物理学报
物理學報
물이학보
2013年
11期
204-210
,共7页
AsCl%势能函数%光谱常数
AsCl%勢能函數%光譜常數
AsCl%세능함수%광보상수
AsCl%potential energy function%spectroscopic parameter
利用原子分子反应静力学推导出AsCl自由基的基态及激发态的理解极限.采用完全活性空间自洽场和含Davidson修正的内收缩多参考组态相互作用理论方法,在aug-cc-pV5Z基组下对AsCl自由基进行结构优化计算及单点能扫描计算.在AsCl自由基基态势能曲线的基础上,通过Molcas程序拟合出了AsCl的光谱常数De, Re,ωe,ωeχe, Be和αe.通过求解双原子分子核运动的径向Schr¨odinger方程,找到了J=0时该分子基态存在的40个振动态.针对每一振动态,计算了其振动能级、转动惯量Bυ和离心畸变常数Dυ,与现有的实验及其他理论相比较,本文的光谱参数和分子常数结果更准确.
利用原子分子反應靜力學推導齣AsCl自由基的基態及激髮態的理解極限.採用完全活性空間自洽場和含Davidson脩正的內收縮多參攷組態相互作用理論方法,在aug-cc-pV5Z基組下對AsCl自由基進行結構優化計算及單點能掃描計算.在AsCl自由基基態勢能麯線的基礎上,通過Molcas程序擬閤齣瞭AsCl的光譜常數De, Re,ωe,ωeχe, Be和αe.通過求解雙原子分子覈運動的徑嚮Schr¨odinger方程,找到瞭J=0時該分子基態存在的40箇振動態.針對每一振動態,計算瞭其振動能級、轉動慣量Bυ和離心畸變常數Dυ,與現有的實驗及其他理論相比較,本文的光譜參數和分子常數結果更準確.
이용원자분자반응정역학추도출AsCl자유기적기태급격발태적리해겁한.채용완전활성공간자흡장화함Davidson수정적내수축다삼고조태상호작용이론방법,재aug-cc-pV5Z기조하대AsCl자유기진행결구우화계산급단점능소묘계산.재AsCl자유기기태세능곡선적기출상,통과Molcas정서의합출료AsCl적광보상수De, Re,ωe,ωeχe, Be화αe.통과구해쌍원자분자핵운동적경향Schr¨odinger방정,조도료J=0시해분자기태존재적40개진동태.침대매일진동태,계산료기진동능급、전동관량Bυ화리심기변상수Dυ,여현유적실험급기타이론상비교,본문적광보삼수화분자상수결과경준학.
The dissociation limit of AsCl free-radical is correctly determined based on group theory and atomic and molecular statics. Poten-tial energy curves (PECs) for the ground state and several low-lying electronic excited states of AsCl free-radical are calculated using the multi-reference configuration interaction method with the basis set of aug-cc-pV5Z where the Davidson correction is considered as an approximation to full CI. Separation parameters (Re,ωe,ωeχe, D0, De, Be andαe) are evaluated using the PEC of AsCl. Spectro-scopic parameters are compared with those reported in the literature, and excellent agreement is found between them. With the PEC of AsCl free-radical, forty vibrational states of AsCl free-radical are predicted when J=0 by numerically solving the radial Schr¨odinger equation of nuclear notion. For each vibrational state, the vibrational levels and inertial rotation constants are reported.