In:
The Journal of Chemical Physics, AIP Publishing, Vol. 78, No. 5 ( 1983-03-01), p. 2231-2239
Abstract:
The absorption and MCD spectra of the 2P ← 2S transition of Cu atoms isolated in argon matrices have been measured over the temperature range 13–25 K. Spectral band moments (up to third order in MCD) have been determined and parameters of interest extracted from them. The observed triplet bands’ separation and MCD 𝒞 term signs are analyzed assuming a static trigonal site distortion. It is shown that a static site distortion model is incapable of reproducing the experimental results. Simultaneous spin orbit and noncubic lattice vibrational couplings (Jahn–Teller effect) are shown to be active in the Cu excited 2P state. The observed triplet of bands and its MCD 𝒞 terms are satisfactorily described by an adiabatic model developed by Moran. Comparison of the observed band shape to ones calculated by Cho using Monte Carlo methods show that simultaneous spin-orbit and e and t2 lattice mode interactions are operative. The observed reduction of 25% in the excited state spin-orbit coupling constant is attributed to the overlap of Cu 4p orbitals with the Ar 3p orbitals. A new method for the determination of the temperature of matrix-isolated samples is described. The temperature dependence of the MCD first moment and absorption zeroth moment of a matrix-isolated paramagnetic species is determined once to find the lowest temperature attainable.
Type of Medium:
Online Resource
ISSN:
0021-9606
,
1089-7690
Language:
English
Publisher:
AIP Publishing
Publication Date:
1983
detail.hit.zdb_id:
3113-6
detail.hit.zdb_id:
1473050-9
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