Author, as appears in the article.: Spivak M; Arcisauskaite V; López X; De Graaf C
Department: Química Física i Inorgànica
URV's Author/s: De Graaf, Cornelis / López Fernández, Javier
Keywords: Ultrasoft pseudopotentials Systems String complexes Self-consistent-field Metal atom chains Low-symmetry distortions Electron-transport Density-functional theory Cr Axial ligand Ab initio 2nd-order perturbation-theory
Abstract: © 2017 The Royal Society of Chemistry. Recently published static DFT and CASSCF/CASPT2 calculations depicted extremely flat Potential Energy Surfaces (PESs) for the Cr-Cr flexibility of Cr3(dpa)4X2 (X = NCS-, CN-, NO3-) extended metal atom chains (EMACs) (M. Spivak, et al., Dalton Trans., 2017, 46, 6202). We herein explore the thermal and crystal packing effects on the structure of EMACs using ab initio molecular dynamics (MD). Car-Parrinello DFT-based simulations of the isolated molecules show that thermal energy favors asymmetric arrangements of the Cr3 chain due, in part, to the bending of the axial ligands (X) and the increased X-Cr distance, both of which weaken X → Cr σ-donation. This effect is even more prominent in the crystalline phase due to the interaction between the axial ligands of neighboring molecules in the unit cell. This could explain the typical discrepancies between the experimental and theoretical characterization of Cr3 EMACs observed in the literature.
Thematic Areas: Química Odontología Medicina ii Materiais Interdisciplinar Inorganic chemistry General medicine Farmacia Ensino Engenharias iv Engenharias iii Engenharias ii Engenharias i Ciências biológicas ii Ciências biológicas i Ciências ambientais Ciências agrárias i Chemistry, inorganic & nuclear Biotecnología Astronomia / física
licence for use: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 14779226
Author's mail: coen.degraaf@urv.cat javier.lopez@urv.cat
Author identifier: 0000-0001-8114-6658 0000-0003-0322-6796
Record's date: 2024-09-07
Papper version: info:eu-repo/semantics/acceptedVersion
Link to the original source: https://pubs.rsc.org/en/Content/ArticleLanding/2017/DT/C7DT03520A#!divAbstract
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Dalton Transactions. 46 (44): 15487-15493
APA: Spivak M; Arcisauskaite V; López X; De Graaf C (2017). Backbone flexibility of extended metal atom chains.: Ab initio molecular dynamics for Cr3(dpa)4X2 (X = NCS, CN, NO3) in gas and crystalline phases. Dalton Transactions, 46(44), 15487-15493. DOI: 10.1039/c7dt03520a
Article's DOI: 10.1039/c7dt03520a
Entity: Universitat Rovira i Virgili
Journal publication year: 2017
Publication Type: Journal Publications
Repositori URV