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Spin-orbit coupling in dioxygen activation and the role of spin in chemistry
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512).
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512).
2012 (English)In: Handbook of Computational Chemistry / [ed] J. Leszczynski, Springer Berlin/Heidelberg, 2012, 1067-1093 p.Chapter in book (Refereed)
Abstract [en]

We review the general concept of nonadiabatic quantum spin transitions in biochemistry. A few important examples are highlighted to illustrate the concept: the role of spin effects in oxidases, cytochromes, in dioxygen binding to heme, in photosynthesis, and in tentative models of consciousness. The most thoroughly studied of these effects are connected with dioxygen activation by enzymes. Discussion on the mechanisms of overcoming spin prohibitions in dioxygen reactions with flavin-dependent oxygenases and with hemoglobin and myoglobin is presented in some detail. We consider spin-orbit coupling (SOC) between the starting triplet state from the entrance channel of the O2 binding to glucose oxidase, to ferrous heme, and the final singlet open-shell state in these intermediates. Both triplet (T) and singlet (S) states in these examples are dominated by the radical-pair structures D+ -O2− induced by charge transfer; the peculiarities of their orbital configurations are essential for the SOC analysis. An account of specific SOC in the open πg-shell of dioxygen helps to explain the probability of T-S transitions in the active site near the transition state. Simulated potential energy surface cross-sections along the reaction coordinates for these multiplets, calculated by density functional theory, agree with the notion of a relatively strong SOC induced inside the oxygen moiety by an orbital angular momentum change in the πg-shell during the T-S transition. The SOC model explains well the efficient spin inversion during the O2 binding with heme and glucose oxidase, which constitutes a key mechanism for understanding metabolism. Other examples of nontrivial roles of spin effects in biochemistry are briefly discussed.

Place, publisher, year, edition, pages
Springer Berlin/Heidelberg, 2012. 1067-1093 p.
National Category
Natural Sciences
URN: urn:nbn:se:kth:diva-90839DOI: 10.1007/978-94-007-0711-5_29OAI: diva2:506797
QC 20120312Available from: 2012-02-29 Created: 2012-02-29 Last updated: 2012-03-12Bibliographically approved

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Minaev, BorisMinaeva, Valentina
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