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Singlet–triplet competition in the low-lying energy states of C4O4−n S n (n = 1–3) molecules

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Abstract

Cyclobutanetetrone, C4O4, has a triplet ground state, although the ground state of C4S4 is singlet. This computational study focuses on the mono-, di-, and trithiosquarate, C4O4−n S n (n = 1–3), molecules as transition stages between the two ending points (C4O4 and C4S4), and investigates the trends for the changes in the energies, geometry, partial atomic charges, partial spin densities, as well as orbital energies of the four low-lying electronic states. As the number of the sulfur atoms is increasing, the singlet spin state becomes energetically more and more preferred. For C4O3S molecule, where only one oxygen atom is substituted by sulfur, the CCSD(T) calculations predict a triplet ground state, but the error of the calculations is most likely higher than the calculated 0.5 kcal/mol singlet–triplet energy gap.

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Scheme 1
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Notes

  1. We note that the discussed trends based on the enthalpy values at 0 K can be applied for the trends based on electronic energies. The zero point energy corrections usually favor to the actual ground electronic state, but the caused energy differences do not exceed the 0.7 kcal/mol. For the first two electronic states of C4O3S structure, where even very small corrections count, the electronic energy difference of the ground state triplet and the first exited state π 8 singlet is 0.5 kcal/mol (the ΔH 0 value is 0.6 kcal/mol).

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Acknowledgments

This work was supported by computing time grants from Minnesota Supercomputing Institute. DGT acknowledges support from the U. S. Department of Energy, Office of Basic Energy Sciences, under Grant No. DE-SC0008666.

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Authors and Affiliations

  1. Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, MN, 55455, USA

    Zoltan Varga & Donald G. Truhlar

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  1. Zoltan Varga
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  2. Donald G. Truhlar
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Correspondence to Zoltan Varga.

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This paper is dedicated to Professor Magdolna Hargittai on the occasion of her 70th birthday.

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Varga, Z., Truhlar, D.G. Singlet–triplet competition in the low-lying energy states of C4O4−n S n (n = 1–3) molecules. Struct Chem 26, 1229–1240 (2015). https://doi.org/10.1007/s11224-015-0633-5

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