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Characterization Of Ground And Excited Electronic State Deprotonation Energies Of Systems Containing Double Bonds Using Natural Bond Orbital Analysis, J. K. Badenhoop, Steve Scheiner

Steve Scheiner

Natural bond orbital analysis is applied to the ground and excited states of a set of neutral, cationic, and anionic doubly bonded species H_nC=XH_n (X=C, N, O) isoelectronic with ethylene. The character of the excitation is correlated with calculated charge shifts and geometry changes upon relaxation. For these planar molecules, depopulation of the π bond or population of the π∗ antibond causes an out‐of‐plane twist or pyramidalization upon relaxation correlated to the amount of charge shift. These nonplanar distortions generally lower the energy more than changes in bond lengths and angles. Population of a σ_XH^{∗ …}