Computational benchmarking for ultrafast electron dynamics: wavefunction methods vs density functional theory

Hdl Handle:
http://hdl.handle.net/10034/558410
Title:
Computational benchmarking for ultrafast electron dynamics: wavefunction methods vs density functional theory
Authors:
Oliveira, Micael J. T.; Mignolet, Benoit; Kus, Tomasz; Papadopoulos, Theodoros A.; Remacle, Francoise; Verstraete, Matthieu J.
Abstract:
Attosecond electron dynamics in small- and medium-sized molecules, induced by an ultrashort strong optical pulse, is studied computationally for a frozen nuclear geometry. The importance of exchange and correlation effects on the nonequilibrium electron dynamics induced by the interaction of the molecule with the strong optical pulse is analyzed by comparing the solution of the time-dependent Schrodinger equation based on the correlated field-free stationary electronic states computed with the equation-of-motion coupled cluster singles and doubles and the complete active space multi-configurational self-consistent field methodologies on one hand, and various functionals in real-time time-dependent density functional theory (TD-DFT) on the other. We aim to evaluate the performance of the latter approach, which is very widely used for nonlinear absorption processes and whose computational cost has a more favorable scaling with the system size. We focus on LiH as a toy model for a nontrivial molecule and show that our conclusions carry over to larger molecules, exemplified by ABCU (C10H19N). The molecules are probed with IR and UV pulses whose intensities are not strong enough to significantly ionize the system. By comparing the evolution of the time-dependent field-free electronic dipole moment, as well as its Fourier power spectrum, we show that TD-DFT performs qualitatively well in most cases. Contrary to previous studies, we find almost no changes in the TD-DFT excitation energies when excited states are populated. Transitions between states of different symmetries are induced using pulses polarized in different directions. We observe that the performance of TD-DFT does not depend on the symmetry of the states involved in the transition.
Affiliation:
University of Chester
Citation:
Computational benchmarking for ultrafast electron dynamics: wavefunction methods vs density functional theory 2015, 11 (5):2221 Journal of Chemical Theory and Computation
Publisher:
American Chemical Society
Journal:
Journal of Chemical Theory and Computation
Publication Date:
12-May-2015
URI:
http://hdl.handle.net/10034/558410
DOI:
10.1021/acs.jctc.5b00167
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acs.jctc.5b00167
Type:
Article
Language:
en_US
ISSN:
1549-9618; 1549-9626
Sponsors:
Belgian Fonds National de la Recherche Collective through project number 2.4545.12 “Control of attosecond dynamics: applications to molecular reactivity”
Appears in Collections:
Natural Sciences

Full metadata record

DC FieldValue Language
dc.contributor.authorOliveira, Micael J. T.en
dc.contributor.authorMignolet, Benoiten
dc.contributor.authorKus, Tomaszen
dc.contributor.authorPapadopoulos, Theodoros A.en
dc.contributor.authorRemacle, Francoiseen
dc.contributor.authorVerstraete, Matthieu J.en
dc.date.accessioned2015-06-22T11:55:21Zen
dc.date.available2015-06-22T11:55:21Zen
dc.date.issued2015-05-12en
dc.identifier.citationComputational benchmarking for ultrafast electron dynamics: wavefunction methods vs density functional theory 2015, 11 (5):2221 Journal of Chemical Theory and Computationen
dc.identifier.issn1549-9618en
dc.identifier.issn1549-9626en
dc.identifier.doi10.1021/acs.jctc.5b00167en
dc.identifier.urihttp://hdl.handle.net/10034/558410en
dc.description.abstractAttosecond electron dynamics in small- and medium-sized molecules, induced by an ultrashort strong optical pulse, is studied computationally for a frozen nuclear geometry. The importance of exchange and correlation effects on the nonequilibrium electron dynamics induced by the interaction of the molecule with the strong optical pulse is analyzed by comparing the solution of the time-dependent Schrodinger equation based on the correlated field-free stationary electronic states computed with the equation-of-motion coupled cluster singles and doubles and the complete active space multi-configurational self-consistent field methodologies on one hand, and various functionals in real-time time-dependent density functional theory (TD-DFT) on the other. We aim to evaluate the performance of the latter approach, which is very widely used for nonlinear absorption processes and whose computational cost has a more favorable scaling with the system size. We focus on LiH as a toy model for a nontrivial molecule and show that our conclusions carry over to larger molecules, exemplified by ABCU (C10H19N). The molecules are probed with IR and UV pulses whose intensities are not strong enough to significantly ionize the system. By comparing the evolution of the time-dependent field-free electronic dipole moment, as well as its Fourier power spectrum, we show that TD-DFT performs qualitatively well in most cases. Contrary to previous studies, we find almost no changes in the TD-DFT excitation energies when excited states are populated. Transitions between states of different symmetries are induced using pulses polarized in different directions. We observe that the performance of TD-DFT does not depend on the symmetry of the states involved in the transition.en
dc.description.sponsorshipBelgian Fonds National de la Recherche Collective through project number 2.4545.12 “Control of attosecond dynamics: applications to molecular reactivity”en
dc.language.isoen_USen
dc.publisherAmerican Chemical Societyen
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.jctc.5b00167en
dc.rightsArchived with thanks to Journal of Chemical Theory and Computationen
dc.subjecttime-dependent density functional theoryen
dc.subjectequation of motionen
dc.subjectultrafast electron density dynamicsen
dc.titleComputational benchmarking for ultrafast electron dynamics: wavefunction methods vs density functional theoryen_US
dc.typeArticleen
dc.contributor.departmentUniversity of Chesteren
dc.identifier.journalJournal of Chemical Theory and Computationen
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