Rotational Spectrum of CBr by Kinetic Microwave Spectroscopy of 193-nm Photolysis Products of Bromoform

Hassouna, Mnasser; Walters, A.; Demuynck, C.; Bogey, M.

doi:10.1006/jmsp.1999.8030

Cited by 9 publications

(7 citation statements)

References 18 publications

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Section: Resultssupporting

confidence: 75%

“…The CBr radical has been the subject of recent microwave and diode laser infrared spectroscopy studies . Our CCSD(T)/aug-cc-pV5Z equilibrium bond length of 1.8231 Å is in very good agreement with the accurate experimental value of 1.81517 Å . The remaining discrepancy is predominately due to the neglect of core−valence correlation and scalar relativity in the geometry optimization (cf.…”

Section: Resultssupporting

confidence: 71%

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Heats of Formation of CBr, CHBr, and CBr₂ from Ab Initio Quantum Chemistry

et al. 2002

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High-level ab initio electronic structure theory has been used to calculate the heats of formation of CBr, CHBr, and CBr2. The calculations were done at the CCSD(T) level with correlation-consistent basis sets up through augmented quintuple-z and were extrapolated to the complete basis set limit. Additional corrections for core/valence correlation, relativistic effects both scalar and spin−orbit, and zero-point energies have been included. The heat of formation at 0 K of CBr (2Π) is 119.92 ± 0.5 kcal/mol, of CHBr (1A‘) is 92.34 ± 0.7 kcal/mol, and of CBr2 (1A1) is 86.92 ± 0.7 kcal/mol.

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Section: Resultssupporting

confidence: 75%

Section: Resultssupporting

confidence: 71%

Heats of Formation of CBr, CHBr, and CBr₂ from Ab Initio Quantum Chemistry

et al. 2002

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“…Note that if one uses the appropriate atomic values for ͗1/r 3 ͘ L and ͗1/r 3 ͘ S to determine the unpaired electron density on the Br atom, the resulting densities are very nearly equal to each other. This is in contrast to the carbon monohalides for which the unpaired electron density derived from the dipolar interaction is slightly lower than that derived from the interaction of the magnetic field induced by the electron orbital motion (45)(46)(47). For CBr (47) the derived densities are approximately 17 and 22% when derived from the dipolar and orbital terms, respectively.…”

Section: Hyperfine Constantscontrasting

confidence: 58%

“…This is in contrast to the carbon monohalides for which the unpaired electron density derived from the dipolar interaction is slightly lower than that derived from the interaction of the magnetic field induced by the electron orbital motion (45)(46)(47). For CBr (47) the derived densities are approximately 17 and 22% when derived from the dipolar and orbital terms, respectively. Also of interest is the negative contact term predicted by the relativistic calculation.…”

Section: Hyperfine Constantscontrasting

confidence: 58%

The Rotational Spectra, Isotopically Independent Parameters, and Interatomic Potentials for the X12Π3/2 and X22Π1/2 States of BrO

Drouin

Miller

Müller

et al. 2001

Journal of Molecular Spectroscopy

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“…The experimentally determined equilibrium bond lengths [18][19][20] of the corresponding diatomic molecules are CF = 1.272 Å, CCl= 1.645 Å, and CBr= 1.815 Å, all very similar to the present ab initio predictions for the GeCX radicals. It is remarkable that the C -X bond lengths predicted for the germanium species are almost identical to those predicted for the corresponding SiCX free radicals.…”

Section: The Gecx X 2 ⌸ I Ground Statesupporting

confidence: 75%

In search of the germanium halomethylidyne (GeC–X; X=F,Cl,Br) free radicals: Ab initio studies of their spectroscopic signatures

Tackett

Clouthier

2006

The Journal of Chemical Physics

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A variety of ab initio methods have been used to calculate the X (2)Pi and A (2)Sigma(+) state spectroscopic parameters of the GeCX (X=F,Cl,Br) free radicals. The theoretical methods and basis sets were tested on GeCH, for which extensive experimental data are available, and found to give predictions sufficiently reliable to guide experimental searches for spectra. In all cases, the linear Ge=C-X species was found to be the global minimum on the potential energy surface, with the bent X-Ge=C ((2)A(')) isomer as a local minimum much higher (62-36 kcal/mol) in energy. In both the ground and excited states, the GeC moiety is very similar to that of GeCH, with a double bond in the lower state and a triple bond in the excited state, indicating that halogenation does not radically perturb the energetics or structure of germanium methylidyne. Ground state GeCX radicals have suitable rotational constants for microwave studies, although they suffer from only modest dipole moments. Matrix infrared experiments are most likely to detect the nu(1) fundamentals in the 1450-1100 cm(-1) region or the nu(3) fundamentals at the transition between the mid- and far-infrared regions. We have used the ab initio values for the Renner-Teller parameter, the average bending frequency, and the spin-orbit coupling constant to calculate the ground state energy levels, which will be helpful in the interpretation of A-X single vibronic level emission spectra, if they can be observed. The electronic absorption spectra of the (2)Pi(32) spin component of the 0(0) (0) bands of all three radicals have been calculated assuming typical jet-expansion conditions and should be useful in future laser-induced fluorescence, resonance enhanced multiphoton ionization, or cavity ringdown searches for the electronic band systems.

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Rotational Spectrum of CBr by Kinetic Microwave Spectroscopy of 193-nm Photolysis Products of Bromoform

Cited by 9 publications

References 18 publications

Heats of Formation of CBr, CHBr, and CBr₂ from Ab Initio Quantum Chemistry

Heats of Formation of CBr, CHBr, and CBr₂ from Ab Initio Quantum Chemistry

The Rotational Spectra, Isotopically Independent Parameters, and Interatomic Potentials for the X12Π3/2 and X22Π1/2 States of BrO

In search of the germanium halomethylidyne (GeC–X; X=F,Cl,Br) free radicals: Ab initio studies of their spectroscopic signatures

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Rotational Spectrum of CBr by Kinetic Microwave Spectroscopy of 193-nm Photolysis Products of Bromoform

Cited by 9 publications

References 18 publications

Heats of Formation of CBr, CHBr, and CBr2 from Ab Initio Quantum Chemistry

Heats of Formation of CBr, CHBr, and CBr2 from Ab Initio Quantum Chemistry

The Rotational Spectra, Isotopically Independent Parameters, and Interatomic Potentials for the X12Π3/2 and X22Π1/2 States of BrO

In search of the germanium halomethylidyne (GeC–X; X=F,Cl,Br) free radicals: Ab initio studies of their spectroscopic signatures

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Product

Resources

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Heats of Formation of CBr, CHBr, and CBr₂ from Ab Initio Quantum Chemistry

Heats of Formation of CBr, CHBr, and CBr₂ from Ab Initio Quantum Chemistry