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Methodological CASPT2 study of the valence excited states of an iron-porphyrin complex

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Abstract

The singlet valence excited states of an iron-porphyrin-pyrazine-carbonyl complex are investigated up to the Soret band (about 3 eV) using multi-state complete active space with perturbation at the second order (MS-CASPT2). This complex is a model for the active site of carboxy-hemoglobin/myoglobin. The spectrum of the excited states is rather dense, comprising states of different nature: d→π* transitions, d→d states, π→π* excitations of the porphyrin, and doubly excited states involving simultaneous intra-porphyrin π→π* and d→d transitions. Specific features of the MS-CASPT2 method are investigated. The effect of varying the number of roots in the state average calculation is quantified as well as the consequence of targeted modifications of the active space. The effect of inclusion of standard ionization potential-electron affinity (IPEA) shift in the perturbation treatment is also investigated.

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Acknowledgements

The authors thank Thomas Applencourt for technical help and acknowledge the computational resources provided by CALMIP (Toulouse).

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  1. Laboratoire de Chimie et Physique Quantiques UMR5626, IRSAMC, CNRS/Université Paul Sabatier, 118 Rte de Narbonne, 31 062, Toulouse Cedex, France

    Nadia Ben Amor, Adrien Soupart & Marie-Catherine Heitz

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  1. Nadia Ben Amor
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  2. Adrien Soupart
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Correspondence to Nadia Ben Amor or Marie-Catherine Heitz.

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This paper belongs to Topical Collection Festschrift in Honor of Henry Chermette

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Ben Amor, N., Soupart, A. & Heitz, MC. Methodological CASPT2 study of the valence excited states of an iron-porphyrin complex. J Mol Model 23, 53 (2017). https://doi.org/10.1007/s00894-017-3226-y

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