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Electronic Structures of Organometallic Complexes of f Elements. 78 [1] Supplementary Information of Polarized Raman Spectra of Oriented Single Crystals and Model Calculations on the Basis of Density Functional Theory for Assigning the Vibrational Spectra of Decamethylosmocene
Author(s) -
Reddmann Hauke,
Prosenc Marc Heinrich,
Amberger HannsDieter
Publication year - 2012
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201100548
Subject(s) - raman spectroscopy , physics , molecule , crystallography , spectral line , proton , atomic physics , chemistry , optics , quantum mechanics
Abstract The far and mid infrared (FIR/MIR) spectra of powdered Os(η 5 ‐C 5 Me 5 ) 2 (OsCp* 2 ) as well as the polarized Raman spectra of an oriented single crystal (where the two molecules of D 5 h symmetry in the unit cell are uniformly oriented) have been recorded. The latter allow the assignment of the observed Raman lines to irreducible representations (irreps) which agree well with the predictions of a calculation applying density functional theory. This finding suggests additional correlation of the observed (unpolarized) bands in the FIR/MIR spectra with the calculated wavenumbers (and their irreps) of IR active normal modes. Neglecting νCH vibrations an r.m.s. deviation of 15.8 cm –1 for 40 assignments (Raman and IR) could be achieved. Skeletal and intra‐ligand vibrations could be identified and a number of previous assignments of the latter had to be revised. Because of mixing with skeletal modes some of the low frequency intra‐ligand vibrations display a noticeable dependence on the mass of the central atom which prevents the direct transfer of the identified γCCH 3 and βCCH 3 normal modes from M Cp* 2 ( M = Fe, Ru, Os) to Ln Cp* 3 ( Ln = La, Ce, Pr, Nd, Sm) complexes.