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Title: On the zeroth-order Hamiltonian for CASPT2 calculations of spin crossover compounds
Author: Vela Llausí, Sergi
Fumanal, M.
Ribas Ariño, Jordi
Robert, V.
Keywords: Ferro
Issue Date: 15-Apr-2016
Publisher: Wiley
Abstract: Complete active space self-consistent field theory (CASSCF) calculations and subsequent second-order perturbation theory treatment (CASPT2) are discussed in the evaluation of the spin-states energy difference (ΔHelec) of a series of seven spin crossover (SCO) compounds. The reference values have been extracted from a combination of experimental measurements and DFT  +  U calculations, as discussed in a recent article (Vela et al., Phys Chem Chem Phys 2015, 17, 16306). It is definitely proven that the critical IPEA parameter used in CASPT2 calculations of ΔHelec, a key parameter in the design of SCO compounds, should be modified with respect to its default value of 0.25 a.u. and increased up to 0.50 a.u. The satisfactory agreement observed previously in the literature might result from an error cancellation originated in the default IPEA, which overestimates the stability of the HS state, and the erroneous atomic orbital basis set contraction of carbon atoms, which stabilizes the LS states.
Note: Versió postprint del document publicat a:
It is part of: Journal of Computational Chemistry, 2016, vol. 37, num. 10, p. 947-953
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ISSN: 0192-8651
Appears in Collections:Articles publicats en revistes (Ciència dels Materials i Química Física)

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