Local density augmentation in neat supercritical fluids: The role of electrostatic interactions

W. Song; M. Maroncelli

doi:10.1016/j.cplett.2003.07.003

Local density augmentation in neat supercritical fluids: The role of electrostatic interactions

W. Song
, M. Maroncelli

Research output: Contribution to journal › Article › peer-review

29 Scopus citations

Abstract

Motivated by a recent study of Saitow et al. [Chem. Phys. Lett. 368 (2003) 209-214 ], computer simulations and dielectric analyses are used to explore the effect electrical interactions have on density augmentation in supercritical fluoroform. Simulations of 2-site models of fluoroform and ethane show that electrical interactions increase local densities but not dramatically. The density augmentation simulated in both fluids (Δρ _max=0.12ρ_c and 0.15ρ_c) is much smaller than the value Δρ_max≅0.5ρ_c deduced by Saitow et al. from Raman measurements. This discrepancy can be reconciled if the observed vibrational shifts reflect mainly dipolar interactions, an interpretation justified by ab initio calculations.

Original language	English (US)
Pages (from-to)	410-419
Number of pages	10
Journal	Chemical Physics Letters
Volume	378
Issue number	3-4
DOIs	https://doi.org/10.1016/j.cplett.2003.07.003
State	Published - Sep 5 2003

All Science Journal Classification (ASJC) codes

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1016/j.cplett.2003.07.003

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title = "Local density augmentation in neat supercritical fluids: The role of electrostatic interactions",

abstract = "Motivated by a recent study of Saitow et al. [Chem. Phys. Lett. 368 (2003) 209-214 ], computer simulations and dielectric analyses are used to explore the effect electrical interactions have on density augmentation in supercritical fluoroform. Simulations of 2-site models of fluoroform and ethane show that electrical interactions increase local densities but not dramatically. The density augmentation simulated in both fluids (Δρ max=0.12ρc and 0.15ρc) is much smaller than the value Δρmax≅0.5ρc deduced by Saitow et al. from Raman measurements. This discrepancy can be reconciled if the observed vibrational shifts reflect mainly dipolar interactions, an interpretation justified by ab initio calculations.",

author = "W. Song and M. Maroncelli",

note = "Funding Information: The authors thank Ken-ichi Saitow for helpful discussions of his work. The present study was funded by a grant from the National Science Foundation (CHE-9980383). ",

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doi = "10.1016/j.cplett.2003.07.003",

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TY - JOUR

T1 - Local density augmentation in neat supercritical fluids

T2 - The role of electrostatic interactions

AU - Song, W.

AU - Maroncelli, M.

N1 - Funding Information: The authors thank Ken-ichi Saitow for helpful discussions of his work. The present study was funded by a grant from the National Science Foundation (CHE-9980383).

PY - 2003/9/5

Y1 - 2003/9/5

N2 - Motivated by a recent study of Saitow et al. [Chem. Phys. Lett. 368 (2003) 209-214 ], computer simulations and dielectric analyses are used to explore the effect electrical interactions have on density augmentation in supercritical fluoroform. Simulations of 2-site models of fluoroform and ethane show that electrical interactions increase local densities but not dramatically. The density augmentation simulated in both fluids (Δρ max=0.12ρc and 0.15ρc) is much smaller than the value Δρmax≅0.5ρc deduced by Saitow et al. from Raman measurements. This discrepancy can be reconciled if the observed vibrational shifts reflect mainly dipolar interactions, an interpretation justified by ab initio calculations.

AB - Motivated by a recent study of Saitow et al. [Chem. Phys. Lett. 368 (2003) 209-214 ], computer simulations and dielectric analyses are used to explore the effect electrical interactions have on density augmentation in supercritical fluoroform. Simulations of 2-site models of fluoroform and ethane show that electrical interactions increase local densities but not dramatically. The density augmentation simulated in both fluids (Δρ max=0.12ρc and 0.15ρc) is much smaller than the value Δρmax≅0.5ρc deduced by Saitow et al. from Raman measurements. This discrepancy can be reconciled if the observed vibrational shifts reflect mainly dipolar interactions, an interpretation justified by ab initio calculations.

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DO - 10.1016/j.cplett.2003.07.003

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EP - 419

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 3-4

ER -

Local density augmentation in neat supercritical fluids: The role of electrostatic interactions

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