Reduced dimension discrete variable representation study of cis-trans isomerization in the S1 state of C2H2

J. H. Baraban; A. R. Beck; A. H. Steeves; J. F. Stanton; R. W. Field

doi:10.1063/1.3570823

Reduced dimension discrete variable representation study of cis-trans isomerization in the S₁ state of C₂H₂

J. H. Baraban, A. R. Beck, A. H. Steeves, J. F. Stanton, R. W. Field

Research output: Contribution to journal › Review article › peer-review

23 Scopus citations

Abstract

Isomerization between the cis and trans conformers of the S₁ state of acetylene is studied using a reduced dimension discrete variable representation (DVR) calculation. Existing DVR techniques are combined with a high accuracy potential energy surface and a kinetic energy operator derived from FG theory to yield an effective but simple Hamiltonian for treating large amplitude motions. The spectroscopic signatures of the S₁ isomerization are discussed, with emphasis on the vibrational aspects. The presence of a low barrier to isomerization causes distortion of the trans vibrational level structure and the appearance of nominally electronically forbidden A1A₂X1g+ transitions to vibrational levels of the cis conformer. Both of these effects are modeled in agreement with experimental results, and the underlying mechanisms of tunneling and state mixing are elucidated by use of the calculated vibrational wavefunctions.

Original language	English
Article number	244311
Journal	Journal of Chemical Physics
Volume	134
Issue number	24
DOIs	https://doi.org/10.1063/1.3570823
State	Published - 28 Jun 2011
Externally published	Yes

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1063/1.3570823

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@article{07e0249f4e3f4bf1877ee8963b36bedf,

title = "Reduced dimension discrete variable representation study of cis-trans isomerization in the S1 state of C2H2 ",

abstract = "Isomerization between the cis and trans conformers of the S1 state of acetylene is studied using a reduced dimension discrete variable representation (DVR) calculation. Existing DVR techniques are combined with a high accuracy potential energy surface and a kinetic energy operator derived from FG theory to yield an effective but simple Hamiltonian for treating large amplitude motions. The spectroscopic signatures of the S1 isomerization are discussed, with emphasis on the vibrational aspects. The presence of a low barrier to isomerization causes distortion of the trans vibrational level structure and the appearance of nominally electronically forbidden A1A2X1g+ transitions to vibrational levels of the cis conformer. Both of these effects are modeled in agreement with experimental results, and the underlying mechanisms of tunneling and state mixing are elucidated by use of the calculated vibrational wavefunctions.",

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

note = "Funding Information: J. H. Baraban would like to thank D. J. Tannor, T. Van Voorhis and A. J. Merer for helpful discussions, and is grateful for support by an NSF Graduate Research Fellowship. This work was supported at MIT by (U.S.) Department of Energy (DOE) Grant No. DE-FG0287ER13671.",

year = "2011",

month = jun,

day = "28",

doi = "10.1063/1.3570823",

language = "English",

volume = "134",

journal = "Journal of Chemical Physics",

issn = "0021-9606",

publisher = "American Institute of Physics",

number = "24",

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T1 - Reduced dimension discrete variable representation study of cis-trans isomerization in the S1 state of C2H2

AU - Baraban, J. H.

AU - Beck, A. R.

AU - Steeves, A. H.

AU - Stanton, J. F.

AU - Field, R. W.

N1 - Funding Information: J. H. Baraban would like to thank D. J. Tannor, T. Van Voorhis and A. J. Merer for helpful discussions, and is grateful for support by an NSF Graduate Research Fellowship. This work was supported at MIT by (U.S.) Department of Energy (DOE) Grant No. DE-FG0287ER13671.

PY - 2011/6/28

Y1 - 2011/6/28

N2 - Isomerization between the cis and trans conformers of the S1 state of acetylene is studied using a reduced dimension discrete variable representation (DVR) calculation. Existing DVR techniques are combined with a high accuracy potential energy surface and a kinetic energy operator derived from FG theory to yield an effective but simple Hamiltonian for treating large amplitude motions. The spectroscopic signatures of the S1 isomerization are discussed, with emphasis on the vibrational aspects. The presence of a low barrier to isomerization causes distortion of the trans vibrational level structure and the appearance of nominally electronically forbidden A1A2X1g+ transitions to vibrational levels of the cis conformer. Both of these effects are modeled in agreement with experimental results, and the underlying mechanisms of tunneling and state mixing are elucidated by use of the calculated vibrational wavefunctions.

AB - Isomerization between the cis and trans conformers of the S1 state of acetylene is studied using a reduced dimension discrete variable representation (DVR) calculation. Existing DVR techniques are combined with a high accuracy potential energy surface and a kinetic energy operator derived from FG theory to yield an effective but simple Hamiltonian for treating large amplitude motions. The spectroscopic signatures of the S1 isomerization are discussed, with emphasis on the vibrational aspects. The presence of a low barrier to isomerization causes distortion of the trans vibrational level structure and the appearance of nominally electronically forbidden A1A2X1g+ transitions to vibrational levels of the cis conformer. Both of these effects are modeled in agreement with experimental results, and the underlying mechanisms of tunneling and state mixing are elucidated by use of the calculated vibrational wavefunctions.

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U2 - 10.1063/1.3570823

DO - 10.1063/1.3570823

M3 - Review article

AN - SCOPUS:79960165703

SN - 0021-9606

VL - 134

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 24

M1 - 244311

ER -

Reduced dimension discrete variable representation study of cis-trans isomerization in the S₁ state of C₂H₂

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