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Controlled dissociation of I2 via optical transitions between the X and B electronic states
Open accessAbstract
Recent progress in both theoretical and experimental methods has led to the widespread belief that control of chemical reactions with ultrashort laser pulses is in principle achievable. In this article, the I2 molecule, which has been the subject of a great deal of femtosecond work, is studied theoretically as a prospect for experimental control. An unconstrained optimization of the electric field is performed, with the objective of dissociation on the B state. Krotov's optimization theory is used for this unconstrained optimization, which reduces the CPU time usage by a factor of four. The field which results from the optimization yields a probability of 99% for B state dissociation. The Husimi transform of the optimal field indicates a simple underlying structure, in contrast with many previous fields obtained by optimal control theory: the optimal field closely resembles a sequence of three Gaussian pulses with the same central frequency. Analysis of the optimal field indicates it operates by a quasi-cw excitation directly into the B continuum. A constrained optimization was then performed: the electric field was restricted onto the frequency interval from 0 to 19752 cm−1 to avoid the quasi-continuous-wave excitation mechanism. The optimal solution of this problem uses a three-photon pump—dump—pump (PDP) mechanism. The optimal field was approximated by sequences of three and four Gaussian-shaped laser pulses; the optimal and the two approximating fields gave 34%, 6% and 11% for the dissociation probability, respectively. The fields from the constrained optimization have fwhm on the order of 30–50 fs and intensities in the range of 1010 W/cm2 and should be experimentally producible with available technology.
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For the spin-chain model, the bound on the minimum transfer time is T_QSL/(N-1) ≥ max{π/(2∆E1); π/(2∆E2)}, which must be satisfied by any H(t) that brings the initial state to the target state in time T.
“The bound on the minimum transfer time is then given by T QSL / ( N -1) ≥ max { π 2∆ E 1 ; π 2∆ E 2 } , which needs to be satisfied by any H ( t ) that brings | ψ (0) 〉 to the target state | ψ G 〉 in a time T .”
From Optimal Control at the Quantum Speed Limit (2009) · cites this paper as [7]
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Goodwin, D. L., & Vinding, M. S. (2023) · Physical Review Research · doi:10.1103/physrevresearch.5.l012042 · Cited by 20
Optimal control of charge transfer for slow H+ + D collisions with shaped laser pulses
Zhang, W., Shu, C., Ho, T., RABITZ, H. A., & Cong, S. (2014) · The Journal of Chemical Physics · doi:10.1063/1.4867057 · Cited by 20
Schröder, M., & Brown, A. (2009) · New Journal of Physics · doi:10.1088/1367-2630/11/10/105031 · Cited by 19
Creating collective many-body states with highly excited atoms
Olmos, B., González‐Férez, R., & Lesanovsky, I. (2010) · Physical Review A · doi:10.1103/physreva.81.023604 · Cited by 19
Wang, X., Kumar, A., Shelton, C. R., & Wong, B. M. (2020) · Physical Chemistry Chemical Physics · doi:10.1039/d0cp03694c · Cited by 19
Time complexity and gate complexity
Koike, T., & Okudaira, Y. (2010) · Physical Review A · doi:10.1103/physreva.82.042305 · Cited by 19
Optimal control of population and coherence in three-level Λ systems
Kumar, P., Malinovskaya, S. A., & Malinovsky, V. S. (2011) · Journal of Physics B Atomic Molecular and Optical Physics · doi:10.1088/0953-4075/44/15/154010 · Cited by 19
Zou, S., Balint‐Kurti, G. G., & Manby, F. R. (2007) · The Journal of Chemical Physics · doi:10.1063/1.2748400 · Cited by 19
Zhu, W., & RABITZ, H. A. (1998) · Physical Review A · doi:10.1103/physreva.58.4741 · Cited by 19
Robust Optimized Pulse Schemes for Atomic Fountain Interferometry
Goerz, M. H., Kasevich, M. A., & Malinovsky, V. S. (2023) · Atoms · doi:10.3390/atoms11020036 · Cited by 18
Discrete-valued-pulse optimal control algorithms: Application to spin systems
Dridi, G., Lapert, M., Salomon, J., Glaser, S. J., & Sugny, D. (2015) · Physical Review A · doi:10.1103/physreva.92.043417 · Cited by 18
Ohtsuki, Y. (2010) · New Journal of Physics · doi:10.1088/1367-2630/12/4/045002 · Cited by 18
Optimal control of orientation and entanglement for two dipole–dipole coupled quantum planar rotors
Yu, H., Ho, T., & RABITZ, H. A. (2018) · Physical Chemistry Chemical Physics · doi:10.1039/c8cp00231b · Cited by 18
Control of quantum dynamics: Concepts, procedures and future prospects
RABITZ, H. A., Turinici, G., & Brown, E. (2003) · Handbook of numerical analysis · doi:10.1016/s1570-8659(03)10016-6 · Cited by 15
Chen, P., Luo, D.-W., & Yu, T. (2025) · Physical Review Research · doi:10.1103/physrevresearch.7.013161 · Cited by 20
“…various control strategies, the Krotov control [51–55] is a versatile algorithm that can be applied to Bose-Einstein condensate [56], photochem-istry [53, 57], non-linear Schr¨odinger equation [52, 56], and optimal control under open systems [58], as well as controlling towards entanglers [59, 60].”
Optimal control of an inhomogeneous spin ensemble coupled to a cavity
Ansel, Q., Probst, S., Bertet, P., Glaser, S. J., & Sugny, D. (2018) · Physical Review A · doi:10.1103/physreva.98.023425 · Cited by 14
Searching for pathways involving dressed states in optimal control theory
von den Hoff, P., Kowalewski, M., & de Vivie‐Riedle, R. (2011) · Faraday Discussions · doi:10.1039/c1fd00031d · Cited by 14
Selective Enhancement of Spectroscopic Features by Quantum Optimal Control
Keefer, D., & Mukamel, S. (2021) · Physical Review Letters · doi:10.1103/physrevlett.126.163202 · Cited by 14
“We use the common Krotov’s formulation of OCT [22] with strict limitations in the frequency domain [23].”
MethodInfluentialOptimal Control in Large Open Quantum Systems: The Case of Transmon Readout and Reset
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A multi target approach to control chemical reactions in their inhomogeneous solvent environment
Keefer, D., Thallmair, S., Zauleck, J. P. P., & de Vivie‐Riedle, R. (2015) · Journal of Physics B Atomic Molecular and Optical Physics · doi:10.1088/0953-4075/48/23/234003 · Cited by 13
Simulating the control of molecular reactions via modulated light fields: from gas phase to solution
Thallmair, S., Keefer, D., Rott, F., & de Vivie‐Riedle, R. (2017) · Journal of Physics B Atomic Molecular and Optical Physics · doi:10.1088/1361-6455/aa6100 · Cited by 13
Acceleration of quantum optimal control theory algorithms with mixing strategies
Castro, A., & Gross, E. K. U. (2009) · Physical Review E · doi:10.1103/physreve.79.056704 · Cited by 13
Metadata
- Authors
- Somlói, J., Kazakov, V. A., & Tannor, D. J.
- Affiliations
- University of Notre Dame (US)
- ORCID
- Tannor, David J.
- Venue
- Chemical Physics
- Publisher
- Elsevier BV
- Published
- 1993-05
- Volume
- 172
- Issue
- 1
- Pages
- 85-98
- ISSN
- 0301-0104 (ISSN-L)
- OpenAlex
- W1971368733
- Cited by
- 188
- References
- 26
- Citations by year
- 2026: 6 · 2025: 8 · 2024: 3 · 2023: 5 · 2022: 4 · 2021: 7 · 2020: 8 · 2019: 8 · 2018: 10 · 2017: 4 · 2016: 9 · 2015: 7 · 2014: 11 · 2013: 5 · 2012: 5
- FWCI
- 2.70
- Type
- journal article
- Language
- en
- Open access
- hybrid
- doi.org
- Licence
- Locations
- Chemical Physics (publishedVersion, cc-by-nc-nd)
- Funders
- University of Illinois at Urbana-Champaign
- National Supercomputing Center, Korea Institute of Science and Technology Information
- Office of Naval Research
- Topics
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Laser-Matter Interactions and Applications
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Spectroscopy and Quantum Chemical Studies
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Photochemistry and Electron Transfer Studies
- Keywords
- molecular iodine, laser-induced dissociation, femtosecond pulses
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