Molecular beam Zeeman effect and dipole moment sign of ClF

Abstract

Molecular beam electric resonance spectroscopy has been used to observe hyperfine, Stark, and Zeeman properties of chlorine monofluoride. The dipole moment from Zeeman data is 0.85(15), −FCl+, in agreement with the known magnitude. The sign obtained here is the opposite of earlier, less precise, Zeeman results but agrees with calculations and van der Waals molecule experiments. Hyperfine, Stark, and Zeeman properties for 35ClF and 37ClF are reported, including polarizability anisotropy, α∥−α⊥=1.32(8) Å3, molecular quadrupole moment, ϑ∥=1.54(7) ×10−26 esu⋅cm2, and the chlorine quadrupole coupling constant derivative, deQq/dR=−90(20) MHz/Å.

Molecular electric moments calculated by using natural orbital functional theory

“…We compare the obtained PNOF6 results with the experimental values reported in the literature [6,10,11,[25][26][27][28], as well as with the theoretically computed values of Bundgen et al who used the multi-reference single and double excitation configuration interaction (MRSD-CI) method, and the coupled-cluster single and doubles (CCSD) values calculated by us. Recall that the CCSD values for one-electron properties differ from full-CI results in only 2% if no multiconfigurational character is observed [29], so they can be considered as benchmark calculations.…”

The Interaction of Water and Dibromine in the Gas Phase: An Investigation of the Complex H2O⋅⋅⋅Br2 by Rotational Spectroscopy and Ab Initio Calculations

“…In the case of the nonpolar dihalogens, this is the order of their electric quadrupole moments which have the values 2.8 Â 10 À40 , 10.8(5) Â 10 À40 and 17.5 Â 10 À40 C m 2 for F 2 , Cl 2 and Br 2 , respectively. [38,39] The complexes in which the dihalogen is polar are all more strongly bound than those involving nonpolar species and the order is the order of the electric dipole moments of the halogen, namely BrCl [40] < ClF [41] < ICl. [42] Secondly, with the exception of H 2 O ¥¥¥ ICl, the order of the potential energy barrier V(f e ) À V(f 0) follows the order of the binding strength.…”

Prereactive Complexes of Dihalogens XY with Lewis Bases B in the Gas Phase: A Systematic Case for the Halogen Analogue B⋅⋅⋅XY of the Hydrogen Bond B⋅⋅⋅HX

“…The order E F 2`E Cl 2`E Br 2`E BrCl`EClF is reasonable in view of the order of the electric quadrupole moments [69,70] of 2.76 Â 10 À40 C m 2 , 10.79(54) Â 10 À40 C m 2 , and 17.52 Â 10 À40 C m 2 for F 2 , Cl 2 , and Br 2 , respectively, and the fact that BrCl and ClF have small electric dipole moments of similar magnitude. [71,72] 3.3. Systematic Behavior among Angular Geometries of B´´´XY…”