Performance of DFT for29Si NMR chemical shifts of silanes

Thomas Heine; Annick Goursot; Gotthard Seifert; Jacques Weber

doi:10.1021/jp002495k

Performance of DFT for²⁹Si NMR chemical shifts of silanes

Thomas Heine, Annick Goursot, Gotthard Seifert, Jacques Weber

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

29 Citations (Scopus)

Abstract

The predictive power of DFT, HF, and MP2 ²⁹Si NMR chemical shift calculations for silane molecules, including fluoro- and methylsilanes (Si_nH_2n+2 (n = 1, ..., 5), Si_nF_2n+2 (n = 1, ..., 3), and SiH_mX_4-m (X = F, CH₃)) is compared. A systematic accumulation of error proportional to the number of hydrogen neighbors to silicon sites is observed for DFT for all applied exchange-correlation functionals, whereas MP2 is not affected by this problem. A proposed empirical correction scheme for DFT provides excellent agreement with experiment with any exchange-correlation functional employed in this study.

Original language	English
Pages (from-to)	620-626
Number of pages	7
Journal	Journal of Physical Chemistry A
Volume	105
Issue number	3
DOIs	https://doi.org/10.1021/jp002495k
Publication status	Published - 2001 Jan 25

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry

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10.1021/jp002495k

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title = "Performance of DFT for29Si NMR chemical shifts of silanes",

abstract = "The predictive power of DFT, HF, and MP2 29Si NMR chemical shift calculations for silane molecules, including fluoro- and methylsilanes (SinH2n+2 (n = 1, ..., 5), SinF2n+2 (n = 1, ..., 3), and SiHmX4-m (X = F, CH3)) is compared. A systematic accumulation of error proportional to the number of hydrogen neighbors to silicon sites is observed for DFT for all applied exchange-correlation functionals, whereas MP2 is not affected by this problem. A proposed empirical correction scheme for DFT provides excellent agreement with experiment with any exchange-correlation functional employed in this study.",

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AU - Heine, Thomas

AU - Goursot, Annick

AU - Seifert, Gotthard

AU - Weber, Jacques

PY - 2001/1/25

Y1 - 2001/1/25

N2 - The predictive power of DFT, HF, and MP2 29Si NMR chemical shift calculations for silane molecules, including fluoro- and methylsilanes (SinH2n+2 (n = 1, ..., 5), SinF2n+2 (n = 1, ..., 3), and SiHmX4-m (X = F, CH3)) is compared. A systematic accumulation of error proportional to the number of hydrogen neighbors to silicon sites is observed for DFT for all applied exchange-correlation functionals, whereas MP2 is not affected by this problem. A proposed empirical correction scheme for DFT provides excellent agreement with experiment with any exchange-correlation functional employed in this study.

AB - The predictive power of DFT, HF, and MP2 29Si NMR chemical shift calculations for silane molecules, including fluoro- and methylsilanes (SinH2n+2 (n = 1, ..., 5), SinF2n+2 (n = 1, ..., 3), and SiHmX4-m (X = F, CH3)) is compared. A systematic accumulation of error proportional to the number of hydrogen neighbors to silicon sites is observed for DFT for all applied exchange-correlation functionals, whereas MP2 is not affected by this problem. A proposed empirical correction scheme for DFT provides excellent agreement with experiment with any exchange-correlation functional employed in this study.

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Performance of DFT for²⁹Si NMR chemical shifts of silanes

Abstract

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