Benchmark CCSD(T) and Density Functional Theory Calculations of Biologically Relevant Catecholic Systems

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Biochemistry

Background:

• Catechols are crucial in biological systems, notably in dopamine biosynthesis.
• Understanding noncovalent interactions of catechols with proteins is vital for biological studies.
• Accurate computational modeling is needed to study these complex interactions.

Purpose of the Study:

• To evaluate the accuracy of various computational methods for catechol-containing complexes.
• To identify reliable density functional theory (DFT) methods for biological applications.
• To benchmark methods against high-level coupled cluster calculations.

Main Methods:

• Performed coupled cluster singles, doubles, and triples (CCSD(T)) calculations with approximate complete basis sets.
• Evaluated twenty-one DFT methods using triple and quadruple-zeta basis sets.
• Assessed the local DPLNO CCSD(T) method against CCSD(T)/CBS benchmarks.

Main Results:

• MN15, M06-2X-D3, ωB97XD, ωB97M-V, and CAM-B3LYP-D3 demonstrated good accuracy compared to CCSD(T)/CBS.
• These selected DFT methods are suitable for studying catechol interactions in biological systems.
• Local DPLNO CCSD(T) agreed well with CCSD(T)/CBS, within 1-3% difference.

Conclusions:

• Several DFT methods provide accurate results for catechol-protein interactions.
• The findings enable more reliable computational studies of biological processes involving catechols.
• Accurate computational tools are essential for advancing our understanding of biochemistry.