On calculating a polymer's enthalpy of formation with quantum chemical methods

Edward Brothers, Artur F. Izmaylov, Alexander A. Rusakov, Gustavo E. Scuseria

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Calculating the enthalpy of formation of a polymer with ab initio methods requires two choices. The first decision is whether to use oligomeric extrapolation or periodic boundary conditions to model the extended system, and the second choice is between formation reactions to be modeled, for example, formation from atoms, formation from standard states, or formation from some set of molecular systems. Utilizing trans-polyacetylene and polyethylene as examples, the oligomeric and periodic techniques are contrasted, leading to a discussion of the larger than minimal unit cell required when frequency calculations only include in-phase vibrations, that is, only the k = 0 frequencies, in an enthalpy of formation calculation. The accuracy of calculating the enthalpy of formation, in light of density functional theory's increased error with larger systems and with respect to various reference states, is also discussed. The calculation of the enthalpy of formation for a polymer is most accurate when the reference states are chosen carefully and most efficient when using periodic boundary conditions.

Original languageEnglish
Pages (from-to)13869-13872
Number of pages4
JournalJournal of Physical Chemistry B
Volume111
Issue number50
DOIs
Publication statusPublished - 20 Dec 2007
Externally publishedYes

Fingerprint

Enthalpy
Polymers
Polyacetylenes
enthalpy
polymers
Polyethylene
Vibration
Boundary conditions
Extrapolation
Density functional theory
Polyethylenes
boundary conditions
polyacetylene
Atoms
polyethylenes
extrapolation
density functional theory
vibration
cells
atoms

ASJC Scopus subject areas

  • Surfaces, Coatings and Films
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

On calculating a polymer's enthalpy of formation with quantum chemical methods. / Brothers, Edward; Izmaylov, Artur F.; Rusakov, Alexander A.; Scuseria, Gustavo E.

In: Journal of Physical Chemistry B, Vol. 111, No. 50, 20.12.2007, p. 13869-13872.

Research output: Contribution to journalArticle

Brothers, Edward ; Izmaylov, Artur F. ; Rusakov, Alexander A. ; Scuseria, Gustavo E. / On calculating a polymer's enthalpy of formation with quantum chemical methods. In: Journal of Physical Chemistry B. 2007 ; Vol. 111, No. 50. pp. 13869-13872.
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