QUANTITATIVE APPLICATION OF RESONANCE THEORY ON EXCITED STATE BEHAVIOURS AND ITS CONSISTENCY WITH MOLECULAR ORBITAL THEORY

【摘要】 <正> Rcsonance theory, the graphic language of valence bond theory, has been applied quantitatively and successfully to a series of excited state behaviours, the so-called properties related to molecalar orbits, such as the p-bands and β-bands of UV spectra, the oxidation and reduction half-wave potentials of polarography. By taking the Kekulé formulae of ground and excited state of molecules as the bases of corresponding wave functions, it is evidenced that the values of ln(excited structure count/ground structure count) correlate lineally with the above-mentioned properties. In practice, the correlations between calculations and experiments of polycyclic aromatic hydrocarbons are all good (|γ|>0.95). On conjugated polyene, polyyne and benzenoid polyacene homologs, the series with excellent correlation among the 150 calculated series exceed 85% (|γ|≥0.99), and for the remainder series, the correlations are all good (|γ|>0.95).更多还原

【Abstract】 Rcsonance theory, the graphic language of valence bond theory, has been applied quantitatively and successfully to a series of excited state behaviours, the so-called properties related to molecalar orbits, such as the p-bands and β-bands of UV spectra, the oxidation and reduction half-wave potentials of polarography. By taking the Kekulé formulae of ground and excited state of molecules as the bases of corresponding wave functions, it is evidenced that the values of ln(excited structure count/ground structure count) correlate lineally with the above-mentioned properties. In practice, the correlations between calculations and experiments of polycyclic aromatic hydrocarbons are all good (|γ|>0.95). On conjugated polyene, polyyne and benzenoid polyacene homologs, the series with excellent correlation among the 150 calculated series exceed 85% (|γ|≥0.99), and for the remainder series, the correlations are all good (|γ|>0.95).更多还原