Isotope effects on the vibrational spectra of the Fe(Phen)2(NCS)2 spin-crossover complex studied by density functional calculations

被引：16
作者：
Pálfi, VK
Guillon, T
Paulsen, H
Molnár, G
Bousseksou, A
机构：
[1] CNRS, UPR 8241, Chim Coordinat Lab, F-31077 Toulouse, France
[2] Eotvos Lorand Univ, Inst Chem, H-1117 Budapest, Hungary
[3] Med Univ Lubeck, Inst Phys, D-23538 Lubeck, Germany
来源：
COMPTES RENDUS CHIMIE | 2005年 / 8卷 / 08期
关键词：
DFT; spin crossover; vibrational frequencies; isotope effect; vibrational entropy;
D O I：
10.1016/j.crci.2004.11.032
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
A geometry optimization and vibrational frequency calculation has been carried out on the Fe(phen)(2)(NCS)(2) (phen = 1, 10 phenantroline) molecule in both spin states (S = 0 and S = 2) using the density functional theory (DFT) method with the B3LYP functional and the 6-31G(d) basis set. The frequency shifts upon Fe-54-Fe-57 and N-14-N-15 isotope substitutions have been calculated and compared with the experimental frequency shifts as well as with calculated data (DFT/BP86) published in the literature. In the low frequency region (100-600 cm(-1)), both DFT methods reproduce correctly the measured isotope shifts. The accuracy of the calculated vibrational entropy change upon the spin crossover (SCO) is lower: reasonable errors (similar to 10%) of the calculated frequencies lead to a relatively large error (similar to 50%) of the total entropy change. (c) 2005 Academie des sciences. Published by Elsevier SAS. All rights reserved.
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收藏
页码：1317 / 1325
页数：9
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