原子与分子物理学报
原子與分子物理學報
원자여분자물이학보
CHINESE JOURNAL OF ATOMIC AND MOLECULAR PHYSICS
2010年
3期
435-440
,共6页
汤清彬%张东玲%张金平%施德恒%余本海
湯清彬%張東玲%張金平%施德恆%餘本海
탕청빈%장동령%장금평%시덕항%여본해
从头算%光谱常数%CCSD(T)方法
從頭算%光譜常數%CCSD(T)方法
종두산%광보상수%CCSD(T)방법
ab initio calculations%spectroscopic constants%CCSD(T) method
利用CCSD(T)方法和系列相关一致基cc-pVXZ及aug-cc-pVXZ(X=D,T,Q,5)对SH和SD分子的基态平衡几何,谐振频率和离解能进行了优化计算.利用优选出的CCSD(T)/aug-cc-pV5Z方法对SH和SD的基态进行单点能计算,并将计算结果拟合成了Murrell-Sorbie函数.利用得到的解析势能函数,计算了SH和SD的其余3个先谱常数(ωeχe,ae和Be),结果表明:除SD的ωeχe值外,其余结果均与实验值符合得相当好,但计算得出的ωeχe值与推导出的值25.134 cm-1符合得很好.
利用CCSD(T)方法和繫列相關一緻基cc-pVXZ及aug-cc-pVXZ(X=D,T,Q,5)對SH和SD分子的基態平衡幾何,諧振頻率和離解能進行瞭優化計算.利用優選齣的CCSD(T)/aug-cc-pV5Z方法對SH和SD的基態進行單點能計算,併將計算結果擬閤成瞭Murrell-Sorbie函數.利用得到的解析勢能函數,計算瞭SH和SD的其餘3箇先譜常數(ωeχe,ae和Be),結果錶明:除SD的ωeχe值外,其餘結果均與實驗值符閤得相噹好,但計算得齣的ωeχe值與推導齣的值25.134 cm-1符閤得很好.
이용CCSD(T)방법화계렬상관일치기cc-pVXZ급aug-cc-pVXZ(X=D,T,Q,5)대SH화SD분자적기태평형궤하,해진빈솔화리해능진행료우화계산.이용우선출적CCSD(T)/aug-cc-pV5Z방법대SH화SD적기태진행단점능계산,병장계산결과의합성료Murrell-Sorbie함수.이용득도적해석세능함수,계산료SH화SD적기여3개선보상수(ωeχe,ae화Be),결과표명:제SD적ωeχe치외,기여결과균여실험치부합득상당호,단계산득출적ωeχe치여추도출적치25.134 cm-1부합득흔호.
The geometries, harmonic frequencies and dissociation energies of SH(X2 Π) and SD(X2Π) are calculated by using CCSD(T) method in combination with the correlation-consistent basis sets ccpVXZ and aug-ee-pVXZ(X=D, T, Q,5) . Then the analytical potential energy curves for the two species are calculated by employing the most accurate method CCSD(T)/aug-cc-pV5Z and are fitted into the analytic Murrell-Sorbie functions. Subsequently the spectroscopic parameters are evaluated from the constructed potential energy functions. The calculated spectroscopic parameters show a good accord with the recent experiments except the ωeχe of SD(X2 Π). But the ωeχe value for SD(X2 Π) is close to the deduced value of 25. 134cm-1.
