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Density functional study on chirospectra of hydrogen-bonded systems X-(H2O) 3 (X = F,Cl,Br,I)
莽朝永, 李珍贵, 吴克琛
2010 (4):
43601-043601.
doi: 10.1088/1674-1056/19/4/043601
摘要
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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.
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