James L. Stauffer

Geometry of the Transition‐Metal Dihalides: The Fluorides of Manganese, Cobalt, Nickel, Copper, and Zinc

The deflection of mass spectrometrically detected beams of CaF2, MnF2, MnCl2, CoF2, NiF2, CuF2, ZnF2, ZnCl2, and HgCl2 by an inhomogeneous electric field has been examined. As found previously, CaF2 deflects in the manner expected for a polar molecule. The remaining molecules listed were found to be nonpolar. These observations are interpreted to imply that while CaF2 has a nonlinear equilibrium geometry the remaining species are linear. The result for HgCl2 is in agreement with a number of previous electron diffraction and spectroscopic studies.

Determination of the Geometry of Lithium Oxide, Li2O(g), by Electric Deflection

A conventional Inghram‐type mass spectrometer has been adapted to permit the study of the polarity of high‐temperature species by electric‐deflection methods. The molecule Li2O has been found to be nonpolar and therefore to have an equilibrium angle close to 180°, as shown by the absence of deflection of a molecular beam by an inhomogeneous electric field. The species LiO, which was found by Berkowitz, Chupka, Blue, and Margrave, has been confirmed to form a small percentage of the vapor in equilibrium with solid Li2O. Gaseous lithium molybdate, Li2MoO4, has been observed. It is readily formed by the reaction of lithium oxide with molybdenum above 1150°C.

Determination of Electronic Symmetry by Electric Deflection: LiO and LaO

The focusing, by means of an electrostatic quadrupole, of polar molecules with first‐ or second‐order Stark effects is discussed. Indications of molecular electronic symmetry may be obtained from quantitative measurements of the intensity of refocusing of beams of diatomic molecules. Such measurements indicate that the ground state of LiO is Π while that of LaO is Σ. It is suggested that the optical spectroscopic data of ScO, YO, and LaO are best explained by assigning the ground states of these three molecules as 2Σ. The observed low‐lying electronic states of these molecules are interpreted in terms of a localized‐orbital picture.

Molecular Structure of XeF6 and IF7

The deflection of molecular beams of XeF2, XeF4, XeF6, and IF7 in an inhomogeneous electric field has been examined. From the defocusing behavior of each of these species, it is concluded that the electric dipole moment μ is less than 0.03 D for XeF4, XeF6, and IF7 if these molecules have rigid structures. The upper limit for the polarity of nonrigid (inverting) structures is (μ / Δ1 / 2) < 0.1 D / (cm−1) / 2, where Δ is the separation between inversion doublets. These results imply molecular structures with symmetry‐forbidden electric dipole moments for XeF4, XeF6, and IF7.

Electric‐Deflection Studies of the Geometry of Some Molecules Containing Cesium

The deflection of molecular beams in an inhomogeneous electric field shows that the species Cs2O is polar and therefore nonlinear. The species Cs2SO4, Cs2O2, and Cs2(OH)2 are found to be nonpolar. H2SO4 is polar in agreement with the C2v heavy‐atom structure deduced previously by Stafford and Chackalackal from infrared spectroscopy.