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Cavity Ground-State Chemistry

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Polaritonic Chemistry

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Abstract

In recent years, the possibility of influencing the thermally driven reactivity of organic molecules in the electronic ground state has been demonstrated by coupling the cavity to vibrational transitions of the molecules (Thomas et al. in Angew Chem Int Ed 55:11462, 2016 [1]; Hiura et al. in ChemRxiv 7234721, 2018 [2]; Lather et al. in ChemRxiv 7531544, 2018 [3]; Thomas et al. in Science 363:615, 2019 [4]). This opens a wide range of possibilities, such as cavity-enabled catalysis and manipulation of ground-state chemical processes. In this chapter we theoretically investigate the possibility of modifying ground-state chemical properties of organic molecules. Other attempts to understanding these experimental observations have been done.

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Notes

  1. 1.

    Do not confuse the photonic displacement \(q_k\) with the generalized nuclear coordinate \(\mathbf {q}\) used in previous chapters. To avoid confusion, in this chapter nuclear coordinates are explicitly denoted \(\mathbf {R}\).

  2. 2.

    Note that the vector dependence is in the coupling constant \(\varvec{\lambda }_k = \lambda _k \mathbf {e}_k\) so that the photonic displacement \(\hat{q}_k\) is a scalar operator.

  3. 3.

    Note that both Eqs. 2.29 and 6.6 represent the same equation if we considered the photonic term \(\frac{\hat{p}_k^2}{2}\) as the kinetic energy of another nuclear DoF.

  4. 4.

    Note that the description used here can also represent a dielectric sphere with a single resonance, such as a phonon mode.

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Authors and Affiliations

  1. Física teórica de la materia condensada, Universidad Autónoma de Madrid, Madrid, Spain

    Dr. Javier Galego Pascual

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Correspondence to Javier Galego Pascual .

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Galego Pascual, J. (2020). Cavity Ground-State Chemistry. In: Polaritonic Chemistry. Springer Theses. Springer, Cham. https://doi.org/10.1007/978-3-030-48698-3_6

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