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Ab Initio Molecular Dynamics of Temporary Anions Using Complex Absorbing Potentials

[Image: see text] Dissociative electron attachment, that is, the cleavage of chemical bonds induced by low-energy electrons, is difficult to model with standard quantum-chemical methods because the involved anions are not bound but subject to autodetachment. We present here a new computational devel...

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Autores principales: Gyamfi, Jerryman A., Jagau, Thomas-C.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9486942/
https://www.ncbi.nlm.nih.gov/pubmed/36054015
http://dx.doi.org/10.1021/acs.jpclett.2c01969
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author Gyamfi, Jerryman A.
Jagau, Thomas-C.
author_facet Gyamfi, Jerryman A.
Jagau, Thomas-C.
author_sort Gyamfi, Jerryman A.
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description [Image: see text] Dissociative electron attachment, that is, the cleavage of chemical bonds induced by low-energy electrons, is difficult to model with standard quantum-chemical methods because the involved anions are not bound but subject to autodetachment. We present here a new computational development for simulating the dynamics of temporary anions on complex-valued potential energy surfaces. The imaginary part of these surfaces describes electron loss, whereas the gradient of the real part represents the force on the nuclei. In our method, the forces are computed analytically based on Hartree–Fock theory with a complex absorbing potential. Ab initio molecular dynamics simulations for the temporary anions of dinitrogen, ethylene, chloroethane, and the five mono- to tetrachlorinated ethylenes show qualitative agreement with experiments and offer mechanistic insights into dissociative electron attachments. The results also demonstrate how our method evenhandedly deals with molecules that may undergo dissociation upon electron attachment and those which only undergo autodetachment.
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spelling pubmed-94869422022-09-21 Ab Initio Molecular Dynamics of Temporary Anions Using Complex Absorbing Potentials Gyamfi, Jerryman A. Jagau, Thomas-C. J Phys Chem Lett [Image: see text] Dissociative electron attachment, that is, the cleavage of chemical bonds induced by low-energy electrons, is difficult to model with standard quantum-chemical methods because the involved anions are not bound but subject to autodetachment. We present here a new computational development for simulating the dynamics of temporary anions on complex-valued potential energy surfaces. The imaginary part of these surfaces describes electron loss, whereas the gradient of the real part represents the force on the nuclei. In our method, the forces are computed analytically based on Hartree–Fock theory with a complex absorbing potential. Ab initio molecular dynamics simulations for the temporary anions of dinitrogen, ethylene, chloroethane, and the five mono- to tetrachlorinated ethylenes show qualitative agreement with experiments and offer mechanistic insights into dissociative electron attachments. The results also demonstrate how our method evenhandedly deals with molecules that may undergo dissociation upon electron attachment and those which only undergo autodetachment. American Chemical Society 2022-09-02 2022-09-15 /pmc/articles/PMC9486942/ /pubmed/36054015 http://dx.doi.org/10.1021/acs.jpclett.2c01969 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/).
spellingShingle Gyamfi, Jerryman A.
Jagau, Thomas-C.
Ab Initio Molecular Dynamics of Temporary Anions Using Complex Absorbing Potentials
title Ab Initio Molecular Dynamics of Temporary Anions Using Complex Absorbing Potentials
title_full Ab Initio Molecular Dynamics of Temporary Anions Using Complex Absorbing Potentials
title_fullStr Ab Initio Molecular Dynamics of Temporary Anions Using Complex Absorbing Potentials
title_full_unstemmed Ab Initio Molecular Dynamics of Temporary Anions Using Complex Absorbing Potentials
title_short Ab Initio Molecular Dynamics of Temporary Anions Using Complex Absorbing Potentials
title_sort ab initio molecular dynamics of temporary anions using complex absorbing potentials
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9486942/
https://www.ncbi.nlm.nih.gov/pubmed/36054015
http://dx.doi.org/10.1021/acs.jpclett.2c01969
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