Experimental and CIS, TD-DFT, ab initio calculations of visible spectra and the vibrational frequencies of sulfonyl azide-azoic dyes

• Published in: Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy Vol. 72; no. 2; pp. 369 - 377
• Main Authors: Teimouri, Abbas, Chermahini, Alireza Najafi, Taban, Keivan, Dabbagh, Hossein A.
• Format: Journal Article
• Language: English
• Published: England Elsevier B.V 01.03.2009
• Subjects: Ab initio; Azides - chemistry; Azo Compounds - chemistry; Azo dyes; CIS; Coloring Agents - chemistry; Models, Chemical; Molecular Conformation; Molecular Structure; Spectrum Analysis, Raman - methods; TD-DFT; Vibration; Vibrational frequencies; Visible spectra; Ab initio; Vibrational frequencies; CIS; Azo dyes; Visible spectra; TD-DFT
• ISSN: 1386-1425
• DOI: 10.1016/j.saa.2008.10.006

The detailed experimental and computational analysis [Hartree-Fock (HF), Time-Dependent Density-Functional Theory (TD-DFT) and Second-Order Møller-Plesset Perturbation Theory (PM2) levels of theory at standard 6-31G* basis set] of structure, infrared spectra and visible spectra of azo dyes are investigated. The optimized geometries and calculated vibrational frequencies are evaluated via comparison with experimental values. The vibrational spectral data obtained from solid phase FT-IR spectra are assigned based on the results of the theoretical calculations. The observed spectra are found to be in good agreement with the calculated values. The geometry optimization yields a planar conformation for phenyl rings with azo moiety. The energy and oscillator strength calculated by Configuration Interaction Singles (CIS) complements the Time-Dependent Density-Functional Theory (TD-DFT) results and the experimental findings. Unfortunately, PM2 method could not predict vibrational frequencies and visible spectra of the azo dyes under conditions of this investigation.