Protocol for Directing Nudged Elastic Band Calculations to the Minimum Energy Pathway: Nurturing Errant Calculations Back to Convergence.

The combination of density functional theory (DFT) and the nudged elastic band (NEB) method offers a practical tool for the discovery of underlying reaction mechanisms related to the synthesis of functional materials. However, in , the lack of a standardized protocol for minimum energy pathway determination too often leads to an inefficient and computationally intensive design process. To that end, we define a verifiable DFT+NEB protocol for efficiently locating and confirming the transition state of a reaction.

Molecular modeling of interfacial layer-by-layer assembly towards functionalized capsule materials.

Encapsulated nanomaterials, such as polymer-coated nanoemulsions, have highly tunable properties leading to versatile applications. A current lack of understanding of the fundamentals governing the choice of "capsule" materials (polyelectrolyte + surfactant) and its ensuing performance effectively precludes their widespread use. Computational methods can start to redress this by discovering molecule-scale attributes that significantly control the design of capsule materials tuned to fit desired properties.

Decomplexation as a rate limitation in the thiol-Michael addition of N-acrylamides.

The thiol-Michael addition is a popular, selective, high-yield "click" reaction utilized for applications ranging from small-molecule synthesis to polymer or surface modification. Here, we combined experimental and quantum mechanical modeling approaches using density functional theory (DFT) to examine the thiol-Michael reaction of N-allyl-N-acrylamide monomers used to prepare sequence-defined oligothioetheramides (oligoTEAs). Experimentally, the reaction was evaluated with two fluorous tagged thiols and several monomers at room temperature (22 °C and 40 °C).

A Quantitative Metric for the Design of Selective Supercritical CO Extraction of Lithium from Geothermal Brine.

As demand grows for lithium, its recovery from geothermal brines provides an attractive alternative to slow mining. One promising extraction method uses crown ethers as extractants in supercritical carbon dioxide with cation exchangers to facilitate extraction from brine. Molecular dynamics modeling is used to understand the mechanism of binding between lithium (or sodium) and combinations of 14-crown-4 ethers and cation exchangers, and the predictive capability of computational modeling to test lithium selectivity is established for four combinations of crown ethers [methylene-14-crown-4 (M14C4) and a fluorinated 14-crown-4 (F14C4)] and cation exchangers [di(2-ethyl-hexyl)phosphoric acid (HDEHP) and tetraethylammonium perfluoro-1-octanesulfonate (TPFOS)].