TY - JOUR

T1 - Optimal control of bond selectivity in unimolecular reactions

AU - Shi, Shenghua

AU - Rabitz, Herschel

N1 - Funding Information:
The authors acknowledge support from the Air Force Office of Scientific Research, the Army Research Office and the Office of Naval Research.
Copyright:
Copyright 2015 Elsevier B.V., All rights reserved.

PY - 1991/2

Y1 - 1991/2

N2 - 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 .

AB - 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 .

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U2 - 10.1016/0010-4655(91)90239-H

DO - 10.1016/0010-4655(91)90239-H

M3 - Article

AN - SCOPUS:0026108259

VL - 63

SP - 71

EP - 83

JO - Computer Physics Communications

JF - Computer Physics Communications

SN - 0010-4655

IS - 1-3

ER -