High-level ab-initio calculations for astrochemically relevant polyynes (HC211H), their isomers (C2H2) and their anions (C2W)

Peter Botschwinat; Rainer Oswald; Gerald Knizia; Hans Joachim Werner

doi:10.1524/zpch.2009.6038

High-level ab-initio calculations for astrochemically relevant polyynes (HC₂11H), their isomers (C₂H₂) and their anions (C₂W)

Peter Botschwinat, Rainer Oswald, Gerald Knizia, Hans Joachim Werner

Chemistry

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

9 Scopus citations

Abstract

The astrochemically relevant molecules of type HC₂H, C ₂H₂ and C₂H (n = 2-4) have been investigated theoretically by means of both standard and explicitly correlated coupled cluster theory. Equilibrium structures and harmonic vibrational frequencies have been calculated for all nine species. Accurate values for the molar enthalpies of isomerization of the C₂H₂ species and for the molar enthalpies of the dissociative electron attachment reactions C₂H ₂ + e - C₂H + H (both at 0 K) are predicted. Both quantities differ substantially from the results of previous hybrid density functional (B₃LYP) calculations. The explicitly correlated CCSD(T)-F12a method in conjunction with Dunning's aug-cc-pVTZ basis is found to yield results in excellent agreement with standard CCSD(T) calculations with much larger basis sets.

Original language	English (US)
Pages (from-to)	447-460
Number of pages	14
Journal	Zeitschrift fur Physikalische Chemie
Volume	223
Issue number	4-5
DOIs	https://doi.org/10.1524/zpch.2009.6038
State	Published - 2009

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry

Access to Document

10.1524/zpch.2009.6038

Cite this

@article{5952773cb6d146e7b1d06486d9533f80,

title = "High-level ab-initio calculations for astrochemically relevant polyynes (HC211H), their isomers (C2H2) and their anions (C2W)",

abstract = "The astrochemically relevant molecules of type HC2H, C 2H2 and C2H (n = 2-4) have been investigated theoretically by means of both standard and explicitly correlated coupled cluster theory. Equilibrium structures and harmonic vibrational frequencies have been calculated for all nine species. Accurate values for the molar enthalpies of isomerization of the C2H2 species and for the molar enthalpies of the dissociative electron attachment reactions C2H 2 + e - C2H + H (both at 0 K) are predicted. Both quantities differ substantially from the results of previous hybrid density functional (B3LYP) calculations. The explicitly correlated CCSD(T)-F12a method in conjunction with Dunning's aug-cc-pVTZ basis is found to yield results in excellent agreement with standard CCSD(T) calculations with much larger basis sets.",

author = "Peter Botschwinat and Rainer Oswald and Gerald Knizia and Werner, {Hans Joachim}",

note = "Funding Information: Financial support by the Fonds der Chemischen Industrie is gratefully acknowledged. G.K. and H.J.W. appreciate funding by priority program 1145 of the Deutsche Forschungsgemeinschaft.",

year = "2009",

doi = "10.1524/zpch.2009.6038",

language = "English (US)",

volume = "223",

pages = "447--460",

journal = "Zeitschrift fur Physikalische Chemie",

issn = "0942-9352",

publisher = "Oldenbourg Wissenschaftsverlag GmbH",

number = "4-5",

}

TY - JOUR

T1 - High-level ab-initio calculations for astrochemically relevant polyynes (HC211H), their isomers (C2H2) and their anions (C2W)

AU - Botschwinat, Peter

AU - Oswald, Rainer

AU - Knizia, Gerald

AU - Werner, Hans Joachim

N1 - Funding Information: Financial support by the Fonds der Chemischen Industrie is gratefully acknowledged. G.K. and H.J.W. appreciate funding by priority program 1145 of the Deutsche Forschungsgemeinschaft.

PY - 2009

Y1 - 2009

N2 - The astrochemically relevant molecules of type HC2H, C 2H2 and C2H (n = 2-4) have been investigated theoretically by means of both standard and explicitly correlated coupled cluster theory. Equilibrium structures and harmonic vibrational frequencies have been calculated for all nine species. Accurate values for the molar enthalpies of isomerization of the C2H2 species and for the molar enthalpies of the dissociative electron attachment reactions C2H 2 + e - C2H + H (both at 0 K) are predicted. Both quantities differ substantially from the results of previous hybrid density functional (B3LYP) calculations. The explicitly correlated CCSD(T)-F12a method in conjunction with Dunning's aug-cc-pVTZ basis is found to yield results in excellent agreement with standard CCSD(T) calculations with much larger basis sets.

AB - The astrochemically relevant molecules of type HC2H, C 2H2 and C2H (n = 2-4) have been investigated theoretically by means of both standard and explicitly correlated coupled cluster theory. Equilibrium structures and harmonic vibrational frequencies have been calculated for all nine species. Accurate values for the molar enthalpies of isomerization of the C2H2 species and for the molar enthalpies of the dissociative electron attachment reactions C2H 2 + e - C2H + H (both at 0 K) are predicted. Both quantities differ substantially from the results of previous hybrid density functional (B3LYP) calculations. The explicitly correlated CCSD(T)-F12a method in conjunction with Dunning's aug-cc-pVTZ basis is found to yield results in excellent agreement with standard CCSD(T) calculations with much larger basis sets.

UR - http://www.scopus.com/inward/record.url?scp=68849085548&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=68849085548&partnerID=8YFLogxK

U2 - 10.1524/zpch.2009.6038

DO - 10.1524/zpch.2009.6038

M3 - Article

AN - SCOPUS:68849085548

SN - 0942-9352

VL - 223

SP - 447

EP - 460

JO - Zeitschrift fur Physikalische Chemie

JF - Zeitschrift fur Physikalische Chemie

IS - 4-5

ER -

High-level ab-initio calculations for astrochemically relevant polyynes (HC₂11H), their isomers (C₂H₂) and their anions (C₂W)

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this