A coupled cluster study of the magnetisability, rotational g-tensor and quadrupole moment of NF3, PF3 and AsF3. (17th September 2017)

• Record Type: Journal Article
• Authors: Field-Theodore, Terri E.; Wilson, David J. D.
• Is Part Of: Molecular physics. Volume 115:Number 17/18(2017)
• Page Start: 2285
• Page End: 2299
• Publication Date: 2017-09-17
• Subjects: Magnetisability -- trifluorides -- coupled-cluster -- Zeeman properties; Molecules -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Molécules -- Périodiques; Chimie physique et théorique -- Périodiques; 539.6.05
• DOI: 10.1080/00268976.2017.1349346
• Languages: English
• ISSNs: 0026-8976

Abstract

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. Abstract :