Simple Protocol for Capturing Both Linear-Response and State-Specific Effects in Excited-State Calculations with...

Area of Science:

• Computational Chemistry
• Theoretical Chemistry
• Spectroscopy

Background:

• Solvatochromism and fluorosolvatochromism are crucial for understanding molecular behavior in different environments.
• Accurate computational modeling of these phenomena is challenging due to complex solvation effects.

Purpose of the Study:

• To present an effective computational protocol, cLR2, for describing both solvatochromism and fluorosolvatochromism.
• To demonstrate the protocol's utility in modeling complex photophysical processes.

Main Methods:

• Coupling the polarizable continuum model (PCM) with time-dependent density functional theory (TD-DFT).
• Simultaneously accounting for linear-response and state-specific solvation effects.

Main Results:

• The cLR2 protocol shows significant benefits for modeling bright excitations with charge-transfer character.
• It accurately models systems requiring a balance between states of various polarities.
• Successful application to solvatochromic and fluorosolvatochromic compounds and excited-state intramolecular proton transfers.

Conclusions:

• The cLR2 protocol offers an effective approach for accurate solvatochromism and fluorosolvatochromism predictions.
• It is particularly valuable for systems with significant charge-transfer character and complex solvation requirements.