Structure-property relationships on thiolate-protected gold nanoclusters.

Area of Science:

• * Materials Science
• * Computational Chemistry
• * Nanotechnology

Background:

• * Thiolate-protected gold nanoclusters (Au NCs) exhibit unique properties and
• magic-number
• stability.
• * Lack of theoretical models for thermodynamic stability and electronic properties as a function of size.
• * Need for predictive tools to guide experimental synthesis.

Purpose of the Study:

• * To rationalize the thermodynamic stability of experimentally determined gold nanoclusters using first principles calculations.
• * To extend the applicability of a recently developed thermodynamic stability theory to larger nanocluster sizes.
• * To establish structure-property relationships linking cluster size to electronic properties.

Main Methods:

• * First principles calculations.
• * Application of a thermodynamic stability theory for small gold nanoclusters.
• * Analysis of fifteen experimentally characterized gold nanoclusters.

Main Results:

• * The thermodynamic stability theory accurately predicts the stability of large gold nanoclusters (e.g., Au₂₇₉(SR)₈₄).
• * The theory's applicability is extended to larger cluster sizes than initially developed.
• * Structure-property relationships were established, correlating ionization potential and electron affinity with the number of gold atoms.

Conclusions:

• * The validated thermodynamic stability theory provides a robust framework for understanding gold nanocluster stability across various sizes.
• * Established structure-property relationships enable the prediction of electronic properties based on cluster size.
• * The computational scheme facilitates targeted synthesis of gold nanoclusters with specific properties.