Variational Density Functional Calculations of Excited States: Conical Intersection and Avoided Crossing in Ethylene Bond Twisting
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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
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Date
2022-05-12
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en
Pages
10
3990-3999
3990-3999
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Journal of Physical Chemistry Letters, Volume 13
Abstract
Theoretical studies of photochemical processes require a description of the energy surfaces of excited electronic states, especially near degeneracies, where transitions between states are most likely. Systems relevant to photochemical applications are typically too large for high-level multireference methods, and while time-dependent density functional theory (TDDFT) is efficient, it can fail to provide the required accuracy. A variational, time-independent density functional approach is applied to the twisting of the double bond and pyramidal distortion in ethylene, the quintessential model for photochemical studies. By allowing for symmetry breaking, the calculated energy surfaces exhibit the correct topology around the twisted-pyramidalized conical intersection even when using a semilocal functional approximation, and by including explicit self-interaction correction, the torsional energy curves are in close agreement with published multireference results. The findings of the present work point to the possibility of using a single determinant time-independent density functional approach to simulate nonadiabatic dynamics, even for large systems where multireference methods are impractical and TDDFT is often not accurate enough.Description
Funding Information: This work was supported by the Icelandic Research Fund (Grant Agreement Nos. 217751, 196070, and 217734). The calculations were carried out at the Icelandic High Performance Computing Center (IHPC). The authors thank Hemanadhan Myneni for useful discussions. Publisher Copyright: © 2022 American Chemical Society.
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Schmerwitz, Y L A, Ivanov, A V, Jónsson, E, Jónsson, H & Levi, G 2022, ' Variational Density Functional Calculations of Excited States : Conical Intersection and Avoided Crossing in Ethylene Bond Twisting ', Journal of Physical Chemistry Letters, vol. 13, no. 18, pp. 3990-3999 . https://doi.org/10.1021/acs.jpclett.2c00741