English
 
User Manual Privacy Policy Disclaimer Contact us
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  Experimental gas phase H-1 NMR spectra and basis set dependence of ab initio GIAO MO calculations of H-1 and C-13 NMR absolute shieldings and chemical shifts of small hydrocarbons

Zuschneid, T., Fischer, H., Handel T, Albert, K., & Hafelinger, G. (2004). Experimental gas phase H-1 NMR spectra and basis set dependence of ab initio GIAO MO calculations of H-1 and C-13 NMR absolute shieldings and chemical shifts of small hydrocarbons. Zeitschrift für Naturforschung B, 59, 1153-1176. Retrieved from http://www.znaturforsch.com/s59b/s59b1153.pdf.

Item is

Basic

show hide
Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0013-D793-2 Version Permalink: http://hdl.handle.net/11858/00-001M-0000-0013-D794-F
Genre: Journal Article

Files

show Files

Locators

show

Creators

show
hide
 Creators:
Zuschneid, T, Author
Fischer, H1, Author              
Handel T, Albert, K, Author
Hafelinger, G, Author
Affiliations:
1Max Planck Institute for Biological Cybernetics, Max Planck Society, ou_1497794              

Content

show
hide
Free keywords: -
 Abstract: High-resolution gas phase measurements of H-1 NMR spectra at 400 MHz and atmospheric pressure of seven small hydrocarbons are presented. The developed new method and the experimental set-up are described. Ab initio GIAO MO calculations of H-1 and C-13 NMR absolute shieldings on the HF, MP2 and B3LYP levels using 25 standard gaussian basis sets are reported for these hydrocarbons, based on experimental r(e) distances. The measured gas phase H-1 chemical shifts have been converted to an absolute sigma(0) shielding scale by use of the literature shielding of methane. These and gas phase C-13 literature values have been transferred with literature ZPV data to estimated sigma(e)(exp) shieldings which are used to evaluate the basis set dependence of the calculated a, shieldings utilizing linear least squares regressions. Exponential extrapolations of Dunning basis set calculations allow the determination of basis set limits for H-1 and C-13 shieldings. H-1 and C-13 chemical shifts have been derived from the HF calculated shieldings with shieldings of TMS which has been geometry optimized and GIAO calculated in each basis. Standard deviations, (esd) as low as 0.09 ppm for H-1 and 0.76 ppm for C-13 calculations have been obtained. The statistically best basis set for simultaneous calculation of H-1 and C-13 absolute shieldings or relative shifts is 6-311G* within the HF and B3LYP methods. Aiming for highest accuracy and precision, H-1 and C-13 have to be treated separately. In this case. best results are obtained using MP2/6-311G** or higher for H-1 shieldings and MP2/cc-pVTZ for C-13 shieldings.

Details

show
hide
Language(s):
 Dates: 2004-10
 Publication Status: Published in print
 Pages: -
 Publishing info: -
 Table of Contents: -
 Rev. Method: -
 Identifiers: URI: http://www.znaturforsch.com/s59b/s59b1153.pdf
BibTex Citekey: 3175
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Zeitschrift für Naturforschung B
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: -
Pages: - Volume / Issue: 59 Sequence Number: - Start / End Page: 1153 - 1176 Identifier: -