caa a22 4500 605488509 CHVBK 20210128100455.0 cr unu---uuuuu 210128e20150201xx s 000 0 eng 10.1007/s00214-014-1605-3 doi (NATIONALLICENCE)springer-10.1007/s00214-014-1605-3 Theoretical analysis of vibrational modes in uranyl aquo chloro complexes [Elektronische Daten] [F. Izquierdo-Ruiz, J. Menéndez, J. Recio] The electronic structure of uranyl-based complexes of water and chlorine, with the general formula $$[\hbox {UO}_2(\hbox {H}_2\hbox {O})_{x}\hbox {Cl}_{y}]^{2-y} \,(y = 1,\, 2,\, 3,\, 4;\, x + y = 4, 5)$$ [ UO 2 ( H 2 O ) x Cl y ] 2 - y ( y = 1 , 2 , 3 , 4 ; x + y = 4 , 5 ) , have been computed both in vacuo and in aqueous solution. Within the density functional theory framework, total and relative energies (including basis set superposition error corrections), equilibrium geometries, and vibrational frequencies were determined and briefly compared with available experimental and previous theoretical data. New results on vibrational modes of these complexes are emphasized. Our focus is on the trend exhibited by the frequency of the stretching mode ( $$\nu _{\mathrm{s}}$$ ν s ) associated to the uranyl moiety at different chlorine concentrations. A charge transfer index (CT) accounting for the number of electrons transferred from the ligands to $$\hbox {UO}_2^{2+}$$ UO 2 2 + is used to rationalize this trend. According to our most accurate calculations, $$\nu _{\mathrm{s}}$$ ν s is red-shifted at a rate between 15 and $$20\,\hbox {cm}^{-1}$$ 20 cm - 1 per 0.1 e transferred. Interestingly enough, a linear trend is displayed using CT as the correlating parameter. Springer-Verlag Berlin Heidelberg, 2015 Uranyl-type complexes nationallicence DFT calculations nationallicence Vibrational modes nationallicence Izquierdo-Ruiz F. Departamento de Química Física y Analítica, Universidad de Oviedo, 33006, Oviedo, Spain aut Menéndez J. Departamento de Química Física y Analítica, Universidad de Oviedo, 33006, Oviedo, Spain aut Recio J. Departamento de Química Física y Analítica, Universidad de Oviedo, 33006, Oviedo, Spain aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/2(2015-02-01), 1-8 1432-881X 134:2<1 2015 134 214 https://doi.org/10.1007/s00214-014-1605-3 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00214-014-1605-3 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Izquierdo-Ruiz F. Departamento de Química Física y Analítica, Universidad de Oviedo, 33006, Oviedo, Spain aut NATIONALLICENCE 700 1- Menéndez J. Departamento de Química Física y Analítica, Universidad de Oviedo, 33006, Oviedo, Spain aut NATIONALLICENCE 700 1- Recio J. Departamento de Química Física y Analítica, Universidad de Oviedo, 33006, Oviedo, Spain aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/2(2015-02-01), 1-8 1432-881X 134:2<1 2015 134 214