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Title: When finite becomes infinite: convergence properties of vibrational spectra of oligomer chains

Abstract

We present a computational study of convergence properties of vibrational IR and Raman spectra for a series of increasingly long units of polyethylene, cis- and trans-polyacetylenes, and polyynes. Convergent behavior to the spectra of infinitely long polymers was observed in all cases when chains reached lengths of approximately 60 carbon atoms, both with respect to the positions of the bands and to their intensities. The vibrational spectra of longer chains are practically indistinguishable. The convergence rate depends on the degree of the π conjugation in a studied system: Vibrational spectra for oligoethylenes converge noticeably faster than the spectra for the conjugated systems. Here, the slowest convergence is observed for skeletal motions of the oligomer chains, which may require more than a hundred carbon atoms in the chain to show deviations smaller than 1 cm–1 to the corresponding solid-state calculations. The results suggest that the boundary between the properties of finite and infinite molecular systems fades away for a surprisingly small number of atoms.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]
+ Show Author Affiliations
  1. Waseda Univ., Tokyo (Japan); National Chiao Tung Univ., Hsinchu (Taiwan)
  2. National Chiao Tung Univ., Hsinchu (Taiwan)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Nagoya Univ. (Japan)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1784147
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Molecular Modeling
Additional Journal Information:
Journal Volume: 24; Journal Issue: 10; Journal ID: ISSN 1610-2940
Publisher:
Springer-Verlag
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Simulations of IR and Raman spectra of polymers; Convergence in size evolution; SCC-DFTB

Citation Formats

Chou, Chien-Pin, Witek, Henryk, and Irle, Stephan. When finite becomes infinite: convergence properties of vibrational spectra of oligomer chains. United States: N. p., 2018. Web. doi:10.1007/s00894-018-3824-3.
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Chou, Chien-Pin, Witek, Henryk, & Irle, Stephan. When finite becomes infinite: convergence properties of vibrational spectra of oligomer chains. United States. https://doi.org/10.1007/s00894-018-3824-3
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Chou, Chien-Pin, Witek, Henryk, and Irle, Stephan. Fri . "When finite becomes infinite: convergence properties of vibrational spectra of oligomer chains". United States. https://doi.org/10.1007/s00894-018-3824-3. https://www.osti.gov/servlets/purl/1784147.
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@article{osti_1784147,
title = {When finite becomes infinite: convergence properties of vibrational spectra of oligomer chains},
author = {Chou, Chien-Pin and Witek, Henryk and Irle, Stephan},
abstractNote = {We present a computational study of convergence properties of vibrational IR and Raman spectra for a series of increasingly long units of polyethylene, cis- and trans-polyacetylenes, and polyynes. Convergent behavior to the spectra of infinitely long polymers was observed in all cases when chains reached lengths of approximately 60 carbon atoms, both with respect to the positions of the bands and to their intensities. The vibrational spectra of longer chains are practically indistinguishable. The convergence rate depends on the degree of the π conjugation in a studied system: Vibrational spectra for oligoethylenes converge noticeably faster than the spectra for the conjugated systems. Here, the slowest convergence is observed for skeletal motions of the oligomer chains, which may require more than a hundred carbon atoms in the chain to show deviations smaller than 1 cm–1 to the corresponding solid-state calculations. The results suggest that the boundary between the properties of finite and infinite molecular systems fades away for a surprisingly small number of atoms.},
doi = {10.1007/s00894-018-3824-3},
journal = {Journal of Molecular Modeling},
number = 10,
volume = 24,
place = {United States},
year = {Fri Sep 21 00:00:00 EDT 2018},
month = {Fri Sep 21 00:00:00 EDT 2018}
}
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