Excited-state calculations with TD-DFT: from benchmarks to simulations in complex environments

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Spectroscopy

Background:

• Time-Dependent Density Functional Theory (TD-DFT) is a key method for calculating electronic excitation energies.
• Accurate simulation of excited states in complex environments remains a challenge.

Purpose of the Study:

• To provide an overview of recent advances in TD-DFT for excited state simulations.
• To highlight the importance of environmental effects and computational strategies.
• To introduce extensions for phenomena like electronic energy transfer.

Main Methods:

• Review of recent TD-DFT benchmarks for excitation energies.
• Coupling TD-DFT with models for chromophore-environment interactions (solvents, surfaces).
• Application examples for excitation properties and electronic energy transfer (EET).

Main Results:

• Summarized average TD-DFT accuracy using conventional approaches.
• Demonstrated successful coupling of TD-DFT with environmental models.
• Illustrated TD-DFT's applicability to processes beyond vertical excitation, like EET.

Conclusions:

• TD-DFT, when coupled with appropriate environmental models, offers a powerful approach for simulating excited states in realistic chemical systems.
• Recent computational strategies enhance the accuracy and scope of TD-DFT.
• The methodology is extendable to complex processes such as electronic energy transfer.