ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
High resolution He i (584 A(ring)) photoelectron spectra of ZnCl2, MnCl2, and NiCl2 were measured using a high temperature supersonic molecular beam source. In ZnCl2, vibrational structures were resolved, and spectroscopic constants were derived for the observed molecular ion states. A single ν1 vibrational progression was observed for the C 2Σ+g state of ZnCl+2. A Franck–Condon factor calculation allowed us to obtain a Zn–Cl equilibrium bond length increase of 0.095(5) A(ring) and a ν1 vibrational frequency of 290(8) cm−1. For the open-shell molecules, MnCl2 and NiCl2, no vibrational structure could be resolved because of their very low bending frequencies. Transitions from the ligand orbital and metal d orbital ionizations were clearly resolved, with those of the d orbitals having considerably narrower band widths. Even though many final states are expected for ionization of the open-shell d orbitals, only a few states were observed. This was explained in MnCl2 by the one-electron spin selection rule: Sf=Si ±1/2. Besides the spin selection rule, a propensity toward high spin was proposed to account for the spectrum of NiCl2. From the metal d orbital and ligand orbital splittings, the degree of covalent bonding was inferred to be in the order of: MnCl2〉NiCl2〉ZnCl2.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.459122
