Accurate Ab initio calculation of ionization potentials of the first-row transition metals with the
Robert E Thomas1, George H Booth2, Ali Alavi3
1The University Chemical Laboratory, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
Abstract:
Accurate ionization potentials of the first-row transition-metal atoms are obtained via the initiator full configuration quantum Monte Carlo technique, performing a stochastic integration of the electronic Schrödinger equation in exponentially large Hilbert spaces, with a mean absolute error of 0.13 kcal/mol (5 meV). This accuracy requires correlation of the 3p semicore electrons and in some cases the 3s manifold, along with extrapolation of the correlation energies to the complete-basis-set limit, and provides a new theoretical benchmark for the ionization potentials of these systems.
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