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.
Affiliation
University of ChesterPublication Date
2015-05-12
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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.Citation
Oliveira, M. J., Mignolet, B., Kus, T., Papadopoulos, T. A., Remacle, F., & Verstraete, M. J. (2015). Computational Benchmarking for Ultrafast Electron Dynamics: Wave Function Methods vs Density Functional Theory. Journal of Chemical Theory and Computation, 11(5), 2221-2233.Publisher
American Chemical SocietyAdditional Links
http://pubs.acs.org/doi/abs/10.1021/acs.jctc.5b00167Type
ArticleLanguage
en_USISSN
1549-9618EISSN
1549-9626Sponsors
Belgian Fonds National de la Recherche Collective through project number 2.4545.12 “Control of attosecond dynamics: applications to molecular reactivity”ae974a485f413a2113503eed53cd6c53
10.1021/acs.jctc.5b00167
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