Ab initio calculation of force constants and equilibrium geometries in poly-atomic molecules. II. Force constants of water
Ab initio calculation of force constants and equilibrium geometries in poly-atomic molecules. II. Force constants of water
复制标题
多原子分子中力常数和平衡几何形状的从头计算。
DOI：
10.1080/00268977000100541
复制
发表时间：
1970
影响因子：
1.7
通讯作者：
P. Pulay
中科院分区：
文献类型：
--
作者：
P. Pulay
使用力法以及 53/31、73/3 + 1 和 95/41 + 2 高斯波瓣基组从 Hartree-Fock 自洽场波函数从头计算水的力常数和平衡几何形状。事实证明，力法非常经济且数值准确。计算值与实验值吻合较好。特别好的是相互作用常数 F rα 的一致性。 95/41 + 2 基础的计算力常数为：Fr = 9·158 mdyn/å，F α = 0·8513 mdyn/å，Frα = +0·3007，F rr = -0·1724；同位素频率的实验值为：Fr = 8·456，F α = 0·762，F rα = +0·246，F rr = -0·100 mdyn/å。 95/41 + 2 基础 r e = 0·9518 å、α = 107·49° 和实验 r e = 0·9572 å、α = 104·52° 的几何一致性也很好。人们发现力常数对基函数的变化非常不敏感，所有三组都给出几乎相同的结果。另一方面，偶极矩导数非常敏感。
The force constants and equilibrium geometry of water were calculated ab initio from Hartree-Fock self-consistent field wavefunctions using the force method, and a 53/31, a 73/3 + 1 and a 95/41 + 2 gaussian lobe basis set. The force method proved to be very economic and numerically accurate. The calculated values agree well with the experimental ones. Especially good is the agreement for the interaction constant F rα . Calculated force constants for the 95/41 + 2 basis are: F r = 9·158 mdyn/å, F α = 0·8513 mdyn/å, F rα = +0·3007, F rr = -0·1724; the experimental values from isotope frequencies are: F r = 8·456, F α = 0·762, F rα = +0·246, F rr = -0·100 mdyn/å. The agreement in the geometry is also good for the 95/41 + 2 basis r e = 0·9518 å, α = 107·49°, and the experimental r e = 0·9572 å, α = 104·52°. Force constants were found to be quite insensitive to variation in the basis functions, all three sets giving almost the same result. On the other hand, the dipole moment derivative is very sensitive.