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Electronic Structures of Organometallic Complexes of f Elements. 80 [1] Is it Possible to Identify the Stretching and Tilting Modes of the Pseudo Trigonal Planar La(η 5 ‐C 5 H 5 ) 3 Moiety in the Vibrational Spectra of [La(η 5 ‐C 5 H 5 ) 3 (NCCH 3 ) 2 ] without the Aid of Model Calculations on the Basis of the Density Functional Theory?
Author(s) -
Amberger HannsDieter,
Reddmann Hauke
Publication year - 2013
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.201200451
Subject(s) - raman spectroscopy , physics , crystallography , irreducible representation , trigonal crystal system , spectral line , moiety , symmetry (geometry) , atomic physics , chemistry , stereochemistry , crystal structure , optics , geometry , quantum mechanics , mathematics
Abstract In order to reliably assign the four previously observed coincidences in the range 210–260 cm –1 in the low temperature vibrational spectra of [LaCp 3 (NCCH 3 ) 2 ] (Cp = η 5 ‐C 5 H 5 – ) ( 1 ) to the expected stretching and tilting modes of the pseudo trigonal planar LaCp 3 moiety, additionally the “polarized“ Raman spectra of an oriented single crystal of 1 were recorded. By this means, the signal of the tilting vibration of the irreducible representation (irrep) E′' could be separated from the remaining skeletal vibrations consisting of the irreps A 1 ′, E' and E′. The bands of the two latter could be identified by applying the less common method of the “symmetry allowed vibronic couplings of electronic zero point transitions“ to the vibronic sidebands of the purely electronic transition 1Γ 1 ( 3 H 4 )→8Γ 1 ( 3 P 0 ) of [LaCp 3 (NCCH 3 ) 2 ]:Pr 3+ ( 2 ). Hence, the remaining band corresponds to the symmetric stretching of A 1 ′ symmetry.