计划项目(20100510
20101512
201215221)
吉林省教育厅"十二五"科学技术研究项目(2011154
2012175
2012176
2013208)
关键词
小分子激发态
自由基
CCCF
从头算
small molecular excited states
free radical
CCCF
ab initio
