Properties of Closed-Shell, Octahedral, Multiply-Charged Hexafluorometallates MF63-, M = Sc, Y, La, ZrF62-, and TaF6-

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• 作者：Maciej Gutowski ; Alexander I. Boldyrev ; Jack Simons ; Janusz Rak ; and Jerzy B//pubs.acs.org/images/entities/lstrok.gif" border="0">a//pubs.acs.org/images/entities/zdot.gif
• 刊名：Journal of the American Chemical Society
• 出版年：1996
• 出版时间：February 7, 1996
• 年：1996
• 卷：118
• 期：5
• 页码：1173 - 1180
• 全文大小：162K
• 年卷期：v.118,no.5(February 7, 1996)
• ISSN：1520-5126

文摘

Properties of multiply-charged hexafluorometallatesMF₆^3-, M = Sc, Y, La,ZrF₆^2-, and TaF₆^-,havebeen examined at the SCF, MP2, and Becke3LYP levels of theory using theSBKJ pseudopotentials and extendedone-electron basis sets. For MF₆^3-, M= Sc, Y, La, our results suggest a different assignment ofvibrational transitionsthan those quoted by Nakamoto¹ and recorded by von Beckeret al.² For the series of isoelectronic complexes,wedocument that the discrepancy between the theoretical gas phasevibrational frequencies and those measured incondensed phase experiments increases as the Becke3LYP HOMO bindingenergies become more positive. Thefrequencies of stretching modes measured in condensed phase experimentsare systematically higher than thosecalculated for the gas phase anions. We suggest that a partialcharge transfer from the multiply-charged anions tocountercations is responsible for the stiffening of vibrational modesin condensed phase environments. The verticalelectron detachment energies were determined at the outer valenceGreen's function, MP2, and B3LYP levels. Thebinding energies of hexafluorometallates with respect to the energiesof atomic ions were also calculated and onlya small contribution of the electron correlation effects wasfound.