Hydrogen and Carbon Vapour Pressure Isotope Effects in Liquid Fluoroform Studied by Density Functional Theory.
H/D and C/C vapour pressure isotope effects (VPIEs) in liquid fluoroform (CHF) were studied at the MPW1PW91/6-31 ++ G(d) level of theory. The CHF monomer and CHF molecules surrounded by other CHF molecules in every direction in CHF clusters were used as model molecules of vapour and liquid CHF. Alth...
| Publicado en: | Zeitschrift für Naturforschung Section A: A Journal of Physical Sciences Vol. 72; no. 3; pp. 193 - 201 |
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| Autores principales: | , , |
| Formato: | Artículo |
| Publicado: |
De Gruyter
Mar2017
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| Sumario: | H/D and C/C vapour pressure isotope effects (VPIEs) in liquid fluoroform (CHF) were studied at the MPW1PW91/6-31 ++ G(d) level of theory. The CHF monomer and CHF molecules surrounded by other CHF molecules in every direction in CHF clusters were used as model molecules of vapour and liquid CHF. Although experimental results in which the vapour pressure of liquid CHF is higher than that of liquid CDF and the vapour pressure of liquid CHF is higher than that of liquid CHF between 125 and 212 K were qualitatively reproduced, the present calculations overestimated the H/D VPIE and underestimated the C/C VPIE. Temperature- dependent intermolecular interactions between hydrogen and fluorine atoms of neighbouring molecules were required to explain the temperature dependences of both H/D and C/C VPIEs. |
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