溶液中的分子.ppt

溶液中的分子计算 一、溶剂效应的物理基础 Coulombic Interaction equation * ? 介电常数 Cavitation energy(空洞能） 把溶剂分子推开形成一个可以放置溶质分子空洞所需的能量 2. Solute-solvent interactions: van der Waals, dispersion hydrogen-bonding ineteraction 二、主要方法 1、分析方程 quantitative structure property relationship (QSPR) 2、基团加和方法（group additivity method) 3、连续介质方法（continuum method) (1) SASA(solvent accessible surface area) σi 区域 的表面张力 Ai 表面积 分子力学 (2) Poisson Equation Onsager model, 建议用MP2 or Hybrid DFT Gaussian程序用SCRF来处理 M. W. Wong, et al. J. Am. Chem. Soc. 113, 4776 (1991). %chk=/s1/dcfang/c2h3f.chk #p b3lyp/6-31g* opt=z-matrix scfcon=6 c2h3f 0 1 c c 1 r1 h 1 r2 2 a1 h 1 r3 2 a2 3 180.0 h 2 r4 1 a3 3 0.0 f 2 r5 1 a4 3 180.0 r1=1.36 r2=1.09 r3=1.09 r4=1.09 r5=1.37 a1=120.0 a2=120.0 a3=120.0 a4=120.0 (1)气相分子几何构型优化 %chk=/s1/dcfang/c2h3f.chk #p b3lyp/6-31g* geom=check guess=read volume scfcon=6 c2h3f 0 1 (2) 求出a0 Recommended a0 for SCRF calculation = 3.30 angstrom ( 6.24 bohr) %chk=/s1/dcfang/c2h3f.chk #p b3lyp/6-31g* geom=check guess=read Scrf=(dipole,solvent=ch2cl2,a0=3.3) scfcon=6 c2h3f 0 1 SCF Done: E(RB+HF-LYP) = -177.820091635 Polarization energy = -0.493054299376E-03 Total energy of solute = -177.820584690 Total energy (include solvent energy) = -177.820091635 Total energy (without reaction field) = -177.819598581 *