title: Estimate of the vibrational contribution to the entropy change associated with the spin transition in the d4 systems [MnIII(pyrol)3tren] and [CrII(depe)2I2].
abstract: The vibrational contribution to DeltaS of the low-spin ((3)T(1)) to high-spin ((5)E) spin transition in two 3d(4) octahedral systems [Mn(III)(pyrol)(3)tren] and [Cr(depe)(2)I(2)] have been estimated by means of DFT calculations (B3LYP/CEP-31G) of the vibrational normal-modes frequencies. The obtained value at the transition temperature for the Mn(iii) complex is DeltaS(vib)(44 K) = 6.3 J K(-1) mol(-1), which is comparable with the proposed Jahn-Teller contribution of R ln3 = 9.1 J K(-1) mol(-1) and which is approximately half of the experimentally determined 13.8 J K(-1) mol(-1). The corresponding value for the Cr(ii) complex is DeltaS(vib)(171.45 K) = 46.5 J K(-1) mol(-1), as compared to the experimental value of 39.45 J K(-1) mol(-1). The analysis of the vibrational normal modes reveals that for the d(4) systems under study, contrary to Fe(ii) d(6) systems, not all metal-ligand stretching vibrations make a contribution. For the Mn(iii) complex, the only vibration that contributes to DeltaS(vib) involve the nitrogens occupying the Jahn-Teller axis, while in the case of Cr(ii) the contributing vibrations involve the Cr-I bonds. Low-frequency modes due to ring vibrations, metal-ligand bending and movement of the molecule as a whole also contribute to the vibrational entropy associated with the spin transition.
authors.affiliation: Unité de Chimie des Matériaux Inorganiques et Organiques, Département de Chimie, Faculté des Sciences, Université Catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve, Belgium.
authors.forename: Yann
authors.initials: Y
authors.lastname: Garcia
authors.forename: Hauke
authors.initials: H
authors.lastname: Paulsen
authors.forename: Volker
authors.initials: V
authors.lastname: Schünemann
authors.forename: Alfred X
authors.initials: AX
authors.lastname: Trautwein
authors.forename: Juliusz A
authors.initials: JA
authors.lastname: Wolny