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Coherent superposition of electronic states, created by ionizing a molecule,can initiate ultrafast dynamics of the electron density. Correlation betweennuclear and electron motions, however, typically dissipates the electroniccoherence in only a few femtoseconds, especially in larger and more flexiblemolecules. We, therefore, use ab initio semiclassical dynamics to studydecoherence in a sequence of analogous organic molecules of increasing size andfind, surprisingly, that extending the carbon skeleton in propynal analogsslows down decoherence and prolongs charge migration. To elucidate thisobservation, we decompose the overall decoherence into contributions fromindividual vibrational modes and show that: (1) The initial decay of electroniccoherence is caused by high- and intermediate-frequency vibrations via momentumseparation of nuclear wavepackets evolving on different electronic surfaces.(2) At later times, the coherence disappears completely due to the increasingposition separation in the low-frequency modes. (3) In agreement with anotherstudy, we observe that only normal modes that preserve the symmetry of themolecule induce decoherence. All together, we justify the enhanced chargemigration by a combination of increased hole-mixing and the disappearance ofdecoherence contributions from specific vibrational modes: CO stretching inbutynal and various H rockings in pentynal.

Can increasing the size and flexibility of a molecule reduce decoherence and prolong charge migration?