Reactions of Metal Atoms. IV. The uv Spectra of CdBr, CdI, ZnBr, and ZnI

Abstract

Ultraviolet absorption spectra were recorded for CdBr, CdI, ZnBr, and ZnI produced in the cophotolysis of the appropriate trifluoromethyl halide and dimethyl metal compounds. Both the Π3/22 − 2Σ andΠ1/22 − 2Σ systems were observed in all cases. Most of the bands analyzed are in agreement with the emission spectra reported earlier in the literature. The Π1/22 − 2Σ system of CdBr and ZnI are reported here for the first time. Complete vibrational analysis of the spectra was performed and the Π2 splitting values compared.

Electronic structure with dipole moment calculation of the low-lying electronic states of ZnBr molecule

“…The experimental observation [5,19] of the analogous B 2 R + -X 2 R + transition of ZnF, ZnCl and ZnI could stimulate further experiments concerning the metal monobromide. The interaction between the adiabatic PECs of the two lowest 2 P states, correlated with the first and second asymptote respectively, results deep minimum for the (2) 2 P at 2336 Å due to an avoided crossing near 2.190 Å The spectroscopic constants determined experimentally for the (2) 2 PX 2 R + transition [2,3,6] are compared to the values of T e = 31,832 cm À1 and x e = 286.4 cm À1 calculated for the upper state. The relative difference ranges between (0.91% Ref.…”

“…The relative difference ranges between (0.91% Ref. [6])6DT e /T e 6(2.21% Ref. [2]) and Dx e /x e = 0.85% [3].…”

Electronic structures and chemical bonding in 4d transition metal monohalides

“…On the other hand, second order pertubational multireference configuration interaction (MRPT2) method46 and DFT47 method were used to study both neutral and charged AgBr. For neutral CdBr, ultraviolet absorption spectra were recorded 48. For cationic CdBr + , ab initio self‐consistent‐field molecular orbital method was available 42.…”

Single Ion Transitions in Ionic Diatomic Molecules

“…4 For example, the 2n band splittings of Zn, Cd, and Hg halides are approximately constant for a given cation, and it has been proposed that they depend on the coupling constant of the corresponding neutral atom. 5 If the ion in the molecule tends to preserve its electronic integrity, then there should be a full correlation between the lower molecular transitions and the free ion excited states. 2 The separation of the free ion levels, however, will be much greater than those of the Coulombically bound ion pair in the molecule because the effective charges on the cores would approximate two and one, respectively.…”