Infrared spectroscopy of CO2–D(H)Br: Molecular structure and its reliability
Zeng, Y. P. ; Sharpe, S. W. ; Shin, S. K. ; Wittig, C. ; Beaudet, R. A.
College Park, Md. : American Institute of Physics (AIP)
Published 1992
College Park, Md. : American Institute of Physics (AIP)
Published 1992
| ISSN: |
1089-7690
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|---|---|
| Source: |
AIP Digital Archive
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| Topics: |
Physics
Chemistry and Pharmacology
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| Notes: |
A high resolution rovibrational absorption spectrum of the weakly bonded CO2–DBr complex has been recorded in the 2350 cm−1 region by exciting the CO2 asymmetric stretch vibration with a tunable diode laser. The CO2–DBr band origin associated with this mode is 2348.2710 cm−1, red-shifted by 0.87 cm−1 from uncomplexed CO2. The position of the hydrogen atom is determined from differences in moments-of-inertia between CO2–DBr and CO2–HBr, i.e., by using the Kraitchman method. From this, we conclude that ground state CO2–H(D)Br has an average geometry that is planar and inertially T-shaped, with essentially parallel HBr and CO2 axes. Average values of intermolecular parameters are: Rcm=3.58 A(ring), θBrCO=79.8°, and θHBrC=93.1°. The validity of using the Kraitchman method, which was designed for use with rigid molecules, with a floppy complex like CO2–HBr is discussed. The experimental structure is corroborated qualitatively by results from Møller–Plesset second-order perturbation calculations, corrected for basis set superposition errors. The theoretical equilibrium geometry for the inertially T-shaped complex is planar with structural parameters: RCBr=3.62 A(ring), θBrCO=89°, and θHBrC=86°. A number of cuts on the four dimensional intermolecular potential surface confirm large zero-point amplitudes, which are known to be characteristic of such systems, and these cuts are used to estimate tunneling splittings. Tunneling is shown to occur by out-of-plane rotation of the H atom, in accord with the experimental observations of Rice et al. There is no significant in-plane tunneling. A quasilinear hingelike isomer (OCO–HBr) with ROH=2.35 A(ring) at equilibrium is calculated to be as stable as the T-shaped complex; however, this species has yet to be observed experimentally. Photoinitiated reactions in CO2–HX complexes are discussed.
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| Type of Medium: |
Electronic Resource
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| URL: |
| _version_ | 1798289741651640320 |
|---|---|
| autor | Zeng, Y. P. Sharpe, S. W. Shin, S. K. Wittig, C. Beaudet, R. A. |
| autorsonst | Zeng, Y. P. Sharpe, S. W. Shin, S. K. Wittig, C. Beaudet, R. A. |
| book_url | http://dx.doi.org/10.1063/1.463799 |
| datenlieferant | nat_lic_papers |
| hauptsatz | hsatz_simple |
| identnr | NLZ21881156X |
| issn | 1089-7690 |
| journal_name | The Journal of Chemical Physics |
| materialart | 1 |
| notes | A high resolution rovibrational absorption spectrum of the weakly bonded CO2–DBr complex has been recorded in the 2350 cm−1 region by exciting the CO2 asymmetric stretch vibration with a tunable diode laser. The CO2–DBr band origin associated with this mode is 2348.2710 cm−1, red-shifted by 0.87 cm−1 from uncomplexed CO2. The position of the hydrogen atom is determined from differences in moments-of-inertia between CO2–DBr and CO2–HBr, i.e., by using the Kraitchman method. From this, we conclude that ground state CO2–H(D)Br has an average geometry that is planar and inertially T-shaped, with essentially parallel HBr and CO2 axes. Average values of intermolecular parameters are: Rcm=3.58 A(ring), θBrCO=79.8°, and θHBrC=93.1°. The validity of using the Kraitchman method, which was designed for use with rigid molecules, with a floppy complex like CO2–HBr is discussed. The experimental structure is corroborated qualitatively by results from Møller–Plesset second-order perturbation calculations, corrected for basis set superposition errors. The theoretical equilibrium geometry for the inertially T-shaped complex is planar with structural parameters: RCBr=3.62 A(ring), θBrCO=89°, and θHBrC=86°. A number of cuts on the four dimensional intermolecular potential surface confirm large zero-point amplitudes, which are known to be characteristic of such systems, and these cuts are used to estimate tunneling splittings. Tunneling is shown to occur by out-of-plane rotation of the H atom, in accord with the experimental observations of Rice et al. There is no significant in-plane tunneling. A quasilinear hingelike isomer (OCO–HBr) with ROH=2.35 A(ring) at equilibrium is calculated to be as stable as the T-shaped complex; however, this species has yet to be observed experimentally. Photoinitiated reactions in CO2–HX complexes are discussed. |
| package_name | American Institute of Physics (AIP) |
| publikationsjahr_anzeige | 1992 |
| publikationsjahr_facette | 1992 |
| publikationsjahr_intervall | 8009:1990-1994 |
| publikationsjahr_sort | 1992 |
| publikationsort | College Park, Md. |
| publisher | American Institute of Physics (AIP) |
| reference | 97 (1992), S. 5392-5402 |
| search_space | articles |
| shingle_author_1 | Zeng, Y. P. Sharpe, S. W. Shin, S. K. Wittig, C. Beaudet, R. A. |
| shingle_author_2 | Zeng, Y. P. Sharpe, S. W. Shin, S. K. Wittig, C. Beaudet, R. A. |
| shingle_author_3 | Zeng, Y. P. Sharpe, S. W. Shin, S. K. Wittig, C. Beaudet, R. A. |
| shingle_author_4 | Zeng, Y. P. Sharpe, S. W. Shin, S. K. Wittig, C. Beaudet, R. A. |
| shingle_catch_all_1 | Zeng, Y. P. Sharpe, S. W. Shin, S. K. Wittig, C. Beaudet, R. A. Infrared spectroscopy of CO2–D(H)Br: Molecular structure and its reliability A high resolution rovibrational absorption spectrum of the weakly bonded CO2–DBr complex has been recorded in the 2350 cm−1 region by exciting the CO2 asymmetric stretch vibration with a tunable diode laser. The CO2–DBr band origin associated with this mode is 2348.2710 cm−1, red-shifted by 0.87 cm−1 from uncomplexed CO2. The position of the hydrogen atom is determined from differences in moments-of-inertia between CO2–DBr and CO2–HBr, i.e., by using the Kraitchman method. From this, we conclude that ground state CO2–H(D)Br has an average geometry that is planar and inertially T-shaped, with essentially parallel HBr and CO2 axes. Average values of intermolecular parameters are: Rcm=3.58 A(ring), θBrCO=79.8°, and θHBrC=93.1°. The validity of using the Kraitchman method, which was designed for use with rigid molecules, with a floppy complex like CO2–HBr is discussed. The experimental structure is corroborated qualitatively by results from Møller–Plesset second-order perturbation calculations, corrected for basis set superposition errors. The theoretical equilibrium geometry for the inertially T-shaped complex is planar with structural parameters: RCBr=3.62 A(ring), θBrCO=89°, and θHBrC=86°. A number of cuts on the four dimensional intermolecular potential surface confirm large zero-point amplitudes, which are known to be characteristic of such systems, and these cuts are used to estimate tunneling splittings. Tunneling is shown to occur by out-of-plane rotation of the H atom, in accord with the experimental observations of Rice et al. There is no significant in-plane tunneling. A quasilinear hingelike isomer (OCO–HBr) with ROH=2.35 A(ring) at equilibrium is calculated to be as stable as the T-shaped complex; however, this species has yet to be observed experimentally. Photoinitiated reactions in CO2–HX complexes are discussed. 1089-7690 10897690 American Institute of Physics (AIP) |
| shingle_catch_all_2 | Zeng, Y. P. Sharpe, S. W. Shin, S. K. Wittig, C. Beaudet, R. A. Infrared spectroscopy of CO2–D(H)Br: Molecular structure and its reliability A high resolution rovibrational absorption spectrum of the weakly bonded CO2–DBr complex has been recorded in the 2350 cm−1 region by exciting the CO2 asymmetric stretch vibration with a tunable diode laser. The CO2–DBr band origin associated with this mode is 2348.2710 cm−1, red-shifted by 0.87 cm−1 from uncomplexed CO2. The position of the hydrogen atom is determined from differences in moments-of-inertia between CO2–DBr and CO2–HBr, i.e., by using the Kraitchman method. From this, we conclude that ground state CO2–H(D)Br has an average geometry that is planar and inertially T-shaped, with essentially parallel HBr and CO2 axes. Average values of intermolecular parameters are: Rcm=3.58 A(ring), θBrCO=79.8°, and θHBrC=93.1°. The validity of using the Kraitchman method, which was designed for use with rigid molecules, with a floppy complex like CO2–HBr is discussed. The experimental structure is corroborated qualitatively by results from Møller–Plesset second-order perturbation calculations, corrected for basis set superposition errors. The theoretical equilibrium geometry for the inertially T-shaped complex is planar with structural parameters: RCBr=3.62 A(ring), θBrCO=89°, and θHBrC=86°. A number of cuts on the four dimensional intermolecular potential surface confirm large zero-point amplitudes, which are known to be characteristic of such systems, and these cuts are used to estimate tunneling splittings. Tunneling is shown to occur by out-of-plane rotation of the H atom, in accord with the experimental observations of Rice et al. There is no significant in-plane tunneling. A quasilinear hingelike isomer (OCO–HBr) with ROH=2.35 A(ring) at equilibrium is calculated to be as stable as the T-shaped complex; however, this species has yet to be observed experimentally. Photoinitiated reactions in CO2–HX complexes are discussed. 1089-7690 10897690 American Institute of Physics (AIP) |
| shingle_catch_all_3 | Zeng, Y. P. Sharpe, S. W. Shin, S. K. Wittig, C. Beaudet, R. A. Infrared spectroscopy of CO2–D(H)Br: Molecular structure and its reliability A high resolution rovibrational absorption spectrum of the weakly bonded CO2–DBr complex has been recorded in the 2350 cm−1 region by exciting the CO2 asymmetric stretch vibration with a tunable diode laser. The CO2–DBr band origin associated with this mode is 2348.2710 cm−1, red-shifted by 0.87 cm−1 from uncomplexed CO2. The position of the hydrogen atom is determined from differences in moments-of-inertia between CO2–DBr and CO2–HBr, i.e., by using the Kraitchman method. From this, we conclude that ground state CO2–H(D)Br has an average geometry that is planar and inertially T-shaped, with essentially parallel HBr and CO2 axes. Average values of intermolecular parameters are: Rcm=3.58 A(ring), θBrCO=79.8°, and θHBrC=93.1°. The validity of using the Kraitchman method, which was designed for use with rigid molecules, with a floppy complex like CO2–HBr is discussed. The experimental structure is corroborated qualitatively by results from Møller–Plesset second-order perturbation calculations, corrected for basis set superposition errors. The theoretical equilibrium geometry for the inertially T-shaped complex is planar with structural parameters: RCBr=3.62 A(ring), θBrCO=89°, and θHBrC=86°. A number of cuts on the four dimensional intermolecular potential surface confirm large zero-point amplitudes, which are known to be characteristic of such systems, and these cuts are used to estimate tunneling splittings. Tunneling is shown to occur by out-of-plane rotation of the H atom, in accord with the experimental observations of Rice et al. There is no significant in-plane tunneling. A quasilinear hingelike isomer (OCO–HBr) with ROH=2.35 A(ring) at equilibrium is calculated to be as stable as the T-shaped complex; however, this species has yet to be observed experimentally. Photoinitiated reactions in CO2–HX complexes are discussed. 1089-7690 10897690 American Institute of Physics (AIP) |
| shingle_catch_all_4 | Zeng, Y. P. Sharpe, S. W. Shin, S. K. Wittig, C. Beaudet, R. A. Infrared spectroscopy of CO2–D(H)Br: Molecular structure and its reliability A high resolution rovibrational absorption spectrum of the weakly bonded CO2–DBr complex has been recorded in the 2350 cm−1 region by exciting the CO2 asymmetric stretch vibration with a tunable diode laser. The CO2–DBr band origin associated with this mode is 2348.2710 cm−1, red-shifted by 0.87 cm−1 from uncomplexed CO2. The position of the hydrogen atom is determined from differences in moments-of-inertia between CO2–DBr and CO2–HBr, i.e., by using the Kraitchman method. From this, we conclude that ground state CO2–H(D)Br has an average geometry that is planar and inertially T-shaped, with essentially parallel HBr and CO2 axes. Average values of intermolecular parameters are: Rcm=3.58 A(ring), θBrCO=79.8°, and θHBrC=93.1°. The validity of using the Kraitchman method, which was designed for use with rigid molecules, with a floppy complex like CO2–HBr is discussed. The experimental structure is corroborated qualitatively by results from Møller–Plesset second-order perturbation calculations, corrected for basis set superposition errors. The theoretical equilibrium geometry for the inertially T-shaped complex is planar with structural parameters: RCBr=3.62 A(ring), θBrCO=89°, and θHBrC=86°. A number of cuts on the four dimensional intermolecular potential surface confirm large zero-point amplitudes, which are known to be characteristic of such systems, and these cuts are used to estimate tunneling splittings. Tunneling is shown to occur by out-of-plane rotation of the H atom, in accord with the experimental observations of Rice et al. There is no significant in-plane tunneling. A quasilinear hingelike isomer (OCO–HBr) with ROH=2.35 A(ring) at equilibrium is calculated to be as stable as the T-shaped complex; however, this species has yet to be observed experimentally. Photoinitiated reactions in CO2–HX complexes are discussed. 1089-7690 10897690 American Institute of Physics (AIP) |
| shingle_title_1 | Infrared spectroscopy of CO2–D(H)Br: Molecular structure and its reliability |
| shingle_title_2 | Infrared spectroscopy of CO2–D(H)Br: Molecular structure and its reliability |
| shingle_title_3 | Infrared spectroscopy of CO2–D(H)Br: Molecular structure and its reliability |
| shingle_title_4 | Infrared spectroscopy of CO2–D(H)Br: Molecular structure and its reliability |
| sigel_instance_filter | dkfz geomar wilbert ipn albert |
| source_archive | AIP Digital Archive |
| timestamp | 2024-05-06T08:05:39.647Z |
| titel | Infrared spectroscopy of CO2–D(H)Br: Molecular structure and its reliability |
| titel_suche | Infrared spectroscopy of CO2–D(H)Br: Molecular structure and its reliability |
| topic | U V |
| uid | nat_lic_papers_NLZ21881156X |