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  Controlling Chemical Reactivity with Optimally Oriented Electric Fields: A Generalization of the Newton Trajectory Method

Bofill, J. M., Quapp, W., Albareda Piquer, G., de Moreira, I. P. R., & Ribas-Ariño, J. (2022). Controlling Chemical Reactivity with Optimally Oriented Electric Fields: A Generalization of the Newton Trajectory Method. Journal of Chemical Theory and Computation, 18(2), 935-952. doi:10.1021/acs.jctc.1c00943.

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https://doi.org/10.1021/acs.jctc.1c00943 (Publisher version)
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 Creators:
Bofill, J. M.1, 2, Author
Quapp, W.3, Author
Albareda Piquer, G.2, 4, 5, Author              
de Moreira, I. P. R.2, 6, Author
Ribas-Ariño, Jordi2, 6, Author
Affiliations:
1Departament de Química Inorgànica i Orgànica, Secció de Química Orgànica, Universitat de Barcelona, ou_persistent22              
2Institut de Química Teòrica i Computacional, (IQTCUB), Universitat de Barcelona, ou_persistent22              
3Mathematisches Institut, Universität Leipzig, ou_persistent22              
4Theory Group, Theory Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_2266715              
5Center for Free-Electron Laser Science, ou_persistent22              
6Departament de Ciència de Materials i Química Física, Secció de Química Física, Universitat de Barcelona, ou_persistent22              

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 Abstract: The use of oriented external electric fields (OEEF) as a tool to accelerate chemical reactions has recently attracted much interest. A new model to calculate the optimal OEEF of the least intensity to induce a barrierless chemical reaction path is presented. A suitable ansatz is provided by defining an effective potential energy surface (PES), which considers the unperturbed or original PES of the molecular reactive system and the action of a constant OEEF on the overall dipole moment of system. Based on a generalization of the Newton Trajectories (NT) method, it is demonstrated that the optimal OEEF can be determined upon locating a special point of the potential energy surface (PES), the so-called “optimal bond-breaking point” (optimal BBP), for which two different algorithms are proposed. At this point, the gradient of the original or unperturbed PES is an eigenvector of zero eigenvalue of the Hessian matrix of the effective PES. A thorough discussion of the geometrical aspects of the optimal BBP and the optimal OEEF is provided using a two-dimensional model, and numerical calculations of the optimal OEEF for a SN2 reaction and the 1,3-dipolar retrocycloaddition of isoxazole to fulminic acid plus acetylene reaction serve as a proof of concept. The knowledge of the orientation of optimal OEEF provides a practical way to reduce the effective barrier of a given chemical process.

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Language(s): eng - English
 Dates: 2021-09-212022-01-192022-02-08
 Publication Status: Published in print
 Pages: 18
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.jctc.1c00943
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Title: Journal of Chemical Theory and Computation
  Other : J. Chem. Theory Comput.
Source Genre: Journal
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Publ. Info: Washington, D.C. : American Chemical Society
Pages: - Volume / Issue: 18 (2) Sequence Number: - Start / End Page: 935 - 952 Identifier: ISSN: 1549-9618
CoNE: https://pure.mpg.de/cone/journals/resource/111088195283832