Radicals in aqueous solution: assessment of density-corrected SCAN functional

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Materials Science

Background:

• Self-interaction errors plague electronic structure calculations, particularly for strongly-correlated systems.
• Accurate modeling of solvated cationic molecular clusters is crucial for understanding chemical phenomena.

Purpose of the Study:

• To investigate and correct self-interaction effects in solvated cationic molecular clusters.
• To evaluate the performance of the DC-r^2SCAN method combined with the auxiliary density matrix approach.

Main Methods:

• Application of the DC-r^2SCAN method with the auxiliary density matrix approach.
• Validation through simulations of bulk liquid water.
• Analysis of solvated cationic molecular clusters, including [CH3S∴CH3SH]+ and [SH∴SH2]+.

Main Results:

• DC-r^2SCAN maintains structural accuracy and resolves spin density localization issues, unlike standard r^2SCAN.
• The hemibonded motif in [CH3S∴CH3SH]+ is disrupted by DC-r^2SCAN.
• DC-r^2SCAN predicts weaker hemibonding in [SH∴SH2]+, influenced by solvent-solute interactions.

Conclusions:

• DC-r^2SCAN offers improved electronic structure calculations for solvated cationic clusters.
• This work advances self-interaction corrected electronic structure theory for condensed phase systems.