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Impact of Spin State Transition on Vibrations of [Fe–(PM–BiA) 2 (NCS) 2 ] and [Fe–(PM–PEA) 2 (NCS) 2 ] Spin Crossover Compounds: Experimental and Theoretical Far IR and Raman Study
Author(s) -
OuldHamouda Amine,
Viquerat Benjamin,
Degert Jérôme,
Matar Samir F.,
Létard Jean François,
Guillaume François,
Freysz Eric
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201700979
Subject(s) - chemistry , raman spectroscopy , spin crossover , spectroscopy , analytical chemistry (journal) , spin states , absorption (acoustics) , absorption spectroscopy , density functional theory , spin (aerodynamics) , wavenumber , molecule , molecular vibration , spectral line , spin transition , infrared spectroscopy , molecular physics , atomic physics , crystallography , computational chemistry , inorganic chemistry , optics , physics , organic chemistry , chromatography , quantum mechanics , astronomy , thermodynamics
Far IR and Raman spectroscopy of [Fe–(PM–BiA) 2 (NCS) 2 ] and [Fe–(PM–PEA) 2 (NCS) 2 ] were performed to record the vibration modes of these complexes and their evolutions during spin state transition. THz spectroscopy was used to measure the far IR absorption of these compounds down to 20 cm –1 . Using density functional theory calculations, we were able to retrieve and to visualize these vibrations in both high‐spin and low‐spin states. In both compounds, Raman spectra recorded in the 800–2250 cm –1 wavenumber range are well accounted for by our computations. For far IR vibration modes, most of the experimental absorption peaks above 100 cm –1 are well reproduced. However, below 100 cm –1 , marked differences were recorded. For [Fe–(PM–BiA) 2 (NCS) 2 ], we demonstrate that the interactions with surrounding molecules impact the computed far IR spectra non‐negligibly and can partly correct this difference.