Performance of diffusion Monte Carlo for the first dissociation energies of transition metal carbonyls -: art. no. 021101

Fixed node diffusion Monte Carlo (FNDMC) calculations are carried out for the first ligand dissociation energies of the prototype transition metal carbonyls Cr(CO)(6), Fe(CO)(5), Ni(CO)(4), and Fe(CO)(4)N-2. Since Hartree-Fock theory performs particularly badly for these type of compounds they are difficult to treat with conventional ab initio methods. We find that a Kohn-Sham determinant from a standard density functional provides a balanced description of the fermionic nodal hyper surfaces of all compounds involved in the dissociation reaction. With one exception, the experimental dissociation enthalpies are reproduced by FNDMC within the statistical accuracy of the method. (C) 2005 American Institute of Physics.