Department of Chemistry, KAIST, Daejeon 305-701, Republic of Korea.
J Chem Phys. 2010 Oct 14;133(14):144309. doi: 10.1063/1.3497189.
Quantum chemical calculations of HgX(n) (X=F, Cl, Br, and I; n=1, 2, and 4) in the gas phase are performed using the density functional theory (DFT), two-component spin-orbit (SO) DFT, and high-level ab initio method with relativistic effective core potentials (RECPs). Molecular geometries, vibrational frequencies, and various thermochemical energies are calculated and compared with available experimental results. We assess the performances of DFT functionals for calculating various molecular properties. The PBE0 functional is generally reasonable for the molecular geometries and the vibrational frequencies, but the M06 functional is more appropriate for estimating thermochemical energies. Both shape-consistent and energy-consistent RECPs correctly describe the SO effect.
采用密度泛函理论（DFT）、双分量自旋轨道（SO）DFT 和相对论有效核势（RECP）的高精度从头算方法，对气相中的 HgX(n)（X=F、Cl、Br 和 I；n=1、2 和 4）进行量子化学计算。计算并比较了分子几何形状、振动频率和各种热化学能与现有实验结果。评估了 DFT 泛函计算各种分子性质的性能。PBE0 泛函通常适用于分子几何形状和振动频率，但 M06 泛函更适合于估算热化学能。形状一致和能量一致的 RECP 正确描述了 SO 效应。
