A microwave and ab initio investigation of N2-SO3, OC-SO3, and OC-SO3-Ar

M. B. Craddock; C. S. Brauer; K. J. Higgins; Kenneth R Leopold

doi:10.1016/S0022-2852(02)00083-8

A microwave and ab initio investigation of N₂-SO₃, OC-SO₃, and OC-SO₃-Ar

M. B. Craddock, C. S. Brauer, K. J. Higgins, Kenneth R Leopold

Chemistry (Twin Cities)

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

5 Scopus citations

Abstract

Microwave spectra have been observed for N₂-SO₃, OC-SO₃, Ar-SO₃-CO, and several of their isotopic derivatives. All three complexes are symmetric tops with little or no out-of-plane distortion of the SO₃. In Ar-SO₃-CO, the Ar and CO lie on opposite sides of the sulfur, an arrangement which has not been previously observed for trimers involving SO₃. In N ₂-SO₃ and OC-SO₃, the N-S and C-S bond lengths are 2.934(12) and 2.854(12), respectively. In Ar-SO₃-CO, the C-S distance is 2.849(4) Å, which is identical, within the estimated uncertainties, to that in OC-SO₃. The Ar-S distance, on the other hand, is 3.411(11) Å, which represents a small but distinct lengthening of 0.061(12) Å relative to that previously determined for Ar-SO ₃. Stark effect measurements for OC-SO₃ and Ar-SO ₃-CO give dipole moments of 0.8488(13) and 0.602(15) D, respectively. The latter is very nearly equal to the difference between the dipole moments of OC-SO₃ and Ar-SO₃, suggesting that the dipole moment of the trimer is simply the vector sum of the unperturbed dimer dipole moments. Counterpoise corrected optimized geometries and binding energies have been computed at the MP2/aug-cc-pVTZ level for Ar-SO₃ (1.08 kcal/mol), N₂-SO₃ (2.60 kcal/mol), OC-SO₃ (3.92kcal/mol), and Ar-SO₃-CO (4.90 kcal/mol). The binding energy of Ar-SO ₃-CO is nearly equal to the sum of the Ar-SO₃ and OC-SO₃ binding energies, indicating that the two-body interactions on opposite sides of the SO₃ plane are not strongly coupled. Taken together, the experimental and theoretical results indicate that Ar-SO ₃-CO is best regarded as a composite of Ar-SO₃ and OC-SO₃ moieties.

Original language	English (US)
Pages (from-to)	63-73
Number of pages	11
Journal	Journal of molecular spectroscopy
Volume	222
Issue number	1
DOIs	https://doi.org/10.1016/S0022-2852(02)00083-8
State	Published - Nov 2003

Bibliographical note

Funding Information:
This work was supported by the National Science Foundation, the Donors of the Petroleum Research Fund, administered by the American Chemical Society, and the Minnesota Supercomputer Institute. We are also grateful to Professor William Klemperer for initially introducing one of us to the virtues of SO 3 , and for the many subsequent years of inspiration and support.

Keywords

Ab initio
Complexes
Dipole moment
Intermolecular forces
Lewis acidity
Molecular structure
Sulfur trioxide

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@article{b71bd38481fa4be38dcfa99919750201,

title = "A microwave and ab initio investigation of N2-SO3, OC-SO3, and OC-SO3-Ar",

abstract = "Microwave spectra have been observed for N2-SO3, OC-SO3, Ar-SO3-CO, and several of their isotopic derivatives. All three complexes are symmetric tops with little or no out-of-plane distortion of the SO3. In Ar-SO3-CO, the Ar and CO lie on opposite sides of the sulfur, an arrangement which has not been previously observed for trimers involving SO3. In N 2-SO3 and OC-SO3, the N-S and C-S bond lengths are 2.934(12) and 2.854(12), respectively. In Ar-SO3-CO, the C-S distance is 2.849(4) {\AA}, which is identical, within the estimated uncertainties, to that in OC-SO3. The Ar-S distance, on the other hand, is 3.411(11) {\AA}, which represents a small but distinct lengthening of 0.061(12) {\AA} relative to that previously determined for Ar-SO 3. Stark effect measurements for OC-SO3 and Ar-SO 3-CO give dipole moments of 0.8488(13) and 0.602(15) D, respectively. The latter is very nearly equal to the difference between the dipole moments of OC-SO3 and Ar-SO3, suggesting that the dipole moment of the trimer is simply the vector sum of the unperturbed dimer dipole moments. Counterpoise corrected optimized geometries and binding energies have been computed at the MP2/aug-cc-pVTZ level for Ar-SO3 (1.08 kcal/mol), N2-SO3 (2.60 kcal/mol), OC-SO3 (3.92kcal/mol), and Ar-SO3-CO (4.90 kcal/mol). The binding energy of Ar-SO 3-CO is nearly equal to the sum of the Ar-SO3 and OC-SO3 binding energies, indicating that the two-body interactions on opposite sides of the SO3 plane are not strongly coupled. Taken together, the experimental and theoretical results indicate that Ar-SO 3-CO is best regarded as a composite of Ar-SO3 and OC-SO3 moieties.",

keywords = "Ab initio, Complexes, Dipole moment, Intermolecular forces, Lewis acidity, Molecular structure, Sulfur trioxide",

author = "Craddock, {M. B.} and Brauer, {C. S.} and Higgins, {K. J.} and Leopold, {Kenneth R}",

note = "Funding Information: This work was supported by the National Science Foundation, the Donors of the Petroleum Research Fund, administered by the American Chemical Society, and the Minnesota Supercomputer Institute. We are also grateful to Professor William Klemperer for initially introducing one of us to the virtues of SO 3 , and for the many subsequent years of inspiration and support. ",

year = "2003",

month = nov,

doi = "10.1016/S0022-2852(02)00083-8",

language = "English (US)",

volume = "222",

pages = "63--73",

journal = "Journal of molecular spectroscopy",

issn = "0022-2852",

publisher = "Academic Press Inc.",

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TY - JOUR

T1 - A microwave and ab initio investigation of N2-SO3, OC-SO3, and OC-SO3-Ar

AU - Craddock, M. B.

AU - Brauer, C. S.

AU - Higgins, K. J.

AU - Leopold, Kenneth R

N1 - Funding Information: This work was supported by the National Science Foundation, the Donors of the Petroleum Research Fund, administered by the American Chemical Society, and the Minnesota Supercomputer Institute. We are also grateful to Professor William Klemperer for initially introducing one of us to the virtues of SO 3 , and for the many subsequent years of inspiration and support.

PY - 2003/11

Y1 - 2003/11

N2 - Microwave spectra have been observed for N2-SO3, OC-SO3, Ar-SO3-CO, and several of their isotopic derivatives. All three complexes are symmetric tops with little or no out-of-plane distortion of the SO3. In Ar-SO3-CO, the Ar and CO lie on opposite sides of the sulfur, an arrangement which has not been previously observed for trimers involving SO3. In N 2-SO3 and OC-SO3, the N-S and C-S bond lengths are 2.934(12) and 2.854(12), respectively. In Ar-SO3-CO, the C-S distance is 2.849(4) Å, which is identical, within the estimated uncertainties, to that in OC-SO3. The Ar-S distance, on the other hand, is 3.411(11) Å, which represents a small but distinct lengthening of 0.061(12) Å relative to that previously determined for Ar-SO 3. Stark effect measurements for OC-SO3 and Ar-SO 3-CO give dipole moments of 0.8488(13) and 0.602(15) D, respectively. The latter is very nearly equal to the difference between the dipole moments of OC-SO3 and Ar-SO3, suggesting that the dipole moment of the trimer is simply the vector sum of the unperturbed dimer dipole moments. Counterpoise corrected optimized geometries and binding energies have been computed at the MP2/aug-cc-pVTZ level for Ar-SO3 (1.08 kcal/mol), N2-SO3 (2.60 kcal/mol), OC-SO3 (3.92kcal/mol), and Ar-SO3-CO (4.90 kcal/mol). The binding energy of Ar-SO 3-CO is nearly equal to the sum of the Ar-SO3 and OC-SO3 binding energies, indicating that the two-body interactions on opposite sides of the SO3 plane are not strongly coupled. Taken together, the experimental and theoretical results indicate that Ar-SO 3-CO is best regarded as a composite of Ar-SO3 and OC-SO3 moieties.

AB - Microwave spectra have been observed for N2-SO3, OC-SO3, Ar-SO3-CO, and several of their isotopic derivatives. All three complexes are symmetric tops with little or no out-of-plane distortion of the SO3. In Ar-SO3-CO, the Ar and CO lie on opposite sides of the sulfur, an arrangement which has not been previously observed for trimers involving SO3. In N 2-SO3 and OC-SO3, the N-S and C-S bond lengths are 2.934(12) and 2.854(12), respectively. In Ar-SO3-CO, the C-S distance is 2.849(4) Å, which is identical, within the estimated uncertainties, to that in OC-SO3. The Ar-S distance, on the other hand, is 3.411(11) Å, which represents a small but distinct lengthening of 0.061(12) Å relative to that previously determined for Ar-SO 3. Stark effect measurements for OC-SO3 and Ar-SO 3-CO give dipole moments of 0.8488(13) and 0.602(15) D, respectively. The latter is very nearly equal to the difference between the dipole moments of OC-SO3 and Ar-SO3, suggesting that the dipole moment of the trimer is simply the vector sum of the unperturbed dimer dipole moments. Counterpoise corrected optimized geometries and binding energies have been computed at the MP2/aug-cc-pVTZ level for Ar-SO3 (1.08 kcal/mol), N2-SO3 (2.60 kcal/mol), OC-SO3 (3.92kcal/mol), and Ar-SO3-CO (4.90 kcal/mol). The binding energy of Ar-SO 3-CO is nearly equal to the sum of the Ar-SO3 and OC-SO3 binding energies, indicating that the two-body interactions on opposite sides of the SO3 plane are not strongly coupled. Taken together, the experimental and theoretical results indicate that Ar-SO 3-CO is best regarded as a composite of Ar-SO3 and OC-SO3 moieties.

KW - Ab initio

KW - Complexes

KW - Dipole moment

KW - Intermolecular forces

KW - Lewis acidity

KW - Molecular structure

KW - Sulfur trioxide

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