Optimal control of bond selectivity in unimolecular reactions

Shenghua Shi, Herschel Rabitz

Research output: Contribution to journalArticlepeer-review

76 Scopus citations

Abstract

The optimal control theory approach to designing optimal fields for bond-selective unimolecular reactions is presented. A set of equations for determining the optimal fields, which will lead to the achievement of the objective of bond-selective dissociation is developed. The numerical procedure given for solving these equations requires the repeated calculation of the time propagator for the system with the time-dependent Hamiltonian. The splitting approximation combined with the fast Fourier transform algorithm is used for computing the short time propagator. As an illustrative example, a model linear triatomic molecule is treated. The model system consists of two Morse oscillators coupled via kinetic coupling. The magnitude of the dipoles of the two Morse oscillators are the same, the fundamental frequencies are almost the same, but the dissociation energies are different. The rather demanding objective under these conditions is to break the stronger bond while leaving the weaker one intact. It is encouraging that the present computational method efficiently gives rise to the optimal field, which leads to the excellent achievement the objective of bond selective dissocivtion .

Original languageEnglish (US)
Pages (from-to)71-83
Number of pages13
JournalComputer Physics Communications
Volume63
Issue number1-3
DOIs
StatePublished - Feb 1991

All Science Journal Classification (ASJC) codes

  • Hardware and Architecture
  • Physics and Astronomy(all)

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