DUGi

X2Y2 isomers: Tuning structure and relative stability through electronegativity differences (X = H, Li, Na, F, Cl, Br, I; Y = O, S, Se, Te)

http://dugi.udg.edu/item/http:@@@@hdl.handle.net@@2072@@296685

We have studied the XYYX and X2YY isomers of the X 2Y2 species (X = H, Li, Na, F, Cl, Br, I; Y = O, S, Se, Te) using density functional theory at the ZORA-BP86/QZ4P level. Our computations show that, over the entire range of our model systems, the XYYX isomers are more stable than the X2YY forms except for X = F and Y = S and Te, for which the F2SS and F2TeTe isomers are slightly more stable. Our results also point out that the Y-Y bond length can be tuned quite generally through the X-Y electronegativity difference. The mechanism behind this electronic tuning is the population or depopulation of the π* in the YY fragment

We thank the following organizations for financial support: the HPC-Europa program of the European Union, The Netherlands Organization for Scientific Research (NWO), the Ministerio de Ciencia e Innovacion (MICINN, project numbers CTQ2011-23156/BQU and CTQ2011-25086/BQU, Ramon y Cajal contract to J.P., and FPI fellowship to M.E-H.), the Catalan Departament d’Innovacio, Universitats i Empresa (DIUE, project no. 2009SGR637 and Xarxa de Referenda en Quimica Teorica i Computacional), the FEDER fund (European Fund for Regional Development) for the grant UNGI08-4E-003, and the National Research School Combination Catalysis (NRSC-C). Support for the research of M.S. was received through the ICREA Academia 2009 prize for excellence in research funded by the DIUE of the Generalitat de Catalunya. Excellent service by the Stichting Academisch Rekencentrum Amsterdam (SARA), the Centre de Serveis Cientifics i Academics de Catalunya (CESCA), and the Barcelona Supercomputing Center Centro Nacional de Supercomputacion (BSC-CNS) is gratefully acknowledged

American Chemical Society (ACS)