Autor según el artículo: Spivak M; Arcisauskaite V; López X; De Graaf C

Departamento: Química Física i Inorgànica

Autor/es de la URV: De Graaf, Cornelis / López Fernández, Javier

Palabras clave: 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

Resumen: © 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.

Áreas temáticas: 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

Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 14779226

Direcció de correo del autor: coen.degraaf@urv.cat javier.lopez@urv.cat

Identificador del autor: 0000-0001-8114-6658 0000-0003-0322-6796

Fecha de alta del registro: 2023-02-26

Versión del articulo depositado: info:eu-repo/semantics/acceptedVersion

Enlace a la fuente original: https://pubs.rsc.org/en/Content/ArticleLanding/2017/DT/C7DT03520A#!divAbstract

URL Documento de licencia: http://repositori.urv.cat/ca/proteccio-de-dades/

Referencia al articulo segun fuente origial: Dalton Transactions. 46 (44): 15487-15493

Referencia de l'ítem segons les normes 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

DOI del artículo: 10.1039/c7dt03520a

Entidad: Universitat Rovira i Virgili

Año de publicación de la revista: 2017

Tipo de publicación: Journal Publications