Nonadiabaticity under compression in metastable carbon monoxide-nitroxide mixtures

TL;DR

This study investigates how CO-N2O mixtures undergo structural and chemical changes under high pressure and temperature, highlighting nonadiabatic pathways and dissociation processes that influence their phase transitions.

Contribution

It introduces comprehensive ab initio simulations of CO-N2O mixtures under extreme conditions, revealing nonadiabatic effects and dissociation pathways not previously characterized.

Findings

N2O dissociation lowers CO polymerization pressure

Nonadiabatic pathways dominate at high temperatures

Sequence from gas to amorphous solid observed

Abstract

Carbon monoxide (CO) and nitrous oxide (N2O) both undergo profound structural and chemical transformations when compressed. While their individual high-P/T phase diagrams have been mapped in considerable detail, comparatively little attention has been paid to the mixtures in which the two species can couple through oxygen transfer, charge redistribution, and nonadiabatic dissociation pathways. Here we use comprehensive ab initio adiabatic/nonadiabatic molecular dynamics simulations, essentially a diabatic trajectory stitching approach, that chart the evolution of CO-N2O mixtures from van-der-Waals fluids to extended amorphous network solids over the range 0-160 GPa and 300-1500 K. We emphasize on (i) the sequence of gas to molecular crystal to polymerized amorphous solid reactive transitions that arise from an interplay between thermal and compression effects in metastable C-N-O mixtures, (ii) the role of N2O unimolecular dissociation in lowering the onset pressure for CO polymerization, and (iii) the emergence of nonadiabatic pathways, via thermal unimolecular dissociation of N2O, accompanied by spin-transition in oxygen atoms that can make C-N-O systems deviate from Born-Oppenheimer dynamics. This dominates the chemistry once the mixture enters the regime of bond-breaking temperatures (T>900 K).