Laser photodissociation dynamics of thionyl chloride: concerted and stepwise cleavage of S-Cl bonds

Wang, Hongxin; Chen, Xirong; Weiner, Brad R.

doi:10.1021/j100149a028

Cited by 37 publications

(56 citation statements)

References 13 publications

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“…At 248 nm, PTS study [24] suggested that the two-body dissociation channel (SOCl 2 +hν→SOCl+Cl) becomes the main channel and the molecular elimination channel (SOCl 2 +hν→SO+Cl 2 ) contributes only insignificantly to the dissociation process [25]; however, no contribution of the three-body dissociation channel (SOCl 2 +hν→SO+2Cl) has been observed at this wavelength. These results agree well with the conclusions obtained by using microwave spectroscopy and laser-induced fluorescence (LIF) at the same wavelength [26]. At 193 nm, however, the dissociation dynamics was remarkably different, a concerted threebody decay has been found to be the main dissociation channel by a PTS study [27].…”

Section: Introductionsupporting

confidence: 89%

Three-Body photodissociation of thionyl chloride

Abulimiti

Hao

Chen

et al. 2018

Chinese Journal of Chemical Physics

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The ultrafast photodissociation dynamics of thionyl chloride after excitation with a 235 nm pump pulse has been studied using a femtosecond time-resolved mass spectroscopy. The observed parent transient suggests that the excited states initiated by 235 nm are very shortlived, that is, approximately 166 fs. Not only a stepwise three-body dissociation pathway but also a concerted three-body dissociation pathway is observed.

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Section: Introductionsupporting

confidence: 89%

Three-Body photodissociation of thionyl chloride

Abulimiti

Hao

Chen

et al. 2018

Chinese Journal of Chemical Physics

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“…Therefore, the key to an SR-based NRS (including NRVS) experiment is to exploit the nanosecond (ns) time delay for the nuclear event and exclude the much faster (fs) electron scattering events. This is similar to the case of laser-induced fluorescence (LIF) spectroscopy [52][53][54][55].…”

Section: Detecting Inelastic Scatteringsupporting

confidence: 72%

Nuclear Resonance Vibrational Spectroscopy: A Modern Tool to Pinpoint Site-Specific Cooperative Processes

et al. 2021

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Nuclear resonant vibrational spectroscopy (NRVS) is a synchrotron radiation (SR)-based nuclear inelastic scattering spectroscopy that measures the phonons (i.e., vibrational modes) associated with the nuclear transition. It has distinct advantages over traditional vibration spectroscopy and has wide applications in physics, chemistry, bioinorganic chemistry, materials sciences, and geology, as well as many other research areas. In this article, we present a scientific and figurative description of this yet modern tool for the potential users in various research fields in the future. In addition to short discussions on its development history, principles, and other theoretical issues, the focus of this article is on the experimental aspects, such as the instruments, the practical measurement issues, the data process, and a few examples of its applications. The article concludes with introduction to non-57Fe NRVS and an outlook on the impact from the future upgrade of SR rings.

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“…The photochemistry of SOCl 2 has been well investigated, producing three dissociation channels: (1) SOCl + Cl, (2) SO + Cl 2 , and (3) SO + 2Cl. The insight into photolysiswavelength dependence of dissociation channels with the related branch ratios, 12,[100][101][102] anisotropy parameter for each channel, 12,13,103 dissociation characterization for the threebody production, 12,104 and nascent vibrational and spin-state distribution of SO 103,105 was mainly gained. The prior studies are essentially focused on probing of the Cl (Cl*) and SO fragments for understanding the dynamical complexity especially for the channels (1) and ( 3).…”

Section: Photodissociation Of Thionyl Chloride and Sulfuryl Chloridementioning

confidence: 99%

Molecular halogen elimination from halogen-containing compounds in the atmosphere

Lin

Tsai

2014

Phys. Chem. Chem. Phys.

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Atmospheric halogen chemistry has drawn much attention, because the halogen atom (X) playing a catalytic role may cause severe stratospheric ozone depletion. Atomic X elimination from X-containing hydrocarbons is recognized as the major primary dissociation process upon UV-light irradiation, whereas direct elimination of the X2 product has been seldom discussed or remained a controversial issue. This account is intended to review the detection of X2 primary products using cavity ring-down absorption spectroscopy in the photolysis at 248 nm of a variety of X-containing compounds, focusing on bromomethanes (CH2Br2, CF2Br2, CHBr2Cl, and CHBr3), dibromoethanes (1,1-C2H4Br2 and 1,2-C2H4Br2) and dibromoethylenes (1,1-C2H2Br2 and 1,2-C2H2Br2), diiodomethane (CH2I2), thionyl chloride (SOCl2), and sulfuryl chloride (SO2Cl2), along with a brief discussion on acyl bromides (BrCOCOBr and CH2BrCOBr). The optical spectra, quantum yields, and vibrational population distributions of the X2 fragments have been characterized, especially for Br2 and I2. With the aid of ab initio calculations of potential energies and rate constants, the detailed photodissociation mechanisms may be comprehended. Such studies are fundamentally important to gain insight into the dissociation dynamics and may also practically help to assess the halogen-related environmental variation.

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Laser photodissociation dynamics of thionyl chloride: concerted and stepwise cleavage of S-Cl bonds

Cited by 37 publications

References 13 publications

Three-Body photodissociation of thionyl chloride

Three-Body photodissociation of thionyl chloride

Nuclear Resonance Vibrational Spectroscopy: A Modern Tool to Pinpoint Site-Specific Cooperative Processes

Molecular halogen elimination from halogen-containing compounds in the atmosphere

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