The AuTi gaseous molecule was for the first time identified in vapors produced at high temperature from a gold–titanium alloy. The homogeneous equilibria AuTi(g) = Au(g) + Ti(g) (direct dissociation) and AuTi(g) + Au(g) = Au2(g) + Ti(g) (isomolecular exchange) were studied by Knudsen effusion mass spectrometry in the temperature range 2111–2229 K. The so determined equilibrium constants were treated by the “third-law method” of thermodynamic analysis, integrated with theoretical calculations, and the dissociation energy at 0 K was derived as (AuTi) = 241.0 ± 5.2 kJ/mol. A similar investigation was carried out for the AuSc and AuFe species, whose dissociation energies were previously reported with large uncertainties. The direct dissociation and the isomolecular exchange with the Au2 dimer were studied in the 1969–2274 and 1842–2092 K ranges for AuSc and AuFe, respectively, and the dissociation energies derived as (AuSc) = 240.4 ± 6.0 and (AuFe) = 186.2 ± 4.2 kJ/mol. The experimental bond energies are compared with those calculated here by coupled cluster with single, double, and perturbative triple excitations with the correlation-consistent basis sets cc-pVXZ(-PP) and cc-pwCVXZ(-PP) (with X = T, Q, 5), also in the limit of complete basis set, and with those from complete active space self-consistent field-multi-reference configuration interaction calculations, recently available in the literature. The stronger bond of AuTi compared to AuFe parallels the trend observed in monochlorides. This analogy is shown to be more generally observed in the AuM and MCl diatomic series (with M = first row transition metal), in accordance with a picture of “pseudo-halogen” bonding behavior of gold.
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28 August 2022
Research Article|
August 23 2022
The AuSc, AuTi, and AuFe molecules: Determination of the bond energies by Knudsen effusion mass spectrometry experiments combined with ab initio calculations
Special Collection:
Nature of the Chemical Bond
Elena Lucci;
Elena Lucci
(Data curation, Investigation)
Department of Chemistry, University of Rome La Sapienza
, p.le A. Moro 5, I-00185 Rome, Italy
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Sara Giarrusso
;
(Data curation, Formal analysis, Investigation, Methodology, Writing – review & editing)
Department of Chemistry, University of Rome La Sapienza
, p.le A. Moro 5, I-00185 Rome, Italy
b)Authors to whom correspondence should be addressed: sgiarrusso@ucmerced.edu and andrea.ciccioli@uniroma1.it
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Guido Gigli;
Guido Gigli
c)
(Conceptualization, Data curation, Formal analysis, Investigation, Methodology, Writing – review & editing)
Department of Chemistry, University of Rome La Sapienza
, p.le A. Moro 5, I-00185 Rome, Italy
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Andrea Ciccioli
(Conceptualization, Data curation, Formal analysis, Investigation, Methodology, Writing – original draft, Writing – review & editing)
Department of Chemistry, University of Rome La Sapienza
, p.le A. Moro 5, I-00185 Rome, Italy
b)Authors to whom correspondence should be addressed: sgiarrusso@ucmerced.edu and andrea.ciccioli@uniroma1.it
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a)
Present address: Department of Chemistry and Biochemistry, University of California Merced, 5200 North Lake Rd. Merced, CA 95343, USA.
b)Authors to whom correspondence should be addressed: sgiarrusso@ucmerced.edu and andrea.ciccioli@uniroma1.it
c)
Presently retired.
Note: This paper is part of the JCP Special Topic on Nature of the Chemical Bond.
J. Chem. Phys. 157, 084303 (2022)
Article history
Received:
April 05 2022
Accepted:
August 03 2022
Citation
Elena Lucci, Sara Giarrusso, Guido Gigli, Andrea Ciccioli; The AuSc, AuTi, and AuFe molecules: Determination of the bond energies by Knudsen effusion mass spectrometry experiments combined with ab initio calculations. J. Chem. Phys. 28 August 2022; 157 (8): 084303. https://doi.org/10.1063/5.0094621
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