The vacuum ultraviolet absorption spectra of the group IVA tetrachlorides

Causley, G. C.; Russell, B. R.

doi:10.1016/0368-2048(77)80015-7

Cited by 49 publications

(35 citation statements)

References 17 publications

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“…In general, the precision and accuracy of the present measurements was better than obtained in previous CCl 4 cross section studies. A comparison of the present results at each wavelength with the previously reported values (Burton et al, 1994;Causley and Russell, 1977;Gillotay and Simon, 1990;Gordus and Bernstein, 1954;Ho, 1998;Hubrich and Stuhl, 1980;Ibuki et al, 1986;Prahlad and Kumar, 1995;Rowland and Molina, 1975;Roxlo and Mandl, 1980;N. Rontu Carlon et al: N 2 O and CCl 4 UV cross sections Seccombe et al, 1999;Simon et al, 1988;Vanlaethem-Meurée et al, 1978) is shown in Fig.…”

Section: Comparison With Previous Studiessupporting

confidence: 74%

“…The different be- Simon et al (1988), the data set currently recommended by JPL06-2 (Sander et al, 2006) for use in atmospheric modeling, are plotted using the cross section and temperature dependence parameterization reported in their work. Data from Causley and Russell (1977), Seccombe et al (1999), Ho (1998), and Roxlo and Mandl (1980) are not included due to the large deviation from the other studies.…”

Section: Uv Absorption Cross Sectionsmentioning

confidence: 99%

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UV absorption cross sections of nitrous oxide (N2O) and carbon tetrachloride (CCl4) between 210 and 350 K and the atmospheric implications

et al. 2010

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Absorption cross sections of nitrous oxide (N₂O) and carbon tetrachloride (CCl₄) are reported at five atomic UV lines (184.95, 202.548, 206.200, 213.857, and 228.8 nm) at temperatures in the range 210–350 K. In addition, UV absorption spectra of CCl₄ are reported between 200–235 nm as a function of temperature (225–350 K). The results from this work are critically compared with results from earlier studies. For N₂O, the present results are in good agreement with the current JPL recommendation enabling a reduction in the estimated uncertainty in the N₂O atmospheric photolysis rate. For CCl₄, the present cross section results are systematically greater than the current recommendation at the reduced temperatures most relevant to stratospheric photolysis. The new cross sections result in a 5–7% increase in the modeled CCl₄ photolysis loss, and a slight decrease in the stratospheric lifetime, from 51 to 50 years, for present day conditions. The corresponding changes in modeled inorganic chlorine and ozone in the stratosphere are quite small. A CCl₄ cross section parameterization for use in atmospheric model calculations is presented

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Section: Comparison With Previous Studiessupporting

confidence: 74%

Section: Uv Absorption Cross Sectionsmentioning

confidence: 99%

UV absorption cross sections of nitrous oxide (N2O) and carbon tetrachloride (CCl4) between 210 and 350 K and the atmospheric implications

et al. 2010

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“…For example, the strongest pole calculated lies at 11.1 eV, while the experi-mental one is at 13.0 eV. In addition, peak assignments in the previous papers 9, 11,26,27 were based on the photoabsorption data obtained in the photon energy region below 11.27 eV ͑110 nm͒. 9 Since the s←t 1 transition is forbidden in a T d symmetry, 28 we assign the first broadband at 8.84 eV as the 4s←3t 2 Rydberg transition as did Robin.…”

Section: Emission Excitation Spectra and The Rydberg Assignmentsmentioning

confidence: 78%

“…The peak positions are given in Table I. The first photoabsorption band at 8.84 eV was originally assigned as the valence excitation of the 3t 2 MO, 26 while Robin has claimed that this band is the 4s←3t 2 Rydberg transition by comparing the photoabsorption bands of the group IV tetrachlorides. 27 He has also assigned the peaks at 9.77 and 10.07 eV to the 4p-and 4 pЈ-terminating Rydberg transitions since the 3t 2 MO is split in the Rydberg excited state by the Jahn-Teller effect.…”

Section: Emission Excitation Spectra and The Rydberg Assignmentsmentioning

confidence: 99%

Photoabsorption and fluorescence cross sections of SiCl4 in the region of 6.2–31 eV

Ibuki

Kono

Asari

et al. 1997

The Journal of Chemical Physics

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Absolute photoabsorption and fluorescence cross sections of gaseous SiCl 4 have been measured in the energy region 6.2-31 eV using synchrotron radiation as the light source. Higher order light from the 1-m Seya monochromator was suppressed by use of an Ar gas filter in the energy range 11.3-15.5 eV ͑110-80 nm͒ and a LiF window at h Ͻ 11.8 eV ͑105 nm͒. Emissions have been observed for the C 2 T 2 →Ã 2 T 2 and C 2 T 2 →X 2 T 1 processes of the SiCl 4 ϩ molecular ion and the Ã 1 B 1 →X 1 A 1 and 3 B 1 →X 1 A 1 of the SiCl 2 radical. The total fluorescence cross section has been determined to be 22.4Ϯ1.0 Mb at 21.22 eV. By comparing with the partial cross section for formation of the C 2 T 2 ionic state ͓Carlson et al., J. Chem. Phys. 84, 641 ͑1986͔͒, it has been concluded that the SiCl 4 ϩ (C 2 T 2 ) formed decays via radiative processes with quantum yield Ϸ1.The experimental results provide information on the breakdown pathways of the SiCl 4 ϩ (C 2 T 2 ) ion state. The bands observed in photoabsorption and fluorescence excitation spectra have been assigned as the ͑4s, np, and npЈ͒←3t 2 , ͑4s and np͒←1e, ͑4s and np͒←1e, ͑4s and 4 p͒←2t 2 , and ͑np and nd͒←2a 1 Rydberg series. The ionization energies for the (2t 2 ) Ϫ1 and (2a 1 ) Ϫ1 processes have been found to be 15.04Ϯ0.03 and 18.17Ϯ0.03 eV, respectively.

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“…3, where A(3p,u*) bands are readily observed in CCl,, GeCl,, and SnCI,, but not in SiC1, (6). In this group, the M-Cl bond is especially strong in SiCl, (88 kcal/mol) compared to the others (ca.…”

Section: Ib Term-value Trends and Bond Strengthsmentioning

confidence: 83%

Antibonding σ* orbitals in molecular spectroscopy

Robin¹

1985

Can. J. Chem.

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This paper is dedicated to Professor Camille Sandorfy on the occasion of his 65th birthdayM. B. ROBIN. Can. J . Chem. 63, 2032Chem. 63, (1985. This paper discusses the role of a* antibonding valence MO's in the electronic spectra of large molecules. Using the term value and antishielding concepts, molecular absorption patterns terminating at a* MO's are systematized and rationalized; the frequencies of such excitations correlate with the ground-state bond strengths of the bonds giving rise to the a* MO's. In unsaturated systems, the 7~ + a* and np + a* excitations can be distinguished on the basis of their term values. Confusion in the past regarding the existence of excitations to a* relates to the fact that a* MO's often can be totally mixed into the surrounding sea of Rydberg levels of the same symmetry, and for all practical purposes can cease to exist except as perturbations on the Rydberg levels. For nonpenetrating Rydberg manifolds there is little or no mixing with a* MO's of the same symmetry, setting the stage for the appearance of valence-shell excitations to a* in high-symmetry molecules which are analogous to the d + f inner-well giant resonances of atomic spectroscopy.M. B. ROBIN. Can. J. Chem. 63, 2032Chem. 63, (1985. Dans ce travail, on discute du r61e des OM de valence antiliante a* dans les spectres Clectroniques des grosses molCcules. Utilisant les concepts de valeur de terme et d'antiblindage, on systimatise et on rationalise les types d'absorptions molCculaires qui se terminent au niveau des OM a*; il existe une correlation entre les frCquences de telles excitations et les longueurs de liaisons dans I'Ctat atomique fondamental qui donne lieu aux OM a*. Dans les systkmes non-saturCs, on peut distinguer les excitations 7~ + a* des excitations np + a* en se basant sur leurs valeurs de terme. La confusion qui a Ct C observte dans le passe relativement a I'existence d'excitations vers les niveaux a* provient du fait que les OM u* peuvent souvent Ctre complktement confondues avec les niveaux de Rydberg de m&me symCtrie qui les entourent et, a toutes fins pratiques, elles cessent d'exister, except6 comme perturbations des niveaux de Rydberg. Pour les Ctats non-pCnCtrants de Rydberg, il y peu ou pas du tout de mtlange avec les OM a* de mCme symCtrie et ceci permet, dans les molCcules de haute symCtrie, de noter ]'apparition d'excitations des couches de valence vers les Ctats a* qui sont semblables aux rksonances @antes d + f de la spectroscopie atomique.[Traduit par le journal]

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The vacuum ultraviolet absorption spectra of the group IVA tetrachlorides

Cited by 49 publications

References 17 publications

UV absorption cross sections of nitrous oxide (N<sub>2</sub>O) and carbon tetrachloride (CCl<sub>4</sub>) between 210 and 350 K and the atmospheric implications

UV absorption cross sections of nitrous oxide (N<sub>2</sub>O) and carbon tetrachloride (CCl<sub>4</sub>) between 210 and 350 K and the atmospheric implications

Photoabsorption and fluorescence cross sections of SiCl4 in the region of 6.2–31 eV

Antibonding σ* orbitals in molecular spectroscopy

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The vacuum ultraviolet absorption spectra of the group IVA tetrachlorides

Cited by 49 publications

References 17 publications

UV absorption cross sections of nitrous oxide (N&lt;sub&gt;2&lt;/sub&gt;O) and carbon tetrachloride (CCl&lt;sub&gt;4&lt;/sub&gt;) between 210 and 350 K and the atmospheric implications

UV absorption cross sections of nitrous oxide (N&lt;sub&gt;2&lt;/sub&gt;O) and carbon tetrachloride (CCl&lt;sub&gt;4&lt;/sub&gt;) between 210 and 350 K and the atmospheric implications

Photoabsorption and fluorescence cross sections of SiCl4 in the region of 6.2–31 eV

Antibonding σ* orbitals in molecular spectroscopy

Contact Info

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Resources

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UV absorption cross sections of nitrous oxide (N<sub>2</sub>O) and carbon tetrachloride (CCl<sub>4</sub>) between 210 and 350 K and the atmospheric implications

UV absorption cross sections of nitrous oxide (N<sub>2</sub>O) and carbon tetrachloride (CCl<sub>4</sub>) between 210 and 350 K and the atmospheric implications