Thermodynamics of phase transitions in Zintl clusters from density functional theory: making and breaking of bonds in Ba3Ge4

Zhao, Y; McGrady, JE

Journal article

Thermodynamics of phase transitions in Zintl clusters from density functional theory: making and breaking of bonds in Ba3Ge4

Abstract:: The reactivity of clusters is known to be strongly influenced by their local atomic environments, and that is the central concept that unites the different chapters in this thesis. I present three distinct theoretical investigations into the electronic structure and reactivity of clusters, covering different aspects of chemical behaviour. The first project concerns the structure of partially-ligated ruthenium carbonyl clusters, and the mechanism of their reactivity in the gaseous phase. The patterns of stable configurations of ligands are identified, and the link between the number and distribution of unsaturated sites on reactivity will be discussed. The second project looks at catalysis from the opposite extreme of unsaturation, specifically for a Ru3-based 'single-cluster catalyst' and its interaction with a surface support. The electronic structures of several models for this system are examined and the significance of subtle details in the model on the stability will be demonstrated. The final project concerns structural phase transitions and temperature effects on the stability of Zintl clusters in solids. The work emphasises the importance of understanding phonon density of states and the origin of changes of entropy when considering the thermodynamics of phase transitions. While all of the research described in this thesis is motivated by experimental observations, the work itself is done purely with theoretical and computational techniques, the aim being to enhance the information content of the experiments. Such understanding is crucial for formulating universal principles of designing advanced catalysts such as single-cluster catalysts

Publication status:: Published

Peer review status:: Peer reviewed

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APA Style

Zhao, Y., & McGrady, J. E. (2024). Thermodynamics of phase transitions in Zintl clusters from density functional theory: making and breaking of bonds in Ba3Ge4. Physical Chemistry Chemical Physics, 26(9), 7318–7328.

MLA Style

Zhao, Y, and JE McGrady. “Thermodynamics of Phase Transitions in Zintl Clusters from Density Functional Theory: Making and Breaking of Bonds in Ba3Ge4.” Physical Chemistry Chemical Physics, vol. 26, no. 9, 2024, pp. 7318–28.

Chicago Style

Zhao, Y, and JE McGrady. 2024. “Thermodynamics of Phase Transitions in Zintl Clusters from Density Functional Theory: Making and Breaking of Bonds in Ba3Ge4.” Physical Chemistry Chemical Physics 26 (9): 7318–28.
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