Anharmonic force fields of cis- and trans-S1 C2H 2

J. H. Baraban; J. F. Stanton; A. J. Merer; R. W. Field

doi:10.1080/00268976.2012.706328

Anharmonic force fields of cis- and trans-S₁ C₂H ₂

J. H. Baraban, J. F. Stanton, A. J. Merer, R. W. Field

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

14 Scopus citations

Abstract

We calculate second-order vibrational perturbation theory (VPT2) anharmonic force fields for the cis and trans conformers of S₁ C ₂H₂, and compare the results to experiment. The vibrational assignments of recently observed levels belonging to the cis well are of particular interest. A refined estimate of the cis origin position (44,870±10 cm^-1) is proposed, and preliminary low-energy fits to the global J=K=0 trans level structure are also described. The performance of perturbation theory in this isomerizing system is examined, and both surprising successes and failures are encountered. We examine these and their causes, and offer practical suggestions for avoiding the pitfalls of applying perturbation theory to systems with large amplitude motions.

Original language	English
Pages (from-to)	2725-2733
Number of pages	9
Journal	Molecular Physics
Volume	110
Issue number	21-22
DOIs	https://doi.org/10.1080/00268976.2012.706328
State	Published - 1 Nov 2012
Externally published	Yes

Keywords

Acetylene
Anharmonic force fields
Cis-trans isomerization
Spectroscopy
Vibrational perturbation theory

ASJC Scopus subject areas

Biophysics
Molecular Biology
Condensed Matter Physics
Physical and Theoretical Chemistry

Access to Document

10.1080/00268976.2012.706328

Cite this

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title = "Anharmonic force fields of cis- and trans-S1 C2H 2",

abstract = "We calculate second-order vibrational perturbation theory (VPT2) anharmonic force fields for the cis and trans conformers of S1 C 2H2, and compare the results to experiment. The vibrational assignments of recently observed levels belonging to the cis well are of particular interest. A refined estimate of the cis origin position (44,870±10 cm-1) is proposed, and preliminary low-energy fits to the global J=K=0 trans level structure are also described. The performance of perturbation theory in this isomerizing system is examined, and both surprising successes and failures are encountered. We examine these and their causes, and offer practical suggestions for avoiding the pitfalls of applying perturbation theory to systems with large amplitude motions.",

keywords = "Acetylene, Anharmonic force fields, Cis-trans isomerization, Spectroscopy, Vibrational perturbation theory",

author = "Baraban, {J. H.} and Stanton, {J. F.} and Merer, {A. J.} and Field, {R. W.}",

note = "Funding Information: This work was supported at MIT by DOE Grant No. DE-FG0287ER13671. AJM thanks Academia Sinica, Taiwan, for financial support and the University of British Columbia for some travel funding. JFS also wishes to acknowledge support from the US National Science Foundation (Grant CHE-1012743).",

year = "2012",

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doi = "10.1080/00268976.2012.706328",

language = "English",

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T1 - Anharmonic force fields of cis- and trans-S1 C2H 2

AU - Baraban, J. H.

AU - Stanton, J. F.

AU - Merer, A. J.

AU - Field, R. W.

N1 - Funding Information: This work was supported at MIT by DOE Grant No. DE-FG0287ER13671. AJM thanks Academia Sinica, Taiwan, for financial support and the University of British Columbia for some travel funding. JFS also wishes to acknowledge support from the US National Science Foundation (Grant CHE-1012743).

PY - 2012/11/1

Y1 - 2012/11/1

N2 - We calculate second-order vibrational perturbation theory (VPT2) anharmonic force fields for the cis and trans conformers of S1 C 2H2, and compare the results to experiment. The vibrational assignments of recently observed levels belonging to the cis well are of particular interest. A refined estimate of the cis origin position (44,870±10 cm-1) is proposed, and preliminary low-energy fits to the global J=K=0 trans level structure are also described. The performance of perturbation theory in this isomerizing system is examined, and both surprising successes and failures are encountered. We examine these and their causes, and offer practical suggestions for avoiding the pitfalls of applying perturbation theory to systems with large amplitude motions.

AB - We calculate second-order vibrational perturbation theory (VPT2) anharmonic force fields for the cis and trans conformers of S1 C 2H2, and compare the results to experiment. The vibrational assignments of recently observed levels belonging to the cis well are of particular interest. A refined estimate of the cis origin position (44,870±10 cm-1) is proposed, and preliminary low-energy fits to the global J=K=0 trans level structure are also described. The performance of perturbation theory in this isomerizing system is examined, and both surprising successes and failures are encountered. We examine these and their causes, and offer practical suggestions for avoiding the pitfalls of applying perturbation theory to systems with large amplitude motions.

KW - Acetylene

KW - Anharmonic force fields

KW - Cis-trans isomerization

KW - Spectroscopy

KW - Vibrational perturbation theory

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DO - 10.1080/00268976.2012.706328

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JO - Molecular Physics

JF - Molecular Physics

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