eprintid: 10204970 rev_number: 7 eprint_status: archive userid: 699 dir: disk0/10/20/49/70 datestamp: 2025-02-19 08:27:46 lastmod: 2025-02-19 08:27:46 status_changed: 2025-02-19 08:27:46 type: article metadata_visibility: show sword_depositor: 699 creators_name: Fortino, Mariagrazia creators_name: Schifino, Gioacchino creators_name: Salvalaglio, Matteo creators_name: Pietropaolo, Adriana title: Stepwise kinetics of the early-stage nucleation in chiral perovskites via ab initio molecular dynamics and free-energy calculations ispublished: inpress divisions: UCL divisions: B04 divisions: F43 note: This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence abstract: This study provides a comprehensive molecular-level understanding of the early-stage nucleation process in chiral hybrid organic-inorganic perovskites (HOIPs). A combination of ab initio molecular dynamics (AIMD) based on density functional theory (DFT) and parallel bias metadynamics simulations was designed to explore a broad spectrum of the nucleation scenarios, disclosing how structural deviations affect the formation of chiral aggregates at the atomic scale. The workflow uses parallel replicas initialized from configurations characterised by different root-mean-square deviations (RMSD) relative to the crystallographic coordinates of the chiral ligands. The free-energy landscape and the kinetic pathways involved in chiral aggregate formation indicate a stepwise mechanism that governs the transition from disordered to chiral states. The computed free-energy barriers and corresponding transition timescales uncover several critical stages in this process, including rapid initial relaxations as well as slower, free-energy-intensive steps, with overall timescales on the order of microseconds as the system approaches its most chiral configuration. date: 2025-02-06 date_type: published publisher: Royal Society of Chemistry (RSC) official_url: https://doi.org/10.1039/d4nr04735d oa_status: green full_text_type: pub language: eng primo: open primo_central: open_green verified: verified_manual elements_id: 2360048 doi: 10.1039/d4nr04735d medium: Print-Electronic lyricists_name: Salvalaglio, Matteo lyricists_id: MSALV72 actors_name: Salvalaglio, Matteo actors_id: MSALV72 actors_role: owner full_text_status: public publication: Nanoscale event_location: England issn: 2040-3364 citation: Fortino, Mariagrazia; Schifino, Gioacchino; Salvalaglio, Matteo; Pietropaolo, Adriana; (2025) Stepwise kinetics of the early-stage nucleation in chiral perovskites via ab initio molecular dynamics and free-energy calculations. Nanoscale 10.1039/d4nr04735d <https://doi.org/10.1039/d4nr04735d>. (In press). Green open access document_url: https://discovery.ucl.ac.uk/id/eprint/10204970/1/d4nr04735d.pdf