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Radiative excitation of the harmonic oscillator with applications to stereomutation in chiral molecules

  • Special Issue Dedicated To Friedrich Hurd On The Occasion Of His 100th Birthday
  • Published:
Zeitschrift für Physik D Atoms, Molecules and Clusters

Abstract

We present theoretical considerations and quantitative numerical simulations of the coherent radiative excitation of chiral molecules exhibiting a double well potential in the electronic ground state (with stable enantiomers) and a harmonic oscillator potential with achiral minimum geometry in the excited electronic state following a scheme proposed in [33]. The one-dimensional short time dynamics is presented on the femtosecond time scale. We demonstrate the phenomena of quasiexponential, radiationless decay of the survival probability in the excited electronic state by simple harmonic oscillator wave packet motion, as well as coherent periodic chiral stereomutation. The differences and similarities of the excited state harmonic oscillator dynamics with two quite different ground state potentials are discussed. A designed pulse sequence allows for chemically efficient laser controlled stereomutation with high enantiomeric specificity. The results are discussed in relation to Friedrich Hund's early work on stereomutation by tunneling and in relation to our current understanding of chiral molecules including dynamical chirality and anharmonic vibrational dynamics on the femtosecond time scale and the violation of parity and other fundamental symmetries.

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  1. Laboratorium für Physikalische Chemie, ETH Zürich (Zentrum), CH-8092, Zürich, Switzerland

    R. Marquardt & M. Quack

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Motto: The Romans used to place statues of those men during their lifetime in the forum Romanum, who had served Rome in an outstanding fashion — so to speak the “Roman Nobel Prize of politics” — but not so for Cato. When Cato was asked by his friends “Why is there no statue of Cato's in the forum Romanum” his reply was: I prefer that they ask “Why is there no statue of Cato's in the forum Romanum?” than that they would ask “Why is there a statue of Cato's in the forum Romanum?”.

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Marquardt, R., Quack, M. Radiative excitation of the harmonic oscillator with applications to stereomutation in chiral molecules. Z Phys D - Atoms, Molecules and Clusters 36, 229–237 (1996). https://doi.org/10.1007/BF01426408

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