The initial value representation (IVR) was proposed five decades ago by Miller [J. Chem. Phys. 53, 3578 (1970)] in order to improve the feasibility and accuracy of semiclassical (SC) scattering calculations. Møller operators, which play a fundamental role in quantum scattering theory, do not appear in his formulation based on action-angle coordinates. These operators were introduced much later by Garashchuk and Light [J. Chem. Phys. 114, 1060 (2001)] in SC-IVR calculations performed in Cartesian coordinates within the Tannor and Weeks [J. Chem. Phys. 98, 3884 (1993)] formulation of quantum scattering theory. Remarkably, Møller operators were found to boost the numerical efficiency of SC-IVR calculations. The purpose of this work is to show within a simple model of light-induced rotational transitions that, in fact, Møller operators were already underlying Miller's pioneering formulation. In line with the results of Garashchuk and Light [J. Chem. Phys. 114, 1060 (2001)], removing the action of these operators in Miller's theory strongly decreases its numerical efficiency.
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http://dx.doi.org/10.1063/5.0023137 | DOI Listing |
J Phys Chem Lett
January 2025
National High Magnetic Field Laboratory, Florida State University, 1800 E. Paul Dirac Dr, Tallahassee, Florida 32310, United States.
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Department of Life Science and Applied Chemistry, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan.
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View Article and Find Full Text PDFJ Phys Chem A
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View Article and Find Full Text PDFJ Phys Chem A
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Department of Physics, University of Northeastern, IMIT-CONICET, Av. Libertad, 5500 Corrientes, Argentina.
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Key Lab of Advanced Transducers and Intelligent Control System, Ministry of Education and Shanxi Province, College of Physics and Optoelectronics, Taiyuan University of Technology, Taiyuan 030024, China.
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