Autodesmotic reactions for general strain energy evaluation in polycyclic aromatic nanocarbons

Area of Science:

• Computational Chemistry
• Materials Science
• Organic Chemistry

Background:

• Strain energy is crucial for nanocarbon properties but difficult to quantify accurately.
• Existing methods have limitations in reference choices, π-energy balance, and computational cost.

Purpose of the Study:

• To introduce a general and efficient framework for accurate strain energy quantification in π-conjugated nanocarbons.
• To overcome limitations of existing methods by providing a reliable and computationally inexpensive approach.

Main Methods:

• Developed autodesmotic reactions to map strained nanocarbons to a defined single-molecule reference.
• Constructed a virtual chemical space using physically motivated models trained on planar benzenoid hydrocarbons.
• Validated the method across various nanocarbon structures including nanobelts, circulenes, helicenes, nanotubes, and fullerenes.

Main Results:

• The autodesmotic reaction framework accurately quantifies strain energy while preserving molecular topology and π-energy balance.
• Benchmarking confirmed the method's accuracy and robustness across diverse strained nanocarbons.
• Applications revealed insightful strain-structure-property relationships.

Conclusions:

• Autodesmotic reactions offer a rigorous, general, and highly efficient route to strain energy evaluation using a single quantum chemical calculation.
• This framework advances the rational design of strained aromatic nanocarbons.
• The platform is extensible with machine-learning strategies for accelerated discovery.