Resonance Raman spectra of octaethylporphyrinato-Ni(II) and m e s o-deuterated and 15N substituted derivatives. I. Observation and assignments of nonfundamental Raman lines

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Abstract
High resolution resonance Raman spectra of octaethylporphyrinato-Ni(II) [Ni (OEP)], its meso-deuterated and 15N substituted derivatives were measured. With excitation near the O–1 transition, about 90 nonfundamental modes and previously unrecognized fundamental modes were observed for each derivative. The analysis of the nonfundamental Raman lines allowed the determination of all the fundamental frequencies in the A1g, B1g, A2g, and B2g species of D4h symmetry. Experimental classification of depolarized Raman lines to the B1g and B2g species was worked out. Combinations of B1g and B2g modes give rise to anomalously-polarized Raman lines while combinations of B1g modes and of B2g modes give rise to polarized lines. The Raman lines of the B1g species of Ni(OEP) with D4h symmetry are correlated with those in the Ag species of H2(OEP) with D2h symmetry while the B2g species of D4h is correlated with the B1g species of D2h. The experimental frequencies of fundamental modes thus determined satisfied the product rule for the isotopic substitution.

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