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Conjugation in Polyyne Rods: To What Extent Is Charge Delocalization Coupled to Geometrical Changes?

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journal contribution
posted on 18.12.2008, 00:00 by Lior Itzhaki, Esther Rozental, Eli Altus, Harold Basch, Shmaryahu Hoz
Ab initio methods were used to calculate the geometry and the charge distribution (natural bond orbital) in end-protonated polyynes. The geometry obtained is practically identical to that of the corresponding anion and the neutral radical. Thus, the geometry is not much dependent on charge dispersal. Moreover, it is shown that regardless of whether the imposed geometry is that of a cumulenic structure which localizes the charge at one end or that of the neutral molecule which localizes the charge at the other end, the same amount of charge is delocalized to the remote end of the protonated molecule regardless of the imposed structure. The same phenomenon is observed also for polyenes. It is interesting to note that regardless of the charge or its absence, as in the case of the radical, the optimal geometry is obtained as the arithmetic sum of the main resonance structures. Thus, it is concluded that, in these cases, the wave function is only weakly coupled to the geometry of the molecule.