Molecular Zeeman Effect of Dimethyl Ether and Dimethyl Sulfide; and Comparison of the Magnetic Susceptibility Anisotropies with Ethylene Sulfide and Ethylene Oxide

Abstract

The rotational Zeeman effect has been observed in dimethyl sulfide and dimethyl ether. The molecular g values (gaa, gbb, and gcc), the magnetic susceptibility anisotropies [(2χaa − χbb − χcc) and (− χaa + 2χbb − χcc)], and the molecular quadrupole moments are obtained and listed below. The a and b axes are in the molecular plane. The b axis bisects the COC or CSC angle. The units of χ are 10−6 erg/G2·mole and the units of Qxx are 10−26 esu·cm2. CH3OCH3CH3SCH3gaa− 0.214 ± 0.0006− 0.0193 ± 0.0007gbb− 0.0093 ± 0.00040.0000 ± 0.0003gcc− 0.0210 ± 0.0006− 0.0083 ± 0.00032χaa − χbb − χcc− 10.4 ± 0.7− 4.2 ± 0.5− χaa + 2χbb − χcc+ 1.2 ± 0.6− 2.8 ± 0.5Qaa+ 3.3 ± 0.6+ 3.2 ± 0.5Qbb− 2.0 ± 0.5− 1.5 ± 0.5Qcc− 1.3 ± 1.0− 1.7 ± 0.8 The anisotropies in the second moment of the electronic charge distribution are also obtained. The susceptibility anisotropies are compared with those of propene, cyclopropene, ethylene sulfide, and ethylene oxide leading to the conclusion that nonlocal contributions to the susceptibility anisotropies in ring molecules have been underestimated.