metaFALCON: A program package for automatic sampling of conical intersection seams using multistate metadynamics
Please always quote using this URN: urn:nbn:de:bvb:20-opus-199258
- The multistate metadynamics for automatic exploration of conical intersection seams and systematic location of minimum energy crossing points in molecular systems and its implementation into the software package metaFALCON is presented. Based on a locally modified energy gap between two Born–Oppenheimer electronic states as a collective variable, multistate metadynamics trajectories are driven toward an intersection point starting from an arbitrary ground state geometry and are subsequently forced to explore the conical intersection seamThe multistate metadynamics for automatic exploration of conical intersection seams and systematic location of minimum energy crossing points in molecular systems and its implementation into the software package metaFALCON is presented. Based on a locally modified energy gap between two Born–Oppenheimer electronic states as a collective variable, multistate metadynamics trajectories are driven toward an intersection point starting from an arbitrary ground state geometry and are subsequently forced to explore the conical intersection seam landscape. For this purpose, an additional collective variable capable of distinguishing structures within the seam needs to be defined and an additional bias is introduced into the off-diagonal elements of an extended (multistate) electronic Hamiltonian. We demonstrate the performance of the algorithm on the examples of the 1,3-butadiene, benzene, and 9H-adenine molecules, where multiple minimum energy crossing points could be systematically located using the Wiener number or Cremer–Pople parameters as collective variables. Finally, with the example of 9H-adenine, we show that the multistate metadynamics potential can be used to obtain a global picture of a conical intersection seam. Our method can be straightforwardly connected with any ab initio or semiempirical electronic structure theory that provides energies and gradients of the respective electronic states and can serve for systematic elucidation of the role of conical intersections in the photophysics and photochemistry of complex molecular systems, thus complementing nonadiabatic dynamics simulations.…
Author: | Joachim O. Lindner, Karina Sultangaleeva, Merle I. S. Röhr, Roland Mitric |
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URN: | urn:nbn:de:bvb:20-opus-199258 |
Document Type: | Preprint |
Faculties: | Fakultät für Chemie und Pharmazie / Institut für Physikalische und Theoretische Chemie |
Language: | English |
Parent Title (English): | Journal of Chemical Theory and Computation |
Year of Completion: | 2019 |
Source: | Journal of Chemical Theory and Computation 2019, 15, 6, 3450-3460. https://doi.org/10.1021/acs.jctc.9b00029 |
URL: | https://doi.org/10.1021/acs.jctc.9b00029 |
Dewey Decimal Classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 541 Physikalische Chemie |
Tag: | Chemical Structure; Computational Chemistry; Hydrocarbons; Hydrogen; Metadynamics |
Release Date: | 2020/01/29 |
Embargo Date: | 2020/04/17 |
EU-Project number / Contract (GA) number: | 646737 |
OpenAIRE: | OpenAIRE |
Note: | This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Chemical Theory and Computation, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see Journal of Chemical Theory and Computation 2019, 15, 6, 3450-3460. https://doi.org/10.1021/acs.jctc.9b00029. |
Licence (German): | Deutsches Urheberrecht |