CAJ | 학술논문

利用耦合簇理论CCSD(T)和相关一致基组cc-pVXZ和aug-co-pVXZ(X=2,3,4,5)计算了SH+和SD+的基态平衡几何re、谐振频率ωe和离解能De.计算结果表明,所用基组越大,得到的结果与实验值之间的差别就越小,因此我们选用了大基组aug-cc-pV5Z在0.07～2.50 nm的核间距范围内对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个光谱常数(ωexe,αe和Be),其结果与实验值符合得相当好.
이용우합족이론CCSD(T)화상관일치기조cc-pVXZ화aug-co-pVXZ(X=2,3,4,5)계산료SH+화SD+적기태평형궤하re、해진빈솔ωe화리해능De.계산결과표명,소용기조월대,득도적결과여실험치지간적차별취월소,인차아문선용료대기조aug-cc-pV5Z재0.07～2.50 nm적핵간거범위내대SH+화SD+적기태진행단점능계산,병장계산결과의합성료Murrell-Sorbie함수.이용득도적해석세능함수,계산료SH+화SD+적기여3개광보상수(ωexe,αe화Be),기결과여실험치부합득상당호.
From the analyses of the influences on the geometries,harmonic frequencies and dissociation energies for the SH+(X3∑-)and SD+(X3∑-)cations by the basis sets cc-pVXZ and aug-cc-pVXZ(X=2,3,4,5)in the CCSD(T)model,such conclusion can be gained that the larger the basis set is.the smaller is the deviation between the theories and the experiments.For the reason of which,the potential energy curves for the two cations are calculated using a very large basis set,aug-cc-pV5Z,in the valence range from 0.07 to 2.50nm and are fitted into the analytic Murrell-Sorbie function.Then the spectroscopic parameters(De,Be,αe,ωexe)are evaluated from the potential energy functions and the dissociation energies are extrapolated to the basis set limits.Comparison shows that the present spectroscopic constants are in excellent agreement with the experimental findings.