中国物理B ›› 2010, Vol. 19 ›› Issue (4): 43601-043601.doi: 10.1088/1674-1056/19/4/043601

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Density functional study on chirospectra of hydrogen-bonded systems X-(H2O) 3 (X = F,Cl,Br,I)

李珍贵1, 莽朝永2, 吴克琛3   

  1. (1)College of Life Science and Chemistry, Dali University, Dali 671000, China; (2)College of Life Science and Chemistry, Dali University, Dali 671000, China;Institute of Eastern-Himalaya Biodiversity Research, Dali University, Dali 671000, China; (3)State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
  • 收稿日期:2009-03-03 修回日期:2009-06-01 出版日期:2010-04-15 发布日期:2010-04-15
  • 基金资助:
    Project supported by the Scientific Foundation of Education Department of Yunnan Province of China (Grant No.~07Z11621), the Innovation Foundation for New Researchers in Dali University (Grant No. KY421040), and the National Natural Science Foundation of

Density functional study on chirospectra of hydrogen-bonded systems X-(H2O) 3 (X = F,Cl,Br,I)

Mang Chao-Yong(莽朝永)a)b)†,Li Zhen-Gui(李珍贵)a), and Wu Ke-Chen(吴克琛)c)‡   

  1. a College of Life Science and Chemistry, Dali University, Dali 671000, China; b Institute of Eastern-Himalaya Biodiversity Research, Dali University, Dali 671000, China; c State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
  • Received:2009-03-03 Revised:2009-06-01 Online:2010-04-15 Published:2010-04-15
  • Supported by:
    Project supported by the Scientific Foundation of Education Department of Yunnan Province of China (Grant No.~07Z11621), the Innovation Foundation for New Researchers in Dali University (Grant No. KY421040), and the National Natural Science Foundation of

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摘要： This paper calculates the molecular structures, infrared, Raman, circular dichroism spectra and optical rotatory powers of some hydrogen-bonded supramolecular systems as a cyclic water trimer, (H2O)3 and its pyramidal halide complexes, $X^-$(H2O)3 ($X$ = F, Cl, Br, I) with the gradient-corrected density functional theory method at the B3LYP/6--311++G(2d,2p) and B3LYP/Aug--cc--pVTZ levels. It finds that the complexation of halide anions with the water trimer can efficiently modulate the chirally optical behaviors. The calculated vibrational circular dichroism spectrum illuminates that the vibrational rotational strength of S(+)--(H2O)3 mostly originates from the O--H rocking modes, whereas chirality of S(--)--$X^-$(H2O)$_{3 }$ ($X$ = F, Cl, Br, I) has its important origin in the O--H stretching modes. The calculated optical rotatory power demonstrates that S(+)--(H2O)3 and S(+)--F$^-$(H2O)$_{3 }$ are positively chiral, whereas S(--)--$X^-$(H2O)$_{3 }$ ($X$ = Cl, Br, I) are negatively chiral. With the polarizable continuum model, calculated bulk solvent effect in the solvents water and carbontetrachloride and argon shows that the positive chirality of S(+)--(H2O)3 is enhanced and the negative chirality of S(--)--$X^-$(H2O)$_{3 }$ ($X$ = Cl, Br, I) and the positive chirality of S(+)--F$^-$(H2O)3 are reduced with an augmentation of the solvent dielectric constant.

Abstract: This paper calculates the molecular structures, infrared, Raman, circular dichroism spectra and optical rotatory powers of some hydrogen-bonded supramolecular systems as a cyclic water trimer, (H2O)3 and its pyramidal halide complexes, $X^-$(H2O)3 ($X$ = F, Cl, Br, I) with the gradient-corrected density functional theory method at the B3LYP/6--311++G(2d,2p) and B3LYP/Aug--cc--pVTZ levels. It finds that the complexation of halide anions with the water trimer can efficiently modulate the chirally optical behaviors. The calculated vibrational circular dichroism spectrum illuminates that the vibrational rotational strength of S(+)--(H2O)3 mostly originates from the O--H rocking modes, whereas chirality of S(--)--$X^-$(H2O)$_{3 }$ ($X$ = F, Cl, Br, I) has its important origin in the O--H stretching modes. The calculated optical rotatory power demonstrates that S(+)--(H2O)3 and S(+)--F$^-$(H2O)$_{3 }$ are positively chiral, whereas S(--)--$X^-$(H2O)$_{3 }$ ($X$ = Cl, Br, I) are negatively chiral. With the polarizable continuum model, calculated bulk solvent effect in the solvents water and carbontetrachloride and argon shows that the positive chirality of S(+)--(H2O)3 is enhanced and the negative chirality of S(--)--$X^-$(H2O)$_{3 }$ ($X$ = Cl, Br, I) and the positive chirality of S(+)--F$^-$(H2O)3 are reduced with an augmentation of the solvent dielectric constant.

Key words: water cluster, hydrogen-bond, vibrational circular dichroism, infrared spectra, density functional theory

中图分类号: 

  • 78.30.Cp
78.20.Fm (Birefringence) 78.20.Ek (Optical activity) 61.20.Gy (Theory and models of liquid structure) 63.50.-x (Vibrational states in disordered systems) 77.22.Ch (Permittivity (dielectric function))