A coupled cluster study of the magnetisability, rotational g-tensor and quadrupole moment of NF₃, PF₃ and AsF₃

ABSTRACT

A coupled-cluster investigation of magnetic and electric properties of NF₃, PF₃ and AsF₃ provides for a comparison with recent experimental data. For PF₃, achieving reliable values for the magnetisability and rotational g-tensor of PF₃ has been particularly challenging. We report the most accurate calculations to date for PF₃; for the vibrationally corrected anisotropic magnetisability, our extrapolated CCSD(T)/CBS value of −0.290 a.u is within the uncertainty limits of the most recent experimental value of −0.286 ± 0.042 a.u. For the rotational g-tensor of PF₃, agreement between theory and experiment for the g_⊥ component is excellent (deviation of less than 0.0006 a.u.). However, the g_|| component remains problematic even though our vibrationally corrected CCSD(T)/CBS value of −0.0387 a.u is in closer agreement with the recently revised experimental value of −0.0470 ± 0.0020 a.u. than the original value of −0.0815 ± 0.0020 a.u. The origin of the remaining discrepancy remains unclear. Dipole and quadrupole moments have also been investigated.

KEYWORDS:

• Magnetisability
• trifluorides
• coupled-cluster
• Zeeman properties

Acknowledgments

Computing resources from La Trobe University, Intersect (project ia1) and NCI-NF (project k02) are acknowledged gratefully.

Disclosure statement

No potential conflict of interest was reported by the authors.

Additional information

Funding

Intersect (project ia1) and NCI-NF (project k02).