First-principles dynamics and mechanisms of fundamental chemical reactions

We describe the three main steps of a first-principles theoretical approach to study the dynamics and mechanisms of polyatomic chemical reactions: (1) benchmark ab initio stationary-point characterization, (2) potential energy surface development, and (3) reaction dynamics computations. We introduce...

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Elmentve itt :
Bibliográfiai részletek
Szerző: Czakó Gábor
Dokumentumtípus: Cikk
Megjelent: 2025
Sorozat:ADVANCES IN QUANTUM CHEMISTRY 94
Tárgyszavak:
doi:10.1016/bs.aiq.2025.01.001

mtmt:36092984
Online Access:http://publicatio.bibl.u-szeged.hu/38430
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520 3 |a We describe the three main steps of a first-principles theoretical approach to study the dynamics and mechanisms of polyatomic chemical reactions: (1) benchmark ab initio stationary-point characterization, (2) potential energy surface development, and (3) reaction dynamics computations. We introduce a composite approach for (1), the ROBOSURFER program systems and robust electronic structure methods for automating (2), and the quasi-classical trajectory method enhanced with mode-specific product vibrational analysis and energy-based Gaussian binning for (3). We apply the above methodology for fundamental radical-molecule and ion-molecule reactions involving 5−10 atoms, revealing new or experimentally-hidden reaction pathways, vibrational and rotational mode specificity, the validity of the Polanyi rules for polyatomic processes, unexpected leaving group effects and front-side complex formation, central atom effects and stereo-specificity, and unprecedented agreement between theory and experiment. © 2025 
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