Gas Phase Silver Thermochemistry from First Principles

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Thermochemistry

Background:

• Accurate thermochemical data for silver compounds are crucial for understanding silver chemistry.
• Existing experimental data are limited, necessitating reliable computational predictions.

Purpose of the Study:

• To predict gas-phase heats of formation and absolute entropies for silver inorganic and organometallic compounds.
• To expand the available thermochemical database for silver species.
• To provide reliable data for testing and training computational chemistry methods.

Main Methods:

• Application of the domain-based local pair natural orbital coupled cluster approach with single, double, and perturbative triple excitations (DLPNO-CCSD(T)).
• Utilized a reduced version of the reaction-based Feller-Peterson-Dixon (FPD) scheme.
• Evaluated existing experimental data for 10 silver substances and predicted data for 90 additional species.

Main Results:

• Achieved a mean average deviation of 1.9 kcal/mol between computed and experimental heats of formation for existing data.
• All predicted heats of formation were within experimental error bounds.
• Generated thermochemical data for 90 new silver species, including heats of formation, entropies, sublimation thermochemistry, and 33 silver bond strengths.

Conclusions:

• The DLPNO-CCSD(T) approach provides highly reliable thermochemical data for silver compounds.
• The generated data significantly enriches the field of silver thermochemistry.
• The results are valuable for advancing the understanding of silver chemistry and for the development of computational chemistry methods.