Quantum optimal control of isomerization dynamics of a one-dimensional reaction-path model dominated by a competing dissociation channel

Journal Article · Tue Jul 28 00:00:00 EDT 2009 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3185565· OSTI ID:21559748

Kurosaki, Yuzuru ^[1]; Artamonov, Maxim; Ho, Tak-San; Rabitz, Herschel ^[2]

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1. Kansai Photon Science Institute, Japan Atomic Energy Agency, Kizugawa, Kyoto 619-0215 (Japan)
2. Department of Chemistry, Princeton University, Princeton, New Jersey 08544 (United States)

Quantum wave packet optimal control simulations with intense laser pulses have been carried out for studying molecular isomerization dynamics of a one-dimensional (1D) reaction-path model involving a dominant competing dissociation channel. The 1D intrinsic reaction coordinate model mimics the ozone open{yields}cyclic ring isomerization along the minimum energy path that successively connects the ozone cyclic ring minimum, the transition state (TS), the open (global) minimum, and the dissociative O{sub 2}+O asymptote on the O{sub 3} ground-state {sup 1}A{sup '} potential energy surface. Energetically, the cyclic ring isomer, the TS barrier, and the O{sub 2}+O dissociation channel lie at {approx}0.05, {approx}0.086, and {approx}0.037 hartree above the open isomer, respectively. The molecular orientation of the modeled ozone is held constant with respect to the laser-field polarization and several optimal fields are found that all produce nearly perfect isomerization. The optimal control fields are characterized by distinctive high temporal peaks as well as low frequency components, thereby enabling abrupt transfer of the time-dependent wave packet over the TS from the open minimum to the targeted ring minimum. The quick transition of the ozone wave packet avoids detrimental leakage into the competing O{sub 2}+O channel. It is possible to obtain weaker optimal laser fields, resulting in slower transfer of the wave packets over the TS, when a reduced level of isomerization is satisfactory.

• OSTI ID: 21559748
• Journal Information: Journal of Chemical Physics, Vol. 131, Issue 4; Other Information: DOI: 10.1063/1.3185565; (c) 2009 American Institute of Physics; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
DISSOCIATION
GROUND STATES
ISOMERIZATION
ISOMERS
LASER RADIATION
ONE-DIMENSIONAL CALCULATIONS
OPTIMAL CONTROL
OXYGEN
OZONE
PHOTOCHEMISTRY
PHOTOLYSIS
POTENTIAL ENERGY
REACTION KINETICS
SIMULATION
SURFACES
TIME DEPENDENCE
WAVE PACKETS
CHEMICAL REACTIONS
CHEMISTRY
CONTROL
DECOMPOSITION
ELECTROMAGNETIC RADIATION
ELEMENTS
ENERGY
ENERGY LEVELS
KINETICS
NONMETALS
PHOTOCHEMICAL REACTIONS
RADIATIONS