A new approach to molecular classical optimal control

Application to the reaction HCN→HC+N

Jair Botina, Herschel Albert Rabitz, Naseem Rahman

Research output: Contribution to journalArticle

41 Citations (Scopus)

Abstract

We present a new method for classical control theory of Hamiltonian systems. This approach is based on a special treatment of the adjoint or Lagrange multiplier equations of motion. The latter function is only asked to preserve the mean of the ensemble of molecular trajectories. In the present case only four such equations are involved greatly simplifying the field design process and making it faster and more stable. Good results are obtained for the selective photodissociation of HCN. The objective is to control the intramolecular reaction HCN→HC+N (i.e., break the stronger bond). Hamilton's equations of motion are employed to model the HCN molecule, initially in its ground state. The control equations are integrated to obtain a high degree of selectivity in the unimolecular dissociation. The robustness of the results to changes in the initial conditions and pulse durations are investigated. An increase of the pulse duration beyond a certain point makes it more difficult to dissociate the N atom due to strong intramolecular coupling. The resultant pulse fields may serve as a basic indicator for future experimental selective dissociation of HCN→HC+N using high power lasers.

Original languageEnglish (US)
Pages (from-to)226-236
Number of pages11
JournalThe Journal of chemical physics
Volume102
Issue number1
DOIs
StatePublished - Jan 1 1995

Fingerprint

optimal control
Equations of motion
molecular trajectories
pulse duration
equations of motion
dissociation
Photodissociation
Hamiltonians
Lagrange multipliers
control theory
High power lasers
multipliers
Control theory
photodissociation
high power lasers
Ground state
selectivity
Trajectories
Atoms
Molecules

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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abstract = "We present a new method for classical control theory of Hamiltonian systems. This approach is based on a special treatment of the adjoint or Lagrange multiplier equations of motion. The latter function is only asked to preserve the mean of the ensemble of molecular trajectories. In the present case only four such equations are involved greatly simplifying the field design process and making it faster and more stable. Good results are obtained for the selective photodissociation of HCN. The objective is to control the intramolecular reaction HCN→HC+N (i.e., break the stronger bond). Hamilton's equations of motion are employed to model the HCN molecule, initially in its ground state. The control equations are integrated to obtain a high degree of selectivity in the unimolecular dissociation. The robustness of the results to changes in the initial conditions and pulse durations are investigated. An increase of the pulse duration beyond a certain point makes it more difficult to dissociate the N atom due to strong intramolecular coupling. The resultant pulse fields may serve as a basic indicator for future experimental selective dissociation of HCN→HC+N using high power lasers.",
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A new approach to molecular classical optimal control : Application to the reaction HCN→HC+N. / Botina, Jair; Rabitz, Herschel Albert; Rahman, Naseem.

In: The Journal of chemical physics, Vol. 102, No. 1, 01.01.1995, p. 226-236.

Research output: Contribution to journalArticle

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