Nanocrystal programmable assembly beyond hard spheres (or shapes) and other (simple) potentials

Travesset, Alex

doi:10.1016/j.cossms.2024.101159

Cited by 1 publication

(1 citation statement)

References 188 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The excellent agreement between simulation and MOLT-CF reported in Figure c provides evidence that the large (∼500 k B T ) cohesive free energies correspond to actual thermodynamic equilibrium. This is because segment–segment interactions are a fraction of k B T , so bonds among CH 2 and CH 3 break and reform many times over simulation time (see refs , for a more detailed discussion). Moreover, the very large cohesive energy does not hinder structural transitions, such as the bcc-fcc Bain transformation, , because the free-energy barrier between phases is also of the order of k B T …”

Section: Structure Of Solvent-swollen Npslsmentioning

confidence: 99%

Solvent Isotherms and Structural Transitions in Nanoparticle Superlattice Assembly

Missoni,

Upah,

Zaldívar

et al. 2024

Nano Lett.

Self Cite

View full text Add to dashboard Cite

We introduce a Molecular Theory for Compressible Fluids (MOLT-CF) that enables us to compute free energies and other thermodynamic functions for nanoparticle superlattices with any solvent content, including the dry limit. Quantitative agreement is observed between MOLT-CF and united-atom molecular dynamics simulations performed to assess the reliability and precision of the theory. Among other predictions, MOLT-CF shows that the amount of solvent within the superlattice decreases approximately linearly with its vapor pressure and that in the late stages of drying, solvent-filled voids form at lattice interstitials. Applied to single-component superlattices, MOLT-CF predicts fcc-to-bcc Bain transitions for decreasing vapor pressure and for increasing ligand length, both in agreement with experimental results. We explore the stability of other single-component phases and show that the C14 Frank-Kasper phase, which has been reported in experiments, is not a global free-energy minimum. Implications for precise assembly and prediction of multicomponent nanoparticle systems are discussed.

show abstract