物理化学学报
物理化學學報
물이화학학보
ACTA PHYSICO-CHIMICA SINICA
2010年
4期
1043-1050
,共8页
剂效应%近似积分方法%解析积分方法%多面体
劑效應%近似積分方法%解析積分方法%多麵體
제효응%근사적분방법%해석적분방법%다면체
Solvation effect%Approximate integration method%Analytical integration method%Polyhedron
采用多面体表面模拟溶质空腔,讨论了溶剂效应计算中近似积分方法和解析积分方法的平行性和收敛性.我们发现:对所研究的40个中性分子,近似方法和解析方法之间的平行性较好;但是,对于20个正离子和27个负离子,当溶质空腔分别为0.002和0.001 a.u.的等电荷密度面时,近似方法和解析方法之间的平行性较差,因此,近似方法的可靠性不一定有保证.我们还发现当多面体的表面无限趋近空腔的表面时,不管采用何种多面体序列,近似方法和解析方法的基态总能量都基本趋向同一极限值.
採用多麵體錶麵模擬溶質空腔,討論瞭溶劑效應計算中近似積分方法和解析積分方法的平行性和收斂性.我們髮現:對所研究的40箇中性分子,近似方法和解析方法之間的平行性較好;但是,對于20箇正離子和27箇負離子,噹溶質空腔分彆為0.002和0.001 a.u.的等電荷密度麵時,近似方法和解析方法之間的平行性較差,因此,近似方法的可靠性不一定有保證.我們還髮現噹多麵體的錶麵無限趨近空腔的錶麵時,不管採用何種多麵體序列,近似方法和解析方法的基態總能量都基本趨嚮同一極限值.
채용다면체표면모의용질공강,토론료용제효응계산중근사적분방법화해석적분방법적평행성화수렴성.아문발현:대소연구적40개중성분자,근사방법화해석방법지간적평행성교호;단시,대우20개정리자화27개부리자,당용질공강분별위0.002화0.001 a.u.적등전하밀도면시,근사방법화해석방법지간적평행성교차,인차,근사방법적가고성불일정유보증.아문환발현당다면체적표면무한추근공강적표면시,불관채용하충다면체서렬,근사방법화해석방법적기태총능량도기본추향동일겁한치.
The parallelism and convergence of the approximate and analytical integration methods on solvation effect calculation were investigated by simulating the solute cavity with polyhedrons.We find that these two methods have excellent parallelism for the 40 neutral molecules studied.The parallelism is poor for the 27 anions and 20 cations studied as the cavity is the 0.001 and 0.002 a.u.isodensity contours.The accuracy of the approximation method is,therefore,not guaranteed.We also find that despite the type of polyhedron used to simulate the cavity,the ground state electronic energies of the solute molecules calculated by the above two methods converge to nearly the same limit as the faces of the polyhedrons approach infinity.
