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The well‐known second‐order perturbation method is used to correlate the bond–bond interaction constants in ground and excited electronic states of triatomic systems of the first‐row elements, and unusual force constants in diazomethane and ketene with the effect of electron relaxation. The third‐ and fourth‐order perturbation schemes are used to determine qualitatively the contributions to the third‐ and fourth‐order parts of the vibrational potential function of carbon dioxide, by the electron relaxation effect. The fourth‐order theory is used to rationalize the negative anharmonicities observed in ketene, diazomethane, the methyl radical, and planar excited states of ammonia

Electron Relaxation and Molecular Vibrations: Triatomic Systems of the First-Row Elements, the Methyl Radical, and Diazomethane and Ketene