Quantum chemical replica-exchange umbrella sampling molecular dynamics simulations reveal the formation mechanism of iron phthalocyanine from iron and phthalonitrile

Ito, Shingo; Wang, Ying; Okamoto, Yuko; Irle, Stephan

doi:10.1063/1.5026956

Title: Quantum chemical replica-exchange umbrella sampling molecular dynamics simulations reveal the formation mechanism of iron phthalocyanine from iron and phthalonitrile

Journal Article · 16 July 2018 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/1.5026956 · OSTI ID:1474873

Ito, Shingo ^[1]; Wang, Ying ^[2];

^[3];

^[4]

Nagoya Univ., Nagoya (Japan)
Nagoya Univ., Nagoya (Japan); Chinese Academy of Sciences, Changchun (People's Republic of China)
Nagoya Univ., Nagoya (Japan); JST-CREST, Nagoya (Japan)
Nagoya Univ., Nagoya (Japan); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Phthalocyanine (Pc) and its metal complexes (MPcs) have been used industrially since their discovery in the early 20th century. The phthalonitrile (PN) method is a well-known synthesis method in which Pc or MPc can be afforded by heating a mixture of PN and metal powders over 280 °C with only moderate yield. However, the formation mechanism of the phthalocyanines and the intermediate stages of this seemingly simple reaction have yet to be fully understood. To study this mechanism computationally, we carried out quantum chemical molecular dynamics (MD) simulations based on the density-functional tight-binding (DFTB) method, applying the replica-exchange umbrella sampling (REUS) method, starting from four PN molecules and one iron atom. The DFTB-REUS-MD simulations successfully yielded FePc, and a metastable structure very similar to FePc but with a reactive nitrene unit was also identified that might explain the incomplete conversion of the reactants into FePc. Furthermore, analysis of the MD trajectories reveals a three-step FePc formation mechanism for the PN method.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1474873

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 7 Vol. 149; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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formation mechanism
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Title: Quantum chemical replica-exchange umbrella sampling molecular dynamics simulations reveal the formation mechanism of iron phthalocyanine from iron and phthalonitrile

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