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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].

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Garcia, Yann [UCL] Paulsen, Hauke Schünemann, Volker Trautwein, Alfred X Wolny, Juliusz A.

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.

Document type Article de périodique (Journal article) – Journal Article, Research Support, Non-U.S. Gov't
Publication date 2007
Journal information "Physical chemistry chemical physics : PCCP" - Vol. 9, no. 10, p. 1194-201 (2007)
Peer reviewed yes
issn 1463-9076
Publication status Publié
Affiliation UCL - SC/CHIM - Département de chimie
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Bibliographic reference Garcia, Yann ; Paulsen, Hauke ; Schünemann, Volker ; Trautwein, Alfred X ; Wolny, Juliusz A.. 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].. In: Physical chemistry chemical physics : PCCP, Vol. 9, no. 10, p. 1194-201 (2007)
Permanent URL http://hdl.handle.net/2078.1/10877