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Intersystem crossing in the entrance channel of the reaction of O(3P) with pyridine

Nature Chemistry volume 14, pages 1405–1412 (2022)Cite this article

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Abstract

Two quantum effects can enable reactions to take place at energies below the barrier separating reactants from products: tunnelling and intersystem crossing between coupled potential energy surfaces. Here we show that intersystem crossing in the region between the pre-reactive complex and the reaction barrier can control the rate of bimolecular reactions for weakly coupled potential energy surfaces, even in the absence of heavy atoms. For O(3P) plus pyridine, a reaction relevant to combustion, astrochemistry and biochemistry, crossed-beam experiments indicate that the dominant products are pyrrole and CO, obtained through a spin-forbidden ring-contraction mechanism. The experimental findings are interpreted—by high-level quantum-chemical calculations and statistical non-adiabatic computations of branching fractions—in terms of an efficient intersystem crossing occurring before the high entrance barrier for O-atom addition to the N-atom lone pair. At low to moderate temperatures, the computed reaction rates prove to be dominated by intersystem crossing.

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Fig. 1: Schematic, simplified representation of the triplet and singlet PESs of the O-plus-pyridine reaction for O(3P) meta and ipso addition.
Fig. 2: Product LAB angular distributions and TOF distributions.
Fig. 3: Best-fit CM product angular and translational energy distributions.
Fig. 4: Total and single-channel rate constants.
Fig. 5: Frontier orbitals of the relevant MECPs.

Data availability

Source data are provided with this paper (and can also be downloaded at https://doi.org/10.6084/m9.figshare.20423616).

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Acknowledgements

This work has been supported by the Italian MUR (PRIN 2017, grant 2017A4XRCA (V.B.); PRIN 2017, grant 2017PJ5XXX (P.C.); PRIN 2020, grant 202082CE3T (C.P.)) and the Italian Space Agency (‘Life in Space’ project, N.2019-3-U.0 (N.B.,V.B.)). We acknowledge the Scuola Normale Superiore (Internal Funds), the University of Bologna (RFO funds), the Italian MUR (Ministry of University and Research) and Università degli Studi di Perugia (within the programme ‘Department of Excellence−2018−2022−Project AMIS’) and the SMART@SNS Laboratory (http://smart.sns.it) for high-performance computer facilities.

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Author notes

  1. Adriana Caracciolo

    Present address: Department of Aerospace Engineering Sciences, University of Colorado, Boulder, CO, USA

  2. Vanessa J. Murray

    Present address: Montana State University, Bozeman, MT, USA

  3. These authors contributed equally: Pedro Recio, Silvia Alessandrini.

Authors and Affiliations

  1. Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, Perugia, Italy

    Pedro Recio, Gianmarco Vanuzzo, Giacomo Pannacci, Demian Marchione, Adriana Caracciolo, Vanessa J. Murray, Piergiorgio Casavecchia & Nadia Balucani

  2. Scuola Normale Superiore, Pisa, Italy

    Silvia Alessandrini & Vincenzo Barone

  3. Dipartimento di Chimica ‘Giacomo Ciamician’, University of Bologna, Bologna, Italy

    Silvia Alessandrini & Cristina Puzzarini

  4. Dipartimento di Chimica, Materiali e Ingegneria Chimica ‘Giulio Natta’, Politecnico di Milano, Milan, Italy

    Alberto Baggioli & Carlo Cavallotti

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Contributions

G.V., G.P., P.R., D.M., A.C. and V.J.M. performed the experiments and analysed the data; S.A. and A.B. performed the QC computations and analysed the results; P.C. and N.B. conceived and guided the experiments and the interpretation of the results; C.C., C.P. and V.B conceived the computational strategy and coordinated the interpretation of its results; and P.C., N.B., C.C., C.P. and V.B. cowrote the paper. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Nadia Balucani, Carlo Cavallotti, Cristina Puzzarini or Vincenzo Barone.

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Supplementary Information

Supplementary Figs. 1–20, Tables 1–6, Results, Methods, details and references.

Supplementary Data 1

Cartesian coordinates of the equilibrium structures of all stationary points on the triplet and singlet PESs.

Supplementary Data 2

Source data for Supplementary Fig. 15.

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Source Data Fig. 2

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Source Data Fig. 3

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Source Data Fig. 4

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Recio, P., Alessandrini, S., Vanuzzo, G. et al. Intersystem crossing in the entrance channel of the reaction of O(3P) with pyridine. Nat. Chem. 14, 1405–1412 (2022). https://doi.org/10.1038/s41557-022-01047-3

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