Friday, August 29, 2008

Chemical Physics Volume 352, Issues 1-3, Pages 320-326

Indirect spin–spin coupling constants in CH4, SiH4 and GeH4 – Gas-phase NMR experiment and ab initio calculations

Andrej Antušeka, Dariusz Ke¸dzierab, Karol Jackowskic, Michał Jaszuńskid, , and Włodzimierz Makulskic

New values of the indirect spin–spin coupling constants in CH4, SiH4 and GeH4, derived from experiment and ab initio calculations, are reported. The new experimental values of 1J(CH), 1J(SiH) and 1J(GeH) are obtained from gas-phase NMR spectra. The dependence of the measured one-bond coupling constants on the density is analysed and the results are extrapolated to zero-density point to eliminate the effects due to intermolecular forces. In the calculation of the coupling constants, at the nonrelativistic level coupled cluster singles and doubles (CCSD) perturbation theory is used and the basis set convergence of the results is discussed. The relativistic corrections are estimated from Dirac–Hartree–Fock (DHF) calculations. The final theoretical values are obtained adding available estimates of the vibrational and temperature corrections. The agreement of the calculated and experimental 1J(XH), X = C, Si, Ge, constants is very satisfying, the differences are approximately 1–3%.

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