Chemical Research in Chinese Universities ›› 1997, Vol. 13 ›› Issue (3): 235-239.

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New Application of bond Function Basis Sets──ab initio Calculations of Nonlinear OpticalProperties of CH4-nFn(n=1,2,3)

Li-Zhi-ru1, TAO Fu-ming2, PAN Yuh-kang3, FENG Ji-kang1, WU Di1, HUANG Xu-ri4, SUN Ghia-Chung4   

  1. 1. Department of Chemistry, Jilin University, Changchun 130023, Caina;
    2. Department of Chemistry, Harvard University, Chmberidge, MA 02138, USA;
    3. Department of Chemistry, Boston College, Chestnut Hill, MA 02167, USA;
    4. Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China
  • Received:1996-06-13 Online:1997-08-24 Published:2011-08-17
  • Supported by:

    Supported by the National Natural Science Foundation of China,State Education Commission of China,the National Laboratory of Theoretical and Computational Chemistry of Jilin University-and the Key Laboratory for Supra Molecular Structure and Spectra of Jilin University and the University Doctoral Subject Foundation.

Abstract: On the basis of adding the bond functions (3s 3p 2d) to the basis sets 6-311G ( 2d 2p ) for increasing the efficiency of the basis sets, we have carried out the MP2 calculations of nonlinear optical properties includintg dipole moment uo,polarizibili- ty μo and hyperpolarizability βo for CH4-nFn (n = 1, 2, 3). The results are in good a- greement with those of experimentsl The roles of the bond functions in the calcula- tions are shown (μo, αo, βo) the improved values of the properties are about 2%-7% at the SCF level and about 6%-30% at the correlated level (MP2). It is shown that the more important role of the bond functions in calculating is the im- provement of the effects of the corrections of electronic correlations and the increase of the effects is in the order of μo<αo<βo In addition, it is also shown that the cal-, culated value of a property does not change with the bond-function location in our calculations except for the regions close to the nuclei in a molecule.

Key words: Bond function, MP2, Nonlinear optical property