Relativistic effects on the nuclear magnetic resonance shielding of FX (X = F, Cl, Br, I, and At) molecular systems

SERGIO S GOMEZ ; GUSTAVO A AUCAR

JOURNAL OF CHEMICAL PHYSICS

AMER INST PHYSICS

Año: 2011 vol. 134 p. 2043141 - 2043148

0021-9606

We present ab inito full four-component and spin-free calculations of the NMR shielding parameter, σ , in the FX (X = F, Cl, Br, I and At) molecular systems. A different expression that overcomes the traditional non-relativistic (NR) approximation used to calculate the relationship between spin-rotation constants and the paramagnetic terms of paramagnetic σ  are given. Large deviations from NR results are obtained for σ (X; X = I and At) and for σ (F; FAt). σ (I; FI) is zero within the NR approach but −447.4 parts per million from our calculations. The electronic origin of relativistic corrections areanalyzed. All passive SO contributions are obtained as a difference between full four-component calculations and spin-free ones. Considering relativistic effects on the anisotropy, we obtain a deviation of 10% for I and 25% for At. σ(SO) (X) is always negative and σ(SF) (X) is always positive; the passive SO becomes larger than the SF one for X = Br, I, and At. Both σ(SO) (X) and σ⊥(SO) (X) have a functional dependence such as a Z X^b being the exponent 3.5 and 3.65, respectively. The passive SO contribution to the anisotropy has a similar functional dependence with an exponent of 3.60, meaning thatits perpendicular component is larger than its corresponding parallel component