Details

Autor(en) / Beteiligte

• Bofill, Josep Maria
• Quapp, Wolfgang
• Albareda, Guillermo
• Moreira, Ibério de P. R
• Ribas-Ariño, Jordi

Titel

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

Ist Teil von

• Journal of chemical theory and computation, 2022-02, Vol.18 (2), p.935-952

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2022

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• 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 S N 2 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.