20.500.12556/RUL-183097 Symmetry-selective ultrafast charge transfer via cyano end groups at the PDIF-CN▫$_2$▫–Au(111) interface Cyano-functionalized perylene diimides provide a platform for engineering orbital-specific electronic transparency at organic‒metal interfaces. Here we resolve the adsorption geometry, orbital symmetry, and ultrafast charge-transfer dynamics of PDIF-CN▫$_2$▫ on Au(111) using polarization-dependent NEXAFS, XPS, resonant Auger spectroscopy with core-hole-clock analysis, and STM. Molecules in the monolayer lie flat with out-of-molecular plane polarized cyano-derived ▫$\pi^*$▫ orbitals aligned toward Au(111). Although the overall electronic structure remains largely molecular, the nearly degenerate cyano ▫$\sigma^*(\pi)/\pi^*(\pi)$▫ doublet becomes distinctly split at the interface, enabling symmetry-selective coupling of cyano orbitals. We use Auger spectator shifts to quantify bidirectional charge exchange within the N 1s core-hole lifetime, yielding injection of ▫$\sim$▫0.43 e▫$^-$▫ from Au into cyano ▫$\pi^*(\pi)$▫ orbital and the transfer of ▫$\sim$▫0.17 e▫$^-$▫ in the opposite direction. These findings establish cyano end groups as symmetry-selective gateways for femtosecond charge transfer at molecule‒metal interfaces. thin films interfaces charge transfer Auger spectroscopy tanki filmi površine prenos naboja Augerjeva spektroskopija true false true Angleški jezik Slovenski jezik Članek v reviji 2026-06-04 11:56:11 2026-06-04 11:56:12 2026-06-07 03:23:36 0000-00-00 00:00:00 2026 0 0 Str. 6983-6990 iss. 21 Vol. 26 May 2026 0000-00-00 Zaloznikova Objavljeno NiDoloceno 0000-00-00 0000-00-00 0000-00-00 544 1530-6984 10.1021/acs.nanolett.6c01061 278874883 https://pubs.acs.org/doi/10.1021/acs.nanolett.6c01061 1 4662dfb6-5ffb-11f1-b0ab-0050569b8976 https://repozitorij.uni-lj.si/Dokument.php?lang=slv&id=234951 symmetry-selective-ultrafast-charge-transfer-via-cyano-end-groups-at-the-pdif-cn2-au(111)-interface.pdf symmetry-selective-ultrafast-charge-transfer-via-cyano-end-groups-at-the-pdif-cn2-au(111)-interface.pdf 1 95FAA52438E8901219DFA9BCC27C5CA4 1e3f01aed0d437ac523fc1483bab0c4e9ed191bc9f81f56f3eae19a5f7c8b19b ea3d4228-5ffb-11f1-b0ab-0050569b8976 https://repozitorij.uni-lj.si/Dokument.php?lang=slv&id=234952 Fakulteta za matematiko in fiziko 0 0 0