Refinement of the experimental dynamic structure factor for liquid para-hydrogen and ortho-deuterium using semi-classical quantum simulation

• Published in: The Journal of chemical physics 2014-01, Vol.140 (3)
• Main Authors: Smith, Kyle K. G., Rossky, Peter J., Poulsen, Jens Aage, Cunsolo, A.
• Format: Article
• Language: English
• Subjects: DEUTERIUM; HYDROGEN; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; LIQUIDS; MOLECULAR DYNAMICS METHOD; POLYMERS; SIMULATION; SPECTRA; STRUCTURE FACTORS; X-RAY DIFFRACTION
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.4851997

The dynamic structure factor of liquid para-hydrogen and ortho-deuterium in corresponding thermodynamic states (T = 20.0 K, n = 21.24 nm{sup −3}) and (T = 23.0 K, n = 24.61 nm{sup −3}), respectively, has been computed by both the Feynman-Kleinert linearized path-integral (FK-LPI) and Ring-Polymer Molecular Dynamics (RPMD) methods and compared with Inelastic X Ray Scattering spectra. The combined use of computational and experimental methods enabled us to reduce experimental uncertainties in the determination of the true sample spectrum. Furthermore, the refined experimental spectrum of para-hydrogen and ortho-deuterium is consistently reproduced by both FK-LPI and RPMD results at momentum transfers lower than 12.8 nm{sup −1}. At larger momentum transfers the FK-LPI results agree with experiment much better for ortho-deuterium than for para-hydrogen. More specifically we found that for k ∼ 20.0 nm{sup −1} para-hydrogen provides a test case for improved approximations to quantum dynamics.