Charge-transfer selectivity and quantum interference in real-time electron dynamics: Gaining insights from time-dependent configuration interaction simulations.

摘要: Many-electron wavepacket dynamics based on time-dependent configuration interaction (TDCI) is a numerically rigorous approach to quantitatively model electron transfer across molecular junctions. TDCI simulations of cyanobenzene thiolates—para- and meta-linked an acceptor gold atom—show donor states conjugating with the benzene π-network allow better through-molecule migration in para isomer compared meta counterpart. For involving non-conjugating states, we find injection stem exclusively from distance-dependent non-resonant quantum mechanical tunneling, which case exhibits dynamics. The computed trend donor-to-acceptor net-electron through differently linked azulene bridges agrees seen low-bias conductivity measurements. Disruption π-conjugation has been shown be cause diminished 1,3-azulene, pathological for graph-based diagnosis destructive interference. Furthermore, demonstrate interference many-electron wavefunctions drive para-vs-meta selectivity coherent evolution superposed π(CN)- σ(NC–C)-type wavepackets. Analyses reveal that para-linked benzene, σ π MOs localized at terminal are in-phase, leading constructive density distribution, while phase-flip one results These findings suggest priori detection orbital coherence conditions can aid device design strategies.