ABINITIOSTUDYOFCD-THIOLCOMPLEXES.docVIP

AB INITIO STUDY OF CD-THIOL COMPLEXES: APPLICATION TO THE MODELLING OF THE METALLOTHIONEIN ACTIVE SITE Mironel ENESCU#?, Jean-Philippe RENAULT, Stanislas POMMERET, Jean-Claude?MIALOCQ and Serge PIN* Supplementary Materials 1. Computational method test We have examined the reliability of different computational methods in reproducing the experimental gas phase geometry of cadmium salts. Accurate experimental data were reported for CdCl2 and CdI2 molecules [1]. Experimental and computed Cd(X (X=Cl or I) distances are compared in Table 1 while the different basis sets are described in Table 2. One can see that the RHF-MP2 calculations with a moderately improved basis set (B2 also denoted as HW(p,d,f) in the main text) give interatomic distances very close to the experimental values. It is worth noting that the addition of the f polarization function ((=0.539) on the Cd atom was essential to obtain the correct bond lengths. Further improvement of the basis set (basis set B3) has modest consequences on the computed values. Accurate energy calculations require additional basis functions. A relevant test was performed on the dimer of CdI2 for which the dissociation free energy is known with good precision [2]. Ab initio calculations show that, in this dimer, each Cd atom is coordinatively bound to three I atoms in a planar structure. A dissociation free energy value of 67.7 kJ/mol, in good agreement with the experimental value of (70.6(6.7) kJ/mol was obtained with the B4 basis set which contains additional functions on the iodine atom: a d polarization and a L diffuse function. For these calculations the BSSE correction was 24.2 kJ/mol. 2. Optimized geometry of cadmium-thiolate clusters Details of the calculated geometries of models A and C are presented in Tables 3 and 4. References (1) K. Ruedenberg, M. W. Schmidt, M. M. Gilbert and S. T. Elbert, Chemical Physics 1982, 71, 41-49. (2) Handbook of Chemistry and Physics, ed. D. R. Linde, 81st-edition, CRC Press Bo