Author, as appears in the article.: López, J. ; Spinak, M. ; Arcisauskaite, V. ; De Graaf, C.

Department: Química Física i Inorgànica

URV's Author/s: LÓPEZ FERNÁNDEZ, JAVIER; Spinak, M. ; Arcisauskaite, V. ; DE GRAAF , CORNELIS

Keywords: metal atom chains Ab initio

Abstract: 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 ¿-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

Research group: Química Quàntica

Thematic Areas: Chemistry Química Química

licence for use: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 1477-9226

Author identifier: 0000-0003-0322-6796; ; ; 0000-0001-8114-6658

Record's date: 2018-02-28

Last page: 15493

Journal volume: 46

Papper version: info:eu-repo/semantics/acceptedVersion

Link to the original source: http://pubs.rsc.org/en/Content/ArticleLanding/2017/DT/C7DT03520A#!divAbstract

Funding program: altres; EPSRC; EP/K021435/1 european; COST Ac- tion ECOSTBio; CM1305 altres; Xarxa d¿R+D+I en Química Teòrica i Computacional; XRQTC altres; Grupos Consolidados; 2014SGR199 plan; Excelencia; CTQ2014-51938-P

Article's DOI: 10.1039/c7dt03520a

Entity: Universitat Rovira i Virgili

Journal publication year: 2017

First page: 15487

Publication Type: Article Artículo Article