Effects of spin contamination on estimating bond dissociation energies of polycyclic aromatic hydrocarbons

Blanquart, Guillaume

doi:10.1002/qua.24904

Title: Effects of spin contamination on estimating bond dissociation energies of polycyclic aromatic hydrocarbons

Abstract

The objective of this work is to investigate the impact of spin contamination on the prediction of the enthalpies of formation of Polycyclic Aromatic Hydrocarbon (PAH) radicals and of the bond dissociation energies of their precursor molecule. These PAH radicals play a major role in the mass growth of soot precursors leading ultimately to the first soot particles. In this work, we highlights the errors due to spin contamination by comparing spin‐unrestricted open‐shell calculations (UHF, UMP2, and Quadratic CI singles and doubles [QCISD(T)]) with spin‐restricted open‐shell calculations (ROHF, ROMP2, and ROCCSD(T)). The results suggest that one should be very careful using any of the spin‐unrestricted methods (even QCISD (T)) unless the values are extremely close to the theoretical value. Following these observations, we propose a new set of best‐estimates for the enthalpies of formation of these critical PAH radicals using spin‐restricted open‐shell ROMP2 and RCCSD(T) calculations. © 2015 Wiley Periodicals, Inc.

Authors:

Blanquart, Guillaume ^[1]

Mechanical and Civil Engineering Department, California Institute of Technology 1200 E. California Blvd Pasadena CA 91125

Publication Date:: Wed Mar 18 00:00:00 EDT 2015

Sponsoring Org.:: USDOE

OSTI Identifier:: 1400908

Resource Type:: Publisher's Accepted Manuscript

Journal Name:: International Journal of Quantum Chemistry

Additional Journal Information:: Journal Name: International Journal of Quantum Chemistry Journal Volume: 115 Journal Issue: 12; Journal ID: ISSN 0020-7608

Publisher:: Wiley Blackwell (John Wiley & Sons)

Country of Publication:: United States

Language:: English

Citation Formats


                    Blanquart, Guillaume. Effects of spin contamination on estimating bond dissociation energies of polycyclic aromatic hydrocarbons.  United States: N. p., 2015. 
Web.  doi:10.1002/qua.24904.

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                    Blanquart, Guillaume. Effects of spin contamination on estimating bond dissociation energies of polycyclic aromatic hydrocarbons.  United States.  https://doi.org/10.1002/qua.24904

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                    Blanquart, Guillaume. Wed .  
"Effects of spin contamination on estimating bond dissociation energies of polycyclic aromatic hydrocarbons".  United States.  https://doi.org/10.1002/qua.24904.

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@article{osti_1400908,

  title        = {Effects of spin contamination on estimating bond dissociation energies of polycyclic aromatic hydrocarbons},

  author       = {Blanquart, Guillaume},

  abstractNote = {The objective of this work is to investigate the impact of spin contamination on the prediction of the enthalpies of formation of Polycyclic Aromatic Hydrocarbon (PAH) radicals and of the bond dissociation energies of their precursor molecule. These PAH radicals play a major role in the mass growth of soot precursors leading ultimately to the first soot particles. In this work, we highlights the errors due to spin contamination by comparing spin‐unrestricted open‐shell calculations (UHF, UMP2, and Quadratic CI singles and doubles [QCISD(T)]) with spin‐restricted open‐shell calculations (ROHF, ROMP2, and ROCCSD(T)). The results suggest that one should be very careful using any of the spin‐unrestricted methods (even QCISD (T)) unless the values are extremely close to the theoretical value. Following these observations, we propose a new set of best‐estimates for the enthalpies of formation of these critical PAH radicals using spin‐restricted open‐shell ROMP2 and RCCSD(T) calculations. © 2015 Wiley Periodicals, Inc.},

  doi          = {10.1002/qua.24904},

  journal      = {International Journal of Quantum Chemistry},

  number       = 12,

  volume       = 115,

  place        = {United States},

  year         = {Wed Mar 18 00:00:00 EDT 2015},

  month        = {Wed Mar 18 00:00:00 EDT 2015}

}

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Works referenced in this record:

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Title: Effects of spin contamination on estimating bond dissociation energies of polycyclic aromatic hydrocarbons

Abstract

Citation Formats

Thermodynamics of the Hydroxyl Radical Addition to Isoprene journal, July 2008

Hydrocarbon Bond Dissociation Enthalpies: From Substituted Aromatics to Large Polyaromatics journal, October 2006

Thermochemical Properties of Polycyclic Aromatic Hydrocarbons (PAH) from G3MP2B3 Calculations journal, July 2007

The C-H Bond Energy of Benzene journal, March 1995

Detailed modeling of PAH and soot formation in a laminar premixed benzene/oxygen/argon low-pressure flame journal, January 2005

Enthalpies of formation of benzenoid aromatic molecules and radicals journal, April 1993

Formation of nascent soot and other condensed-phase materials in flames journal, January 2011

Kinetic modeling of soot formation with detailed chemistry and physics: laminar premixed flames of C2 hydrocarbons journal, April 2000

On the extent of spin contamination in open‐shell coupled‐cluster wave functions journal, July 1994

An Assessment of Theoretical Procedures for Predicting the Thermochemistry and Kinetics of Hydrogen Abstraction by Methyl Radical from Benzene journal, July 2006

Hydrogen Abstraction Acetylene Addition and Diels−Alder Mechanisms of PAH Formation: A Detailed Study Using First Principles Calculations journal, September 2005

Thermodynamic properties of the species resulting from the phenyl radical with O 2 reaction system journal, September 2008

Chemical mechanism for high temperature combustion of engine relevant fuels with emphasis on soot precursors journal, March 2009

Evaluation of S 2 for correlated wave functions and spin projection of unrestricted Mo/ller–Plesset perturbation theory journal, October 1994

Spin-unrestricted character of Kohn-Sham orbitals for open-shell systems journal, November 1995

Detailed modeling of soot particle nucleation and growth journal, January 1991

Formation of polycyclic aromatic hydrocarbons and their growth to soot—a review of chemical reaction pathways journal, August 2000

Analyzing the effects of temperature on soot formation with a joint volume-surface-hydrogen model journal, August 2009

High-Temperature Reactions of OH Radicals with Benzene and Toluene journal, April 2006

Modeling the spin-dependent properties of open-shell Fe(III)-containing systems: towards a computational description of nitrile hydratase journal, March 2003

Thermochemical properties of free radicals from G3MP2B3 calculations journal, January 2002

Formation Mechanism of Polycyclic Aromatic Hydrocarbons beyond the Second Aromatic Ring journal, May 2013

Formation pathways of ethynyl-substituted and cyclopenta-fused polycyclic aromatic hydrocarbons journal, January 2000

G3-RAD and G3X-RAD: Modified Gaussian-3 (G3) and Gaussian-3X (G3X) procedures for radical thermochemistry journal, March 2003

A detailed kinetic modeling study of aromatics formation in laminar premixed acetylene and ethylene flames journal, July 1997

Thermochemistry and Kinetics of Hydrogen Abstraction by Methyl Radical from Polycyclic Aromatic Hydrocarbons journal, December 2006

Gaussian-3 theory using density functional geometries and zero-point energies journal, April 1999

Energetics and Site Specificity of the Homolytic C−H Bond Cleavage in Benzenoid Hydrocarbons: An ab Initio Electronic Structure Study journal, January 1996

Thermodynamics of the Hydroxyl Radical Addition to Isoprene
journal, July 2008

Hydrocarbon Bond Dissociation Enthalpies: From Substituted Aromatics to Large Polyaromatics
journal, October 2006

Thermochemical Properties of Polycyclic Aromatic Hydrocarbons (PAH) from G3MP2B3 Calculations
journal, July 2007

The C-H Bond Energy of Benzene
journal, March 1995

Detailed modeling of PAH and soot formation in a laminar premixed benzene/oxygen/argon low-pressure flame
journal, January 2005

Enthalpies of formation of benzenoid aromatic molecules and radicals
journal, April 1993

Formation of nascent soot and other condensed-phase materials in flames
journal, January 2011

Kinetic modeling of soot formation with detailed chemistry and physics: laminar premixed flames of C2 hydrocarbons
journal, April 2000

On the extent of spin contamination in open‐shell coupled‐cluster wave functions
journal, July 1994

An Assessment of Theoretical Procedures for Predicting the Thermochemistry and Kinetics of Hydrogen Abstraction by Methyl Radical from Benzene
journal, July 2006

Hydrogen Abstraction Acetylene Addition and Diels−Alder Mechanisms of PAH Formation: A Detailed Study Using First Principles Calculations
journal, September 2005

Thermodynamic properties of the species resulting from the phenyl radical with O ₂ reaction system
journal, September 2008

Chemical mechanism for high temperature combustion of engine relevant fuels with emphasis on soot precursors
journal, March 2009

Evaluation of S ² for correlated wave functions and spin projection of unrestricted Mo/ller–Plesset perturbation theory
journal, October 1994

Spin-unrestricted character of Kohn-Sham orbitals for open-shell systems
journal, November 1995

Detailed modeling of soot particle nucleation and growth
journal, January 1991

Formation of polycyclic aromatic hydrocarbons and their growth to soot—a review of chemical reaction pathways
journal, August 2000

Analyzing the effects of temperature on soot formation with a joint volume-surface-hydrogen model
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High-Temperature Reactions of OH Radicals with Benzene and Toluene
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Modeling the spin-dependent properties of open-shell Fe(III)-containing systems: towards a computational description of nitrile hydratase
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Thermochemical properties of free radicals from G3MP2B3 calculations
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journal, January 2000

G3-RAD and G3X-RAD: Modified Gaussian-3 (G3) and Gaussian-3X (G3X) procedures for radical thermochemistry
journal, March 2003

A detailed kinetic modeling study of aromatics formation in laminar premixed acetylene and ethylene flames
journal, July 1997

Thermochemistry and Kinetics of Hydrogen Abstraction by Methyl Radical from Polycyclic Aromatic Hydrocarbons
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Gaussian-3 theory using density functional geometries and zero-point energies
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Energetics and Site Specificity of the Homolytic C−H Bond Cleavage in Benzenoid Hydrocarbons: An ab Initio Electronic Structure Study
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