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

作者：Field Theodore Terri E; Wilson David J D^*

来源：Molecular Physics, 2017, 115(17-18): 2285-2299.

DOI：10.1080/00268976.2017.1349346

• Magnetisability
• trifluorides
• coupled-cluster
• Zeeman properties

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(perpendicular to) 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.