000108336 001__ 108336
000108336 005__ 20231127095532.0
000108336 0247_ $$2doi$$a10.1039/d0cp04878j
000108336 0248_ $$2sideral$$a121251
000108336 037__ $$aART-2020-121251
000108336 041__ $$aeng
000108336 100__ $$0(orcid)0000-0002-8021-8709$$aCuartero, V.
000108336 245__ $$aInterplay between local structure, vibrational and electronic properties on CuO under pressure
000108336 260__ $$c2020
000108336 5060_ $$aAccess copy available to the general public$$fUnrestricted
000108336 5203_ $$aThe electronic and local structural properties of CuO under pressure have been investigated by means of X-ray absorption spectroscopy (XAS) at Cu K edge and ab initio calculations, up to 17 GPa. The crystal structure of CuO consists of Cu motifs within CuO4 square planar units and two elongated apical Cu-O bonds. The CuO4 square planar units are stable in the studied pressure range, with Cu-O distances that are approximately constant up to 5 GPa, and then decrease slightly up to 17 GPa. In contrast, the elongated Cu-O apical distances decrease continuously with pressure in the studied range. An anomalous increase of the mean square relative displacement (EXAFS Debye-Waller, s2) of the elongated Cu-O path is observed from 5 GPa up to 13 GPa, when a drastic reduction takes place in s2. This is interpreted in terms of local dynamic disorder along the apical Cu-O path. At higher pressures (P > 13 GPa), the local structure of Cu2+ changes from a 4-fold square planar to a 4+2 Jahn-Teller distorted octahedral ion. We interpret these results in terms of the tendency of the Cu2+ ion to form favorable interactions with the apical O atoms. Also, the decrease in Cu-O apical distance caused by compression softens the normal mode associated with the out-of-plane Cu movement. CuO is predicted to have an anomalous rise in permittivity with pressure as well as modest piezoelectricity in the 5-13 GPa pressure range. In addition, the near edge features in our XAS experiment show a discontinuity and a change of tendency at 5 GPa. For P < 5 GPa the evolution of the edge shoulder is ascribed to purely electronic effects which also affect the charge transfer integral. This is linked to a charge migration from the Cu to O, but also to an increase of the energy band gap, which show a change of tendency occurring also at 5 GPa.
000108336 536__ $$9info:eu-repo/grantAgreement/ES/MICINN/FJCI-2016-27921$$9info:eu-repo/grantAgreement/ES/MICINN/PGC2018-097520-A-100$$9info:eu-repo/grantAgreement/ES/MICINN/RyC-2016-20301$$9info:eu-repo/grantAgreement/ES/MINECO/RED2018-102612-T
000108336 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000108336 590__ $$a3.676$$b2020
000108336 591__ $$aPHYSICS, ATOMIC, MOLECULAR & CHEMICAL$$b8 / 37 = 0.216$$c2020$$dQ1$$eT1
000108336 591__ $$aCHEMISTRY, PHYSICAL$$b77 / 162 = 0.475$$c2020$$dQ2$$eT2
000108336 592__ $$a1.052$$b2020
000108336 593__ $$aPhysics and Astronomy (miscellaneous)$$c2020$$dQ1
000108336 593__ $$aPhysical and Theoretical Chemistry$$c2020$$dQ1
000108336 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000108336 700__ $$aMonteseguro, V.
000108336 700__ $$aOtero-De-La-Roza, A.
000108336 700__ $$aEl Idrissi, M.
000108336 700__ $$aMathon, O.
000108336 700__ $$aShinmei, T.
000108336 700__ $$aIrifune, T.
000108336 700__ $$aSanson, A.
000108336 773__ $$g22, 42 (2020), 24299-24309$$pPhys. chem. chem. phys.$$tPhysical chemistry chemical physics$$x1463-9076
000108336 8564_ $$s1244140$$uhttps://zaguan.unizar.es/record/108336/files/texto_completo.pdf$$yPostprint
000108336 8564_ $$s2493981$$uhttps://zaguan.unizar.es/record/108336/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000108336 909CO $$ooai:zaguan.unizar.es:108336$$particulos$$pdriver
000108336 951__ $$a2023-11-27-09:47:10
000108336 980__ $$aARTICLE