Spin–orbit branching in the photofragmentation of HCl at long wavelength

Lambert, Henry; Dagdigian, Paul J.; Alexander, Millard H.

doi:10.1063/1.475857

Cited by 69 publications

(74 citation statements)

References 27 publications

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“…16 The branching ratio was found to be dependent on excitation energy, with the fraction of Cl* from HCl being greater than that from DCl. 23 In contrast to HBr, 29 the X 1 ⌺ ϩ -a 3 ⌸ 0 mixing is of little importance in the photodissociation of HCl according to recent calculations. 23 Beyond this fundamental interest, the quantitative data are also useful for understanding the photochemistry of interstellar medium 30 and planetary atmospheres.…”

Section: Introductionmentioning

confidence: 95%

“…The spin-orbit branching between products Cl* ( 2 P 1/2 ) and Cl ( 2 P 3/2 ) upon vacuum ultraviolet ͑VUV͒ photolysis of a͒ Corresponding author: Electronic mail: bmcheng@srrc.gov.tw b͒ HCl or DCl have been extensively studied both experimentally 12,13,23,25,27,28 and theoretically; 15,16,21,23,25 agreement among them are satisfactory except at shorter wavelengths. The product branching is governed by the spin-orbit coupling between the initially excited A 1 ⌸ state and both the a 3 ⌸ and 1 3 ⌺ ϩ states.…”

Section: Introductionmentioning

confidence: 99%

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Quantitative spectral analysis of HCl and DCl in 120–220 nm: Effects of singlet–triplet mixing

Cheng

Chung

Bahou

et al. 2002

The Journal of Chemical Physics

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Articles you may be interested inAn ab initio investigation of the ground and low-lying singlet and triplet electronic states of XNO2 and XONO (X = Cl, Br, and I) Theoretical study of the absorption and nonradiative deactivation of 1-nitronaphthalene in the low-lying singlet and triplet excited states including methanol and ethanol solvent effects J. Chem. Phys. 137, 054307 (2012); 10.1063/1.4738757Excited-state geometries and vibrational frequencies studied using the analytical energy gradients of the direct symmetry-adapted cluster-configuration interaction method. I. HAX-type molecules Photoabsorption cross sections of HCl and DCl in the spectral region 120-220 nm were measured using synchrotron radiation as a light source. The absorption contour of the A 1 ⌸←X 1 ⌺ ϩ band of HCl in the 134 -195 nm region is slightly asymmetric, whereas that of DCl is symmetric, with wavelength of absorption maximum shifted from ϳ153.9 nm for HCl to ϳ155.8 nm. The asymmetry in HCl and the atypical direction of shift in peak wavelengths upon deuteration are attributed to singlet-triplet mixing in its ground X 1 ⌺ ϩ state of HCl; this triplet component contributes to the oscillator strengths of the A -X band of HCl via transition to the repulsive triplet state 1 3 ⌺ ϩ . The small triplet character in HCl is further supported by an observation that the oscillator strength of the ͑0,0͒ band for the b 3 ⌸ -X 1 ⌺ ϩ transition of DCl is ϳ17% smaller than that of HCl. This triplet component may account for greater values of spin-orbit branching ratios for products, Cl*( 2 P 1/2 )/Cl( 2 P 3/2 ) , observed upon photolysis of HCl in the 143-167 nm region. For both HCl and DCl, ratios of observed oscillator strengths to calculated Franck-Condon factors of the C 1 ⌸ state decrease with vibrational levels, whereas those of the b 3 ⌸ state increases with increasing vibrational levels. Such a variation was attributed to perturbation between the b and C states, for which quantitative data are established in this study.

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Section: Introductionmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Quantitative spectral analysis of HCl and DCl in 120–220 nm: Effects of singlet–triplet mixing

Cheng

Chung

Bahou

et al. 2002

The Journal of Chemical Physics

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“…This has been studied in detail for the relatively simple HCl and OH molecules. 1,2 The photodissociation of O 2 in the Herzberg continuum is complicated since already in the excitation step several electronically excited states are involved. Both parallel and perpendicular electronic transitions contribute.…”

Section: Introductionmentioning

confidence: 99%

Photodissociation of O2 in the Herzberg continuum. II. Calculation of fragment polarization and angular distribution

Vroonhoven

Groenenboom

2002

The Journal of Chemical Physics

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Articles you may be interested inIon-pair dissociation dynamics of O2 in the range 17.2-17.5 eV studied by XUV laser and velocity map imaging method State-to-state photodissociation dynamics of OH radical via the A 2 Σ + state: Fine-structure distributions of the O ( 3 P J ) product Parallel and perpendicular components of the Herzberg I, II, and III transitions contribute to the photodissociation of O 2 in the Herzberg continuum. The photodissociation dynamics determines the O( 3 P j ), jϭ0,1, and 2 atomic fine-structure branching ratios and angular distributions, which were determined in ion imaging experiments at ϭ236, 226, and 204 nm by Buijsse et al. ͓J. Chem. Phys. 108, 7229 ͑1998͔͒. In the preceding paper we presented potential energy curves for all eight ungerade O 2 states that correlate with the O( 3 P)ϩO( 3 P) dissociation limit, and the R-dependent spin-orbit and the nonadiabatic radial derivative couplings between these states. Here, we employ these potentials and couplings in a semiclassical calculation of the fine-structure branching ratios, atomic polarizations, and fine-structure resolved anisotropy parameters. We discuss the adiabaticity of the dissociation by comparing the results with adiabatic and diabatic models. The O( 3 P j ) 2ϩ1 REMPI detection scheme used in the experiment is sensitive to the polarization of the atomic fragments. We predict an important effect of the polarization on the anisotropy of the jϭ1 and jϭ2 ion images at low energies ͑Ͼ236 nm͒. The agreement between the semiclassical calculations and experiment is reasonable, possible explanations for the remaining differences are discussed.

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“…4 and is compared with the near quantitative experimental data by Lambert et al [34]. It is clear that the wavelength dependence of the branching fraction of Cl * can be reproduced in principle, and the theoretical prediction at most wavelengths is consistent with experiment, despite their smaller magnitude.…”

Section: Model Calculations Of the Branching Fractions Of CL *mentioning

confidence: 60%

Investigation on the photofragmentation of hydrogen chloride

Zhang¹

2008

Chemical Physics

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Spin–orbit branching in the photofragmentation of HCl at long wavelength

Cited by 69 publications

References 27 publications

Quantitative spectral analysis of HCl and DCl in 120–220 nm: Effects of singlet–triplet mixing

Quantitative spectral analysis of HCl and DCl in 120–220 nm: Effects of singlet–triplet mixing

Photodissociation of O2 in the Herzberg continuum. II. Calculation of fragment polarization and angular distribution

Investigation on the photofragmentation of hydrogen chloride

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