Charge-Transfer Excitations: A Challenge for Time-Dependent Density Functional Theory That Has Been Met
نویسندگان
چکیده
منابع مشابه
Charge transfer, double and bond-breaking excitations with time-dependent density matrix functional theory.
Time-dependent density functional theory (TDDFT) in its current adiabatic implementations exhibits three remarkable failures: (a) completely wrong behavior of the excited state surface along a bond-breaking coordinate; (b) lack of doubly excited configurations; (c) much too low charge transfer excitation energies. These TDDFT failure cases are all strikingly exhibited by prototype two-electron ...
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We identify the key property that the exchange-correlation (XC) kernel of time-dependent density-functional theory must have in order to describe long-range charge-transfer excitations. We show that the discontinuity of the XC potential as a function of particle number induces a spaceand frequency-dependent discontinuity of the XC kernel that diverges as r → ∞. In a combined donor-acceptor syst...
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An approximate solution to the time-dependent density-functional theory response equations for finite systems is developed, yielding corrections to the single-pole approximation. These explain why allowed Kohn-Sham transition frequencies and oscillator strengths are usually good approximations to the true values, and why sometimes they are not. The approximation yields simple expressions for Gö...
متن کاملCharge transfer in time-dependent density functional theory.
Charge transfer plays a crucial role in many processes of interest in physics, chemistry, and bio-chemistry. In many applications the size of the systems involved calls for time-dependent density functional theory (TDDFT) to be used in their computational modeling, due to its unprecedented balance between accuracy and efficiency. However, although exact in principle, in practise approximations ...
متن کاملAsymptotic correction of the exchange-correlation kernel of time-dependent density functional theory for long-range charge-transfer excitations.
Time-dependent density functional theory (TDDFT) calculations of charge-transfer excitation energies omegaCT are significantly in error when the adiabatic local density approximation (ALDA) is employed for the exchange-correlation kernel fxc. We relate the error to the physical meaning of the orbital energy of the Kohn-Sham lowest unoccupied molecular orbital (LUMO). The LUMO orbital energy in ...
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ژورنال
عنوان ژورنال: Advanced Energy Materials
سال: 2017
ISSN: 1614-6832
DOI: 10.1002/aenm.201700440