Maximum hardness in P<sub>6</sub> isomers

Phosphorus is critical to humans on many fronts, yet we do not have a mechanistic understanding of some of its most basic transformations and reactionsnamely the oligomerization of white phosphorus to red. With heat or under ultraviolet (UV) exposure, it has been experimentally demonstrated that white phosphorus dissociates into diphosphorus units which readily form red phosphorus. However, the mechanism of this process is unknown. The ab initio nanoreactor approach was used to explore the potential energy surface of phosphorus clusters. Density functional theory and metadynamics simulations were used to characterize potential reaction pathways. A mechanism for oligomerization is proposed to take place via diphosphorus additions at π-bonds and weak σ-bonds through three membered ring intermediates. Downhill paths through P6 and P8 clusters eventually result in P10 clusters that can oligomerize into red phosphorus chains. The initial, rate limiting step for this process has an energy barrier of 24.2 kcal/mol.

show abstract

A Theoretical Study on the Structures of Phosphorus Clusters P12

Chen¹,

Luo²,

Qiu³

et al. 2000

Main Group Metal Chemistry

View full text Add to dashboard Cite

Twenty-eight structures of P12 were acquired with molecular graphics and optimizations were carried out with molecular mechanics, PM3 semi-empirical and ab initio calculations. In these structures, the phosphorus atoms could be two-fold, threefold or four-fold coordinated. The model of D3d symmetry derived from condensing two cuneane Ρβ via the sharing of four atoms is the most stable isomer. The imaging of enough cluster models can help to locate the global minimum. Many P12 structures are characterized by atoms in three-fold mode and those that have atoms(s) in two-fold coordination have high energies. Both tetrahedral P 4 and cuneane Pe are common components and could be important candidates for the construction of larger clusters. A planar pentagonal structure is more popular than a hexagonal one in phosphorus clusters.

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

Maximum hardness in P₆ isomers

Cited by 3 publications

References 7 publications

First principles study of the evolution of the properties of neutral and charged phosphorus clusters

First principles study of the evolution of the properties of neutral and charged phosphorus clusters

Two P, Ten P, White P, Red P: Mechanistic Exploration of the Oligomerization of Red Phosphorus from Diphosphorus with the Ab Initio Nanoreactor

A Theoretical Study on the Structures of Phosphorus Clusters P12

Contact Info

Product

Resources

About

Maximum hardness in P6 isomers

Cited by 3 publications

References 7 publications

First principles study of the evolution of the properties of neutral and charged phosphorus clusters

First principles study of the evolution of the properties of neutral and charged phosphorus clusters

Two P, Ten P, White P, Red P: Mechanistic Exploration of the Oligomerization of Red Phosphorus from Diphosphorus with the Ab Initio Nanoreactor

A Theoretical Study on the Structures of Phosphorus Clusters P12

Contact Info

Product

Resources

About

Maximum hardness in P₆ isomers