Abstract <p>Classical and quantum dynamical studies are undertaken on a model for post-transition state bifurcation (PTSB) reactions exhibiting a valley ridge inflection (VRI) point on the potential energy surface. We seek the quantum manifestations of the dynamical influence of VRIs highlighted in the recent work by García-Garrido and Wiggins.<sup><CitationRef CitationID="CR1">1</CitationRef></sup> We show that the quantum wave packet dynamics does show sensitivity to the VRI location. Moreover, the quantum eigenstates of the system exhibit several avoided crossings upon varying the VRI point. We discuss the possible connections of such avoided crossings with the classical recrossing dynamics. We also show that the quantum cumulative reaction probabilities are sensitive to the location of the VRI point due to the change in the shape of the potential surface near the different transition states.</p> Graphical abstract <p></p>

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Quantum dynamical studies on a model for reactions exhibiting post-transition state bifurcation

  • Atul Kumar,
  • Srihari Keshavamurthy

摘要

Abstract

Classical and quantum dynamical studies are undertaken on a model for post-transition state bifurcation (PTSB) reactions exhibiting a valley ridge inflection (VRI) point on the potential energy surface. We seek the quantum manifestations of the dynamical influence of VRIs highlighted in the recent work by García-Garrido and Wiggins.1 We show that the quantum wave packet dynamics does show sensitivity to the VRI location. Moreover, the quantum eigenstates of the system exhibit several avoided crossings upon varying the VRI point. We discuss the possible connections of such avoided crossings with the classical recrossing dynamics. We also show that the quantum cumulative reaction probabilities are sensitive to the location of the VRI point due to the change in the shape of the potential surface near the different transition states.

Graphical abstract