The NMR indirect nuclear spin–spin coupling constant of the HD molecule

Abstract

We present new calculated and experimental values of the NMR indirect nuclear spin–spin coupling constant in HD. In the quantum-chemical ab initio calculations, the full configuration-interaction (FCI) method is used, yielding an equilibrium value of 41.22 Hz in the basis-set limit. Adding a calculated zero-point vibrational correction of 1.89 Hz and a temperature correction of 0.20 Hz at 300 K, we obtain a total calculated spin–spin coupling constant of J _FCI(HD) = 43.31(5) Hz at 300 K. This result is within the error bars of the experimental gas-phase NMR value, J _exp(HD) = 43.26(6) Hz, obtained by extrapolating values measured in HD–He mixtures to zero density.

Keywords:

• indirect nuclear spin–spin coupling constants
• HD molecule
• ab initio FCI calculations
• gas-phase ²H NMR

Acknowledgements

We are indebted to Dr. Micah Ledbetter of the University of California at Berkeley for providing us with the motivation for this study and to Dr. Frank Jensen of the Aarhus University for providing us with the aug-pcJ-5 basis set. P.G. was supported by the Foundation for Polish Science MPD Programme co-financed by the European Union (EU) European Regional Development Fund. This work was supported by the Norwegian Research Council through the CoE Centre for Theoretical and Computational Chemistry (CTCC) Grant No. 179568/V30.