11B and 23 Na solid-state NMR and density functional theory studies of electric field gradients at boron sites in ulexite

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dc.contributor.author Zhou, Bing
dc.contributor.author Michaelis, Vladimir K.
dc.contributor.author Kroeker, Scott
dc.contributor.author Wren, John E. C.
dc.contributor.author Yao, Yefeng
dc.contributor.author Sherriff, Barbara L.
dc.contributor.author Pan, Yuanming
dc.date.accessioned 2013-11-27T23:05:46Z
dc.date.available 2013-11-27T23:05:46Z
dc.date.issued 2013-07-31
dc.identifier.citation CrystEngComm 2013, 15 8739-8747 en_US
dc.identifier.uri http://hdl.handle.net/1993/22290
dc.description This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. en_US
dc.description.abstract Nuclear magnetic resonance (NMR) parameters of 11B in borates and borosilicates, unlike those of many other nuclei such as 29Si and 27Al, vary only over limited ranges and have been thought to be insensitive to local structural environments. High-resolution NMR spectroscopy at high (14 T) and ultrahigh (21 T) fields yield precise 11B and 23Na NMR parameters for ulexite, which contains the pentaborate polyanion ([B5O6(OH)6]3−) as the fundamental building block (FBB). These NMR parameters are compared with ab initio theoretical calculations as implemented in WIEN2K, including optimization of the ulexite structure, determination of the electric field gradients (EFG) and consequently the nuclear quadrupole interaction (QI) parameters at the five distinct B sites, and calculations of the density of states (DOS). These calculations show that the magnitudes and signs of the EFG for [3]B and [4]B are determined by multiple factors, including the electron distributions in the B 2pz orbitals and their interactions with Ca-3p/O-2s orbitals. Most importantly, the calculated B 2pz orbitals at all B sites in ulexite are predominantly affected by the atoms within the fundamental building block, resulting in the insensitivity of the 11B QI parameters to the weak interunit interactions among FBB. Calculations with the water molecules removed from the ulexite structure provide further support for the strong intraunit interactions in FBB as a cause for the poor sensitivity of 11B NMR parameters to local structural environments, including hydrogen bonding, in borates. en_US
dc.description.sponsorship B. Z. received a research grant of the “One Hundred People Plan” provided by Chinese Academy of Geological Sciences for this study. Funding was also provided by the Canada Foundation for Innovation, Natural Sciences and Engineering Research Council of Canada (Discovery Grant (S. K., B. L. S.); PGSD3 (V. K. M.)) and the Government of Manitoba. Y. Y. acknowledges financial support from NSFC grant no. 20804016. en_US
dc.publisher Royal Society of Chemistry en_US
dc.rights info:eu-repo/semantics/openAccess
dc.subject NMR crystallography en_US
dc.subject density functional theory en_US
dc.subject boron en_US
dc.subject ulexite en_US
dc.title 11B and 23 Na solid-state NMR and density functional theory studies of electric field gradients at boron sites in ulexite en_US
dc.type Article en_US
dc.type info:eu-repo/semantics/article
dc.identifier.doi http://dx.doi.org/10.1039/C3CE41251B

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