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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 organic molecules of increasing size and find,surprisingly, that extending the carbon skeleton in propynal analogs slows downdecoherence and extends the duration of 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 preserving the molecule's symmetryinduce decoherence. All together, we justify the enhanced charge migration by acombination of increased hole-mixing and the disappearance of decoherencecontributions from specific vibrational modes CO stretching in butynal andvarious H rockings in pentynal.

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