Pressure-induced conformation transition of o -phenylene solvated in bulk hydrocarbons

Massimo Riello, Giovanni Doni, Sorin V. Filip, Martin Gold, Alessandro De Vita*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

3 Citations (Scopus)


The conformational behavior of o-phenylene 8-mers and 10-mers solvated in a series of linear alkane solvents by means of classical molecular dynamics and first-principles calculations was studied. Irrespective of the solvent used, we find that at ambient pressure the molecule sits in the well-defined close-helical arrangement previously observed in light polar solvents. However, for pressures greater than 50 atm, and for tetradecane or larger solvent molecules, our simulations predict that o-phenylene undergoes a conformational transition to an uncoiled, extended geometry with a 35% longer head-to-tail distance and a much larger overlap between its lateral aromatic ring groups. The free energy barrier for the transition was studied as a function of pressure and temperature for both solute molecules in butane and hexadecane. Gas-phase density functional theory-based nudged elastic band calculations on 8-mer and 10-mer o-phenylene were used to estimate how the pressure-induced transition energy barrier changes with solute length. Our results indicate that a sufficiently large solvent molecule size is the key factor enabling a configuration transition upon pressure changes and that longer solute molecules associate with higher conformation transition energy barriers. This suggests the possibility of designing systems in which a solute molecule can be selectively activated by a controlled conformation transition achieved at a predefined set of pressure and temperature conditions.

Original languageEnglish
Pages (from-to)13689-13696
Number of pages8
Issue number47
Publication statusPublished - 26 Nov 2014


Dive into the research topics of 'Pressure-induced conformation transition of o -phenylene solvated in bulk hydrocarbons'. Together they form a unique fingerprint.

Cite this