On the nature of the surprisingly small (red) shift in the halothane...acetone complex.
作者： Kristýna Pluháčková , Pavel Hobza
关键词: Basis set 、 Hydrogen bond 、 Blueshift 、 Fluoroform 、 Computational chemistry 、 Molecular vibration 、 Chemistry 、 Hyperconjugation 、 Density functional theory 、 Natural bond orbital 、 Chemical physics
摘要: The halothaneacetone and fluoroformacetone complexes are studied using the second-order Moller-Plesset (MP2) method with a cc-pVTZ basis set density functional theory (DFT) TZVP set. Whereas halothane exhibits small red shift upon complexation, fluoroform shows pronounced blue shift. To explain this difference in behavior, we perform symmetry-adapted perturbation (SAPT) natural bond orbital (NBO) analyses. Although composition of total stabilization energy each complex is different, that alone does not provide satisfactory explanation for spectral shifts. This interpreted as result interplay hyperconjugation rehybridization mechanisms. surprising C-H stretching frequency halothane, which resulted from complexation species acetone,is explained by compensation two above-mentioned On other hand, C--H most likely reason being concerted occurrence calculated vibration frequencies (+27 cm(-1)) agree experimental value +5 cm(-1).
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