甲烷水合物的氢键、次级作用、基组重叠误差的量子化学研究和DFT中色散能的修正-物理化学专业论文.docxVIP

天津师范火学颂十论文 天津师范火学颂十论文 摘要 Abstract In this study several quantum chemistry methods arg used in the calculation of water-water binding energy,hydrogen bonding energ)，cooperation interaction end B$SE of water pentamer and water hexamer,which the unit cell of methane hydrate structure—I，11．The dispersion correction method of DFT is proposed．The interaction of water dimmer and methane．water dimmer in methane hydrate structure—I is calculated by the accurate advanced method configuration interaction(e1)．To get the better intermolecular energies．which are calculated with DF’T’method，we amend the source code ofDFT demon software and the benchmark of energy correction is set as the energy difference bet、veen DFT and configuration interaction．The energy correction for dispersion interactions may includes dispersion，configuration interaction，and other effects．The particular research is as follows： (1)TheHartree．Fock，MP2．DF，Imethodsand basis set5 6-3IG(d，p)and 6-311G(d，P)are used in calculation of the water-water binding energy,hydrogen bonding energy， cooperation interaction and BSSE in water pentamer and water hexamer．The newly developed DFT program deMon，in which the dispersion term is involved in the functional， is used to calculate the dispersion energy in water pentamer．In the method BLYP of DMol3 the large numerical basis set DNP is used to minimize the BSSE．nle BSSE in B3LYP／6—3 1G(d，p)method is corrected by counterpoise(CP)method．The water-water binding energy is modified with CP(counterpoise recipe)correction for the basis set superposition error(BSSE)．The results of Gaussian03 show that the average hydrogen bonding energy ofwater pentamer and water hexamer is-25．20 v,J／mol and一25．12 kJ／mol respectively,the maximum dispersion energy is 0．8 kJ／m01． (2)A general empirical method is proposed for correction of London dispersion and other effects in