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Pierre-Francois Loos 2020-01-07 16:03:40 +01:00
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@ -189,8 +189,8 @@ Our aim is to know whether or not the BSE formalism is able to reproduce faithfu
The features of ground- and excited-state potential energy surfaces (PES) are critical for the faithful description and a deeper understanding of photochemical and photophysical processes. \cite{Bernardi_1996,Olivucci_2010,Robb_2007} The features of ground- and excited-state potential energy surfaces (PES) are critical for the faithful description and a deeper understanding of photochemical and photophysical processes. \cite{Bernardi_1996,Olivucci_2010,Robb_2007}
For example, chemoluminescence, fluorescence and other related processes are associated with geometric relaxation of excited states, and structural changes upon electronic excitation. \cite{Navizet_2011} For example, chemoluminescence, fluorescence and other related processes are associated with geometric relaxation of excited states, and structural changes upon electronic excitation. \cite{Navizet_2011}
Reliable predictions of these mechanisms which have attracted much experimental and theoretical interest lately require exploring the ground- and excited-state PES. Reliable predictions of these mechanisms which have attracted much experimental and theoretical interest lately require exploring the ground- and excited-state PES.
From a theoretical point of view, the accurate prediction of excited electronic states remains a challenge, especially for large systems where state-of-the-art computational techniques (such as multiconfigurational methods \cite{Andersson_1990,Andersson_1992,Roos_1996,Angeli_2001}) cannot be afforded. From a theoretical point of view, the accurate prediction of excited electronic states remains a challenge, \cite{Gonzales_2012, Loos_2020a} especially for large systems where state-of-the-art computational techniques (such as multiconfigurational methods \cite{Andersson_1990,Andersson_1992,Roos_1996,Angeli_2001}) cannot be afforded.
For such systems, one has to rely on more approximate, yet computationally cheaper approaches. For such systems, one has to rely on more approximate, yet computationally cheaper approaches. \cite{Grimme_2004a,Ghosh_2018}
For the last two decades, time-dependent density-functional theory (TD-DFT) \cite{Casida} has been the go-to method to compute absorption and emission spectra in large molecular systems. For the last two decades, time-dependent density-functional theory (TD-DFT) \cite{Casida} has been the go-to method to compute absorption and emission spectra in large molecular systems.
At a relatively low computational cost, TD-DFT can provide accurate vertical and adiabatic transition energies for low-lying excited states of organic molecules with a typical error of $0.2$--$0.4$ eV. \cite{Loos_2019b} At a relatively low computational cost, TD-DFT can provide accurate vertical and adiabatic transition energies for low-lying excited states of organic molecules with a typical error of $0.2$--$0.4$ eV. \cite{Loos_2019b}