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Title: Adding flexibility to the “particles-on-a-sphere” model for large-amplitude motion: POSflex force field for protonated methane

Abstract

The so-called “particles-on-a-sphere” (POS) model has been introduced a while ago in order to describe in simple terms large-amplitude motion of polyatomic hydrides, XH{sub n}. The POS model of protonated methane, CH{sub 5}{sup +}, has been shown to capture well the essence of the fluxional nature of this enigmatic floppy molecule. Here, we extend this model to the POSflex force field by adding flexibility to the C–H bonds, which are constrained to a common fixed bond length in the original model. This makes the present model extremely efficient for computer simulation, including path integral molecular dynamics in order to assess the crucial quantum effects on nuclear motion at low temperatures. Moreover, the POSflex force field can be conveniently used to study microsolvation effects upon combining it with intermolecular pair potentials to account for solute-solvent interactions. Upon computing static properties as well as thermal and quantum fluctuation effects at ambient and low temperatures, respectively, it is shown that the POSflex model is very well suited to describe the structural properties of bare CH{sub 5}{sup +}, including hydrogen scrambling and thus fluxionality in the first place. The far- to mid-infrared spectrum up to the bending band is roughly described, whereas the modelmore » fails to account for the well-structured stretching band by construction.« less

Authors:
; ; ;  [1]
  1. Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, 44780 Bochum (Germany)
Publication Date:
OSTI Identifier:
22308905
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 10; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AMPLITUDES; BOND LENGTHS; COMPUTERIZED SIMULATION; FLEXIBILITY; FLUCTUATIONS; INFRARED SPECTRA; INTERACTIONS; METHANE; MOLECULAR DYNAMICS METHOD; MOLECULES; SOLUTES; SOLVENTS

Citation Formats

Uhl, Felix, Walewski, Łukasz, Forbert, Harald, and Marx, Dominik. Adding flexibility to the “particles-on-a-sphere” model for large-amplitude motion: POSflex force field for protonated methane. United States: N. p., 2014. Web. doi:10.1063/1.4895473.
Uhl, Felix, Walewski, Łukasz, Forbert, Harald, & Marx, Dominik. Adding flexibility to the “particles-on-a-sphere” model for large-amplitude motion: POSflex force field for protonated methane. United States. doi:10.1063/1.4895473.
Uhl, Felix, Walewski, Łukasz, Forbert, Harald, and Marx, Dominik. Sun . "Adding flexibility to the “particles-on-a-sphere” model for large-amplitude motion: POSflex force field for protonated methane". United States. doi:10.1063/1.4895473.
@article{osti_22308905,
title = {Adding flexibility to the “particles-on-a-sphere” model for large-amplitude motion: POSflex force field for protonated methane},
author = {Uhl, Felix and Walewski, Łukasz and Forbert, Harald and Marx, Dominik},
abstractNote = {The so-called “particles-on-a-sphere” (POS) model has been introduced a while ago in order to describe in simple terms large-amplitude motion of polyatomic hydrides, XH{sub n}. The POS model of protonated methane, CH{sub 5}{sup +}, has been shown to capture well the essence of the fluxional nature of this enigmatic floppy molecule. Here, we extend this model to the POSflex force field by adding flexibility to the C–H bonds, which are constrained to a common fixed bond length in the original model. This makes the present model extremely efficient for computer simulation, including path integral molecular dynamics in order to assess the crucial quantum effects on nuclear motion at low temperatures. Moreover, the POSflex force field can be conveniently used to study microsolvation effects upon combining it with intermolecular pair potentials to account for solute-solvent interactions. Upon computing static properties as well as thermal and quantum fluctuation effects at ambient and low temperatures, respectively, it is shown that the POSflex model is very well suited to describe the structural properties of bare CH{sub 5}{sup +}, including hydrogen scrambling and thus fluxionality in the first place. The far- to mid-infrared spectrum up to the bending band is roughly described, whereas the model fails to account for the well-structured stretching band by construction.},
doi = {10.1063/1.4895473},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 10,
volume = 141,
place = {United States},
year = {2014},
month = {9}
}