Journal ArticleDOI
Failure of time-dependent density functional theory for excited state surfaces in case of homolytic bond dissociation
TLDR
In this article, it was shown that the ATDDFT has much too low excitation energies at long bond length in (dissociating) electron pair bonds, and this easily escapes attention due to the occurrence of the problems at slightly longer distances than the equilibrium geometry.About:
This article is published in Chemical Physics Letters.The article was published on 2008-08-20. It has received 53 citations till now. The article focuses on the topics: Excited state & Ground state.read more
Citations
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Progress in Time-Dependent Density-Functional Theory
TL;DR: The objective of this article is to continue where a previous review of TD-DFT in Volume 55 of the Annual Review of Physical Chemistry left off and highlight some of the problems and solutions from the point of view of applied physical chemistry.
Journal ArticleDOI
The Kohn–Sham gap, the fundamental gap and the optical gap: the physical meaning of occupied and virtual Kohn–Sham orbital energies
Evert Jan Baerends,Evert Jan Baerends,Evert Jan Baerends,Oleg V. Gritsenko,Oleg V. Gritsenko,R. van Meer,R. van Meer +6 more
TL;DR: A number of consequences of the presence of the exchange-correlation hole potential in the Kohn-Sham potential are elucidated and the spurious nature of HF LUMOs if the orbital energy is positive is stressed.
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Computing chiroptical properties with first-principles theoretical methods: background and illustrative examples.
TL;DR: This "tutorial style" review outlines the theoretical foundation for computations of chiroptical properties for optically active molecules and highlights the strengths and weaknesses of currently popular time-dependent density functional methods.
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Physical Meaning of Virtual Kohn-Sham Orbitals and Orbital Energies: An Ideal Basis for the Description of Molecular Excitations.
TL;DR: This work highlights the advantages of (close to) exact Kohn-Sham orbitals and orbital energies for a simple description, very often as just a single orbital-to-orbital transition, of molecular excitations and stresses that such advantages are completely lost in time-dependent Hartree-Fock and partly in hybrid approaches.
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Assessing Excited State Methods by Adiabatic Excitation Energies
TL;DR: A 109-membered benchmark set of adiabatic excitation energies (AEEs) from high-resolution gas-phase experiments, which includes a variety of organic chromophores with up to 46 atoms, radicals, and inorganic transition metal compounds, is compiled.
References
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Journal ArticleDOI
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
TL;DR: In this paper, a detailed study of correlation effects in the oxygen atom was conducted, and it was shown that primitive basis sets of primitive Gaussian functions effectively and efficiently describe correlation effects.
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A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
TL;DR: In this article, a new hybrid exchange-correlation functional named CAM-B3LYP is proposed, which combines the hybrid qualities of B3LYP and the long-range correction presented by Tawada et al.
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Adiabatic time-dependent density functional methods for excited state properties
Filipp Furche,Reinhart Ahlrichs +1 more
TL;DR: In this paper, the authors present theory, implementation, and validation of excited state properties obtained from time-dependent density functional theory (TDDFT), based on a fully variational expression for the excited state energy, a compact derivation of first order properties is given.
Book
Recent Advances in Density Functional Methods Part III
TL;DR: In this article, Ciofini et al. used DFT to calculate the correlation energy for Isoelectronic series of atoms by the Line Integral Method (LIM) and to predict the structural and electronic properties of polymeric systems.
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Long-range charge-transfer excited states in time-dependent density functional theory require non-local exchange
TL;DR: In this paper, the electrostatic attraction between the separated charges in long-range excited charge-transfer states originates from the non-local Hartree-Fock exchange potential and is a nonlocal property.