The structure of PX3 (X = Cl, Br, I) molecular liquids from X-ray diffraction, molecular dynamics simulations, and reverse Monte Carlo modeling

Szilvia Pothoczki, László Temleitner, L. Pusztai

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Synchrotron X-ray diffraction measurements have been conducted on liquid phosphorus trichloride, tribromide, and triiodide. Molecular Dynamics simulations for these molecular liquids were performed with a dual purpose: (1) to establish whether existing intermolecular potential functions can provide a picture that is consistent with diffraction data and (2) to generate reliable starting configurations for subsequent Reverse Monte Carlo modelling. Structural models (i.e., sets of coordinates of thousands of atoms) that were fully consistent with experimental diffraction information, within errors, have been prepared by means of the Reverse Monte Carlo method. Comparison with reference systems, generated by hard sphere-like Monte Carlo simulations, was also carried out to demonstrate the extent to which simple space filling effects determine the structure of the liquids (and thus, also estimating the information content of measured data). Total scattering structure factors, partial radial distribution functions and orientational correlations as a function of distances between the molecular centres have been calculated from the models. In general, more or less antiparallel arrangements of the primary molecular axes that are found to be the most favourable orientation of two neighbouring molecules. In liquid PBr3 electrostatic interactions seem to play a more important role in determining intermolecular correlations than in the other two liquids; molecular arrangements in both PCl3 and PI3 are largely driven by steric effects.

Original languageEnglish
Article number054504
JournalThe Journal of Chemical Physics
Volume140
Issue number5
DOIs
Publication statusPublished - 2014

Fingerprint

Molecular dynamics
molecular dynamics
X ray diffraction
Computer simulation
Liquids
liquids
diffraction
x rays
simulation
Diffraction
reference systems
Coulomb interactions
Synchrotrons
radial distribution
Distribution functions
Monte Carlo method
phosphorus
synchrotrons
Monte Carlo methods
estimating

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

The structure of PX3 (X = Cl, Br, I) molecular liquids from X-ray diffraction, molecular dynamics simulations, and reverse Monte Carlo modeling. / Pothoczki, Szilvia; Temleitner, László; Pusztai, L.

In: The Journal of Chemical Physics, Vol. 140, No. 5, 054504, 2014.

Research output: Contribution to journalArticle

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