TY - JOUR

T1 - Niobium and tantalum octahedral Halides: Vibrational properties and Intra–Cluster interactions

AU - Shamshurin, Maxim V.

AU - Martynova, Svetlana A.

AU - Sokolov, Maxim N.

AU - Benassi, Enrico

N1 - Funding Information: The authors are grateful to Dr. Maxim A. Mikhaylov for helpful discussions and to Dr. Boris A. Kolesov for recording the Raman spectra. The computational part of this work was carried out thanks to the resources kindly provided by the Siberian Supercomputer Centre (SSCC) ICMMG SB RAS. The technical personnel are also gratefully thanked. MS received financial support by the Russian Science Foundation (grant number 19–73–10027). The analytical research was supported by the Ministry of Science and Higher Education of the Russian Federation, №121031700313–8. Publisher Copyright: © 2022 Elsevier Ltd

PY - 2022/11/1

Y1 - 2022/11/1

N2 - IR and Raman spectroscopies are important characterisation methods for Nb and Ta octahedral halide clusters [M6Xi12Xa6]x (M = Nb, Ta; X = Cl, Br; x = 4–, 3–, 2–; i – “inner”, bridging ligand belonging to the cluster core, a – “ausser” or “apical” terminal ligand) and the polymeric Ta6I14. The structural and spectroscopic data of these compounds (x = 4–) and their corresponding {M6X12}2+ core clusters were systematically investigated and analysed by means of quantum chemical calculations. The intra–cluster interactions were studied in details by means of Natural Bond Orbital and Bader's Atoms–In–Molecules theory analyses, and the results were related to the spectroscopical features, in particular to the composition of the main vibrational normal modes in terms of the contribution of the internal coordinates.

AB - IR and Raman spectroscopies are important characterisation methods for Nb and Ta octahedral halide clusters [M6Xi12Xa6]x (M = Nb, Ta; X = Cl, Br; x = 4–, 3–, 2–; i – “inner”, bridging ligand belonging to the cluster core, a – “ausser” or “apical” terminal ligand) and the polymeric Ta6I14. The structural and spectroscopic data of these compounds (x = 4–) and their corresponding {M6X12}2+ core clusters were systematically investigated and analysed by means of quantum chemical calculations. The intra–cluster interactions were studied in details by means of Natural Bond Orbital and Bader's Atoms–In–Molecules theory analyses, and the results were related to the spectroscopical features, in particular to the composition of the main vibrational normal modes in terms of the contribution of the internal coordinates.

KW - Bader's atoms-in-molecules theory

KW - Natural bond orbital analysis

KW - Niobium and tantalum halides

KW - Quantum chemical calculations

KW - Vibrational spectroscopies

UR - http://www.scopus.com/inward/record.url?scp=85137291847&partnerID=8YFLogxK

U2 - 10.1016/j.poly.2022.116107

DO - 10.1016/j.poly.2022.116107

M3 - Article

AN - SCOPUS:85137291847

VL - 226

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

M1 - 116107

ER -