GIPAW (gauge including projected augmented wave) and local dynamics in 13C and 29Si solid state NMR: the study case of silsesquioxanes (RSiO1.5)8

文献信息

发布日期 2009-06-26
DOI 10.1039/B907450C
影响因子 3.676
作者

Christel Gervais, Laure Bonhomme-Coury, Francesco Mauri, Florence Babonneau, Christian Bonhomme


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摘要

Octameric silsesquioxanes (RSiO1.5)8 are versatile and interesting nano building blocks, suitable for the synthesis of nanocomposites with controlled porosity. In this paper, we revisit the 29Si and 13C solid state NMR spectroscopy for this class of materials, by using GIPAW (gauge including projected augmented wave) first principles calculations [Pickard & Mauri, Phys. Rev. B, 2001, 63, 245101]. Full tensorial data, including the chemical shift anisotropies (CSA) and the absolute orientation of the corresponding principal axes systems (PAS), were calculated. Subsequent averaging of the calculated tensors (due to fast reorientation of the R groups around the Si–C bonds) allowed for the interpretation of the strong reduction of CSA and dipolar couplings for these derivatives. Good agreement was observed between the averaged calculated data and the experimental parameters. Interesting questions related to the interplay between X-ray crystallography and solid state NMR are raised and will be emphasized.

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来源期刊

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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