Name:
Silver_Inorg_Chem_14_05_2019.pdf
Size:
1.258Mb
Format:
PDF
Description:
Accepted Manuscript
Type
ArticleKAUST Department
Chemical ScienceChemical Science Program
KAUST Catalysis Center
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Date
2019-06-07Online Publication Date
2019-06-07Print Publication Date
2019-06-17Embargo End Date
2020-06-07Permanent link to this record
http://hdl.handle.net/10754/656009
Metadata
Show full item recordAbstract
Domain-based local pair natural orbital coupled cluster approach with single, double, and perturbative triple excitations, DLPNO–CCSD(T), has been applied within a framework of a reduced version of the reaction-based Feller–Peterson–Dixon (FPD) scheme to predict gas phase heats of formation and absolute entropies of silver inorganic and organometallic compounds. First, we evaluated all existing experimental data currently limited by thermodynamic functions of 10 silver substances (AgH, AgF, AgBr, AgI, Ag2, Ag2S, Ag2Se, Ag2Te, AgCN, AgPO2). The mean average deviation between computed and experimental heats of formation was found to be 1.9 kcal/mol. Notably, all predicted heats of formation turned out to be within the error bounds of their experimental counterparts. Second, we predicted heats of formation and entropies for additional 90 silver species with no experimental data available, substantially enriching silver thermochemistry. Combination of gas phase heats of formation ΔHf and entropies S° of AgNO2, AgSCN, Ag2SO4, and Ag2SeO4 obtained in this work, with respective solid-state information, resulted in accurate sublimation thermochemistry of these compounds. Complementation of predicted ΔHf with heats of formation of some neutrals and positive ions produced 33 silver bond strengths of high reliability. Obtained thermochemical data are promising for developing the concepts of silver chemistry. In addition, derived heats of formation and bond dissociation enthalpies, due to their high diversity, are found to be relevant for testing and training of computational chemistry methods.Citation
Minenkova, I., Sliznev, V. V., Cavallo, L., & Minenkov, Y. (2019). Gas Phase Silver Thermochemistry from First Principles. Inorganic Chemistry, 58(12), 7873–7885. doi:10.1021/acs.inorgchem.9b00556Sponsors
We gratefully acknowledge Prof. J. J. P. Stewart, Stewart Computational Chemistry, Colorado Springs, CO, for helpful discussions.Publisher
American Chemical Society (ACS)Journal
Inorganic ChemistryAdditional Links
http://pubs.acs.org/doi/10.1021/acs.inorgchem.9b00556ae974a485f413a2113503eed53cd6c53
10.1021/acs.inorgchem.9b00556