Charge transfer dynamics from adsorbates to surfaces with single active electron and configuration interaction based approaches

•We model electron dynamics across cyano alkanethiolates attached to gold cluster.•We present electron transfer time scales from TD-DFT and TD-CI based simulations.•Both DFT and CI methods qualitatively predict the trend in time scales.•TD-CI predicts the experimental relative time scale very accurately.

We employ wavepacket simulations based on many-body time-dependent configuration interaction (TD-CI), and single active electron theories, to predict the ultrafast molecule/metal electron transfer time scales, in cyano alkanethiolates bonded to model gold clusters. The initial states represent two excited states where a valence electron is promoted to one of the two virtual π∗ molecular orbitals localized on the cyanide fragment. The ratio of the two time scales indicate the efficiency of one charge transfer channel over the other. In both our one-and many-electron simulations, this ratio agree qualitatively with each other as well as with the previously reported experimental time scales (Blobner et al., 2012), measured for a macroscopic metal surface. We study the effect of cluster size and the description of electron correlation on the charge transfer process.

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