Benchmark calculations of the complete configuration-interaction limit of Born-Oppenheimer diagonal corrections to the saddle points of isotopomers of the H+ H 2 reaction

Steven L. Mielke; David W. Schwenke; Kirk A. Peterson

doi:10.1063/1.1917838

Benchmark calculations of the complete configuration-interaction limit of Born-Oppenheimer diagonal corrections to the saddle points of isotopomers of the H+ H ₂ reaction

Steven L. Mielke
, David W. Schwenke
, Kirk A. Peterson

Chemistry (Twin Cities)

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

40 Scopus citations

Abstract

We present a detailed ab initio study of the effect that the Born-Oppenheimer diagonal correction (BODC) has on the saddle-point properties of the H3 system and its isotopomers. Benchmark values are presented that are estimated to be within 0.1 cm-1 of the complete configuration-interaction limit. We consider the basis set and correlation treatment requirements for accurate BODC calculations, and both are observed to be more favorable than for the Born-Oppenheimer energies. The BODC raises the H+ H2 barrier height by 0.1532 kcalmol and slightly narrows the barrier-with the imaginary frequency increasing by ∼2%.

Original language	English (US)
Article number	224313
Journal	Journal of Chemical Physics
Volume	122
Issue number	22
DOIs	https://doi.org/10.1063/1.1917838
State	Published - Jun 8 2005

Bibliographical note

Funding Information:
We are grateful to Dr. Bruce Garrett for helpful discussions. This work was supported by the National Science Foundation (Grant No. CHE-0111282 to KAP) and the Chemical Sciences Division in the Office of Basic Energy Sciences of the U.S. Department of Energy. Part of this research was performed in the W. R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Pacific Northwest National Laboratory is operated for the Department of Energy by Battelle.

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10.1063/1.1917838

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title = "Benchmark calculations of the complete configuration-interaction limit of Born-Oppenheimer diagonal corrections to the saddle points of isotopomers of the H+ H 2 reaction",

abstract = "We present a detailed ab initio study of the effect that the Born-Oppenheimer diagonal correction (BODC) has on the saddle-point properties of the H3 system and its isotopomers. Benchmark values are presented that are estimated to be within 0.1 cm-1 of the complete configuration-interaction limit. We consider the basis set and correlation treatment requirements for accurate BODC calculations, and both are observed to be more favorable than for the Born-Oppenheimer energies. The BODC raises the H+ H2 barrier height by 0.1532 kcalmol and slightly narrows the barrier-with the imaginary frequency increasing by ∼2\%.",

author = "Mielke, \{Steven L.\} and Schwenke, \{David W.\} and Peterson, \{Kirk A.\}",

note = "Funding Information: We are grateful to Dr. Bruce Garrett for helpful discussions. This work was supported by the National Science Foundation (Grant No. CHE-0111282 to KAP) and the Chemical Sciences Division in the Office of Basic Energy Sciences of the U.S. Department of Energy. Part of this research was performed in the W. R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy{\textquoteright}s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Pacific Northwest National Laboratory is operated for the Department of Energy by Battelle.",

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AU - Mielke, Steven L.

AU - Schwenke, David W.

AU - Peterson, Kirk A.

N1 - Funding Information: We are grateful to Dr. Bruce Garrett for helpful discussions. This work was supported by the National Science Foundation (Grant No. CHE-0111282 to KAP) and the Chemical Sciences Division in the Office of Basic Energy Sciences of the U.S. Department of Energy. Part of this research was performed in the W. R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Pacific Northwest National Laboratory is operated for the Department of Energy by Battelle.

PY - 2005/6/8

Y1 - 2005/6/8

N2 - We present a detailed ab initio study of the effect that the Born-Oppenheimer diagonal correction (BODC) has on the saddle-point properties of the H3 system and its isotopomers. Benchmark values are presented that are estimated to be within 0.1 cm-1 of the complete configuration-interaction limit. We consider the basis set and correlation treatment requirements for accurate BODC calculations, and both are observed to be more favorable than for the Born-Oppenheimer energies. The BODC raises the H+ H2 barrier height by 0.1532 kcalmol and slightly narrows the barrier-with the imaginary frequency increasing by ∼2%.

AB - We present a detailed ab initio study of the effect that the Born-Oppenheimer diagonal correction (BODC) has on the saddle-point properties of the H3 system and its isotopomers. Benchmark values are presented that are estimated to be within 0.1 cm-1 of the complete configuration-interaction limit. We consider the basis set and correlation treatment requirements for accurate BODC calculations, and both are observed to be more favorable than for the Born-Oppenheimer energies. The BODC raises the H+ H2 barrier height by 0.1532 kcalmol and slightly narrows the barrier-with the imaginary frequency increasing by ∼2%.

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