Ab initio quantum-classical molecular dynamics of electron attached states is presented as an alternative approach for the modeling of electron transport through the single-molecule junctions. Observations on the nature and mechanism of the process are made by time-resolved analysis of energy differences, non-adiabatic transition probabilities and the spatial distribution of the excess electron. The role of molecular vibrations that facilitate the transport by being responsible for the periodic behaviour of the relevant quantities is shown using normal mode analysis. The results for the case of 1-4-biaminobenzene (BDA) suggest a mechanism involving the electron’s direct hopping between the electrodes, without its presence on the molecule, with the prime importance of the bending vibrations that periodically alter the molecule–electrode interactions. No relevant differences are found between results provided by the ADC(2) and SOS-ADC(2) excited state models. Our approach provides an alternative insight into the role of nuclear motions in the electron transport process, one which is more expressive from the chemical perspective.

First-principles interpretation of electron transport though single-molecule junctions using molecular dynamics of electron attached states

ACS Spring 2022

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