Abstract The rotational Zeeman effect has been observed in methanimine which was produced from ethylenediamine by flash pyrolysis. The observed vibronic ground state expectation values of the molecular g-values, the magnetic susceptibility anisotropies and the molecular electric quadrupole moments are: gaa = -1.27099(22), gbb= -0.18975(7), gcc= -0.03440(8), 2ξaa-ξbb-ξcc = 12.49(19) · 10-6 ergG-2mol-1, 2ξbb-ξcc-ξaa = 5.22(11) · 10-6 ergG-2 mol-1 Qaa = 0.43(17) · 10-26esu cm2, Qbb= 1.08(10) · 10-26 esu cm2, and Qcc= -1.51 (26) . 10-26 esu cm2. With the TZVP ab initio value for the out-off plane electronic second moment as additional input, reliable values can be given also for the individual components of the magnetic susceptibility tensor and for the bulk susceptibility:ξ = (ξaa + ξbb + ξcc)/3=-13.13(88) · 10-6 erg G -2 mol-1. From low-J a-and b-type zero field transitions the spin-rotation coupling constants and the 14N nuclear quadrupole coupling constants could be redetermined with improved accuracy. These data are compared with our new theoretical results.
Thermodynamic approach to electric quadrupole moments