The Cu + F2 chemiluminescent reaction revisited. I. Spectroscopy of the CuF product

Baltayan, P.; Hartmann, F.; Pebay-Peyroula, J.C.; Sadeghi, N.

doi:10.1016/0301-0104(88)87214-8

Cited by 24 publications

(16 citation statements)

References 18 publications

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“…10 The calculated position of the a 3 S 0 À state, which also is metastable, is only 97 cm À1 below the a 3 S þ 1 state 28 and some collisional mixing of populations in these states may occur. The relative positions of the metastable CuF* states are similar and experimental T 0 values for the a 3 S þ 1 and b 3 P 1 states are 14 605 cm À1 33 and 17 545 cm À1 , 5 respectively. The T 0 values of the c( 3 D 1 ) states of CuF* and CuCl* are 22 803 30 and 25 269 cm À1 , 22 respectively and only CuF*(c 3 D) formation can be expected.…”

Section: Introductionsupporting

confidence: 62%

“…have been extensively studied in recent years. [2][3][4][5][6][7][8][9][10][11] In our laboratory, we have systematically investigated the reactions with F 2 , [5][6][7] Cl 2 10,11 and Br 2 8 with a focus on the chemiluminescent component. The measurement of the reaction rate constants and the observation of partitioning of the energy into electronic, vibrational and rotational product channels provided insight into reaction mechanisms.…”

Section: Introductionmentioning

confidence: 99%

“…The Cu atoms were generated by a hollow-cathode sputtering source. 5,6 Copper metastable atoms in 2 D 3/2 or 2 D 5/2 states could be selected by optical pumping with a Cu-vapor laser. The chemiluminescence of CuCl* and CuF* was recorded in the spectral range of 400-700 nm.…”

Section: Introductionmentioning

confidence: 99%

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The Cu*(2D5/2 and 2D3/2) chemiluminescent reactions with ClF

Sadeghi

Kowalczyk

Setser

2003

Phys. Chem. Chem. Phys.

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The chemiluminescence from CuCl* and CuF* molecules formed by the reaction of metastable 2 D 3/2 and 2 D 5/2 copper atoms with ClF was studied at room temperature. The Cu* atoms were generated in a hollowcathode, flowing-afterglow reactor. A strong preference ($15:1) for production of electronically excited CuCl* over excited CuF* was found. Computer simulations of the observed spectra provided electronic branching ratios, as well as vibrational distributions within each CuCl* and CuF* electronic state. The vibrational energy disposal for CuCl*, h f v i ¼ 0.06-0.32, was similar to, or smaller than, the statistical value, whereas h f v i was much larger (%0.6) for the CuF* products. The total rate constants for the reaction of ground 2 S and metastable 2 D 5/2 and 2 D 3/2 states of Cu atoms with ClF were measured as 28 AE 3, 8.8 AE 2.5 and 10 AE 3 Â 10 À11 cm 3 molecule À1 s À1 . The highest observed CuF*(b 3 P 0 + ,1 ) vibrational levels from the ClF and F 2 reactions were used to recommend D 0 (CuF) ¼ 34 300 cm À1 . The results from ClF were compared with the data from the analogous F 2 , Cl 2 and Br 2 reactions. The branching fractions for chemiluminescent products decline in the order F 2 > Cl 2 > ClF > Br 2 , and the formation of CuX(X) from reactions of the Cu*( 2 D 5/2 and 2 D 3/2 ) atoms becomes more important in the series. The reactions of the ground and metastable-state copper atoms with SOCl 2 , CCl 4 and PCl 3 also are discussed.

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Section: Introductionsupporting

confidence: 62%

Section: Introductionmentioning

confidence: 99%

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The Cu*(2D5/2 and 2D3/2) chemiluminescent reactions with ClF

Sadeghi

Kowalczyk

Setser

2003

Phys. Chem. Chem. Phys.

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“…Partitioning of Excess Energy. Fits to the individual bands were obtained by using literature values 26,27 for diatomic molecular parameters to calculate the excited and ground state vibrational and rotational energy levels. The fitting parameters were the Boltzmann temperatures used to determine the populations of rotational and vibrational levels in the excited states.…”

Section: Discussionmentioning

confidence: 99%

Copper Fluoride Luminescence during UV Photofragmentation of Bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)copper(II) in the Gas Phase

Talaga

Zink

1996

Inorg. Chem.

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Gas phase 308 and 350-370 nm photolysis of bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)copper(II), Cu(hfac)(2), produces CuF as well as copper atoms and dimers. These metal-containing fragments, identified by luminescence spectroscopy, are studied under a variety of gas phase conditions ranging from 1 bar in a static chamber to 10(-4) mbar in a collision-free molecular beam. Copper atom and dimer luminescence is observed at the higher pressures, whereas at low pressures (total pressure no greater than the vapor pressure of the sample) exclusively CuF emission is observed. The a, A (omega = 0, 1, 2), B, and C excited states at 681.0, 567.6, and 505.1, and 491.7 nm are observed. The (3)Pi(0)(-) component of the A state is observed for the first time. The CuF luminescence obeys a quadratic power law with 308 nm excitation. The partitioning of excess energy into fragment degrees of freedom is determined from the intensities of the emission lines. The vibrational and rotational temperatures of the CuF fragment are in excess of 1700 K. Mechanisms of CuF formation, comparisons with the free ligand and with other volatile copper complexes, and the implications for laser-assisted chemical vapor deposition are discussed.

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“…Only for the lightest halide, CuF, the nature of the low-lying excited states has been well established both theoretically [1][2][3][4][5][6] and experimentally. [7][8][9] For CuCl the situation is less clear. Although it is generally agreed that all excitations reported have a common lower state, the ground state X 1 ⌺ ϩ , Cu ϩ (3d 10 )Cl Ϫ (3s 2 3p 6 ) and that the excited states involved in such transitions arise from the Cu ϩ (3d 9 4s 1 )Cl Ϫ (3s 2 3p 6 ) ionic configuration, the assignment of the observed bands to particular states is still not well established.…”

Section: Introductionmentioning

confidence: 99%

Theoretical characterization of the low-lying excited states of the CuCl molecule

Sousa

Jong

Broer

et al. 1997

The Journal of Chemical Physics

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Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. The character of the low-lying excited states of diatomic CuCl is studied primarily by means of the complete active space self-consistent field ͑CASSCF͒, method and a second order perturbation approach with the CASSCF wave function as reference state ͓complete active space perturbation theory to second order ͑CASPT2͔͒. For comparison, the lower levels of the spectra of the Cu ϩ ion are also analyzed. A first order treatment of the scalar relativistic effects, the mass-velocity and Darwin terms, is included in the calculations. The importance of spin-orbit interactions is investigated by comparing our nonrelativistic valence shell CI ͑VCI͒ and relativistic results obtained with our four-component program suite MOLFDIR. The six lowest excited states of the CuCl molecule, which are related to the Cu ϩ (3d 9 4s 1 )Cl Ϫ (3s 2 3p 6 ) ionic configuration, are assigned. The assignments agree with earlier theoretical work. Where they can be compared, the calculated spectroscopic constants are in good agreement with the experimental data. © 1997 American Institute of Physics. ͓S0021-9606͑97͒03017-1͔

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The Cu + F2 chemiluminescent reaction revisited. I. Spectroscopy of the CuF product

Cited by 24 publications

References 18 publications

The Cu*(2D5/2 and 2D3/2) chemiluminescent reactions with ClF

The Cu*(2D5/2 and 2D3/2) chemiluminescent reactions with ClF

Copper Fluoride Luminescence during UV Photofragmentation of Bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)copper(II) in the Gas Phase

Theoretical characterization of the low-lying excited states of the CuCl molecule

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