Understanding the Phase-Dependent Reactivity of Chlorine Dioxide Using Resonance Raman Spectroscopy

Reid, Philip J.

doi:10.1021/ar010064u

Cited by 33 publications

(19 citation statements)

References 48 publications

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“…57 The field of solvation dynamics has played an important role in understanding how 'hot', nascent photoproducts dissipate their excess energy by coupling to the solvent bath, and the spectral density of the solvent is now recognised as a key factor in determining the frequency (and mode) dependent 'cooling' rates of out-of-equilibrium, (ro)vibrationally excited photoproducts.…”

Section: 56mentioning

confidence: 99%

“…55,56 Solvents are not rigid or purely mechanical entities that surround solute molecules, but the solutesolvent dynamic dipolar and electrostatic interactions can have major influences on the outcome and time scales of chemical reactions. 57 The field of solvation dynamics has played an important role in understanding how 'hot', nascent photoproducts dissipate their excess energy by coupling to the solvent bath, and the spectral density of the solvent is now recognised as a key factor in determining the frequency (and mode) dependent 'cooling' rates of out-of-equilibrium, (ro)vibrationally excited photoproducts.…”

Section: Historical Contextmentioning

confidence: 99%

“…71 The remainder of this Review is devoted to comparing selected molecular photodissociation processes in the gas and condensed phases. 57,72,73 Two themes have been chosen, to illustrate (i) the extents to which dynamical insights from gas-phase (isolated molecule) studies can inform our understanding of the corresponding solution-phase photochemistry and (ii) how, in the specific case of photoinduced ring opening reactions, solution-phase studies can provide dynamical insights complementary to (and in some cases more clearly than) those revealed by the corresponding gas-phase study.…”

Section: -61mentioning

confidence: 99%

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Molecular Photofragmentation Dynamics in the Gas and Condensed Phases

Ashfold

Murdock

Oliver

2017

Annu. Rev. Phys. Chem.

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This is the submitted manuscript. The final published version (version of record) is available online via Annual Review of Physical Chemistry at http://www.annualreviews.org/doi/10.1146/annurev-physchem-052516-050756 . Please refer to any applicable terms of use of the publisher University of Bristol -Explore Bristol Research General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above. Full terms of use are available: http://www.bristol.ac.uk/pure/about/ebr-terms 1 Molecular Photofragmentation Dynamics in the Gas and Condensed PhasesMichael N.R. Ashfold, Daniel Murdock and Thomas A.A. Oliver School of Chemistry, University of Bristol, Bristol, U.K., BS8 1TS AbstractExciting a molecule with a UV photon often leads to bond fission, but the final outcome of the bond cleavage is typically both molecule and phase dependent. The photodissociation of an isolated gasphase molecule can be viewed as closed system: energy and momentum are conserved, and the fragmentation is irreversible. The same is not true in a solution-phase photodissociation process.Solvent interactions may dissipate some of the photoexcitation energy prior to bond fission, and will dissipate any excess energy partitioned into the dissociation products. Products that have no analogue in the corresponding gas-phase study may arise by, for example, geminate recombination. Here we illustrate the extents to which dynamical insights from gas-phase studies can inform our understanding of the corresponding solution-phase photochemistry and how, in the specific case of photoinduced ring-opening reactions, solution-phase studies can in some cases reveal dynamical insights more clearly than the corresponding gas-phase study.Keywords photochemistry, photodissociation, photoinduced ring opening, non-adiabatic dynamics, conical intersections. 2 HISTORICAL CONTEXTCiamician is recognised as a pioneer of (organic) photochemistry and an early advocate for fuel production by means of artificial photo'synthesis'. 1 His studies were performed in solution and usually driven by sunlight, at a time when the concept of the photon was yet to be fully accepted.Identifying the ultimate reaction products was in itself a major achievement, and any ideas regarding reaction mechanism were rudimentary. Even the concatenation of ideas like ground and excited electronic states, radiative and non-radiative transitions, spin multiplicity, etc, into what would later be termed a Jablonski diagram 2 still lay far in the future.A potentially more fruitful path at that time for those curious about the mechanisms of photochemical reactions was to focus on very simple molecular systems -diatomic and 'diatomic-like' molecules. generally polychromatic) light sources were now available, and the development of grating spectrometers enabled the recording of electronic absorption spectra for many small gas-phase molecules. Vibrational and even rotational fine structure was resolved and interpreted in many such ...

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Section: 56mentioning

confidence: 99%

Section: Historical Contextmentioning

confidence: 99%

Section: -61mentioning

confidence: 99%

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Molecular Photofragmentation Dynamics in the Gas and Condensed Phases

Ashfold

Murdock

Oliver

2017

Annu. Rev. Phys. Chem.

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“…The photochemical reaction dynamics of halooxides, including OCIO, have been of interest for well over a decade because of the participation of this compound in many stratospheric photochemical processes ( 9–15 ). The following reaction channels are available to OCIO after photoexcitation resonant with the 2 B 1 ‐ 2 A 2 electronic transition centered at ∼360 nm ( 11 ):…”

Section: Chlorine Dioxidementioning

confidence: 99%

The Phase‐dependent Photochemical Reaction Dynamics of Halooxides and Nitrosyl Halides^¶

Cooksey

Reid

2004

Photochem & Photobiology

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Recent progress in understanding the phasedependent reactivity of halooxides and nitrosyl halides is outlined. Halooxide reactivity is represented by the photochemistry of chlorine dioxide (OCIO) and dichlorine monoxide (ClOCl). The gas phase photochemical dynamics of OClO are contrasted with the dynamics in condensed environments. The role of excited-state symmetry in defining the reaction dynamics and the observation of photoisomerization resulting in the production of ClOO are discussed. The current understanding of the excited-state reaction dynamics of ClOCl and evidence for photoisomerization of this species resulting in the production of ClClO are outlined. Finally, the photochemical reaction dynamics of the nitrosyl halide ClNO are presented. The main difference between the gas and condensed phase reaction dynamics of this species is that whereas photodissociation to form Cl and NO dominates the gas phase reaction dynamics, photoisomerization resulting in ClON production occurs to an appreciable extent in condensed environments. The observation of photoisomerization for OClO, ClOCl and ClNO suggests that this process is a general feature of the condensed phase reaction dynamics for smaller halooxides and nitrosyl halides. Finally, future areas for study in both halooxide and nitrosyl halide photoreactivity are outlined.

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“…The experimental work was strongly complemented and expanded by elegant theoretical calculations [65,72]. The partitioning between all possible product channels is a strong function of the molecule's environment [40,[73][74][75][76][77]. For example, the major gas phase channel leads to ClO production while in condensed phase reaction to Cl and O 2 becomes important and increases as the temperature is lowered.…”

Section: Excited Electronic State Photochemical Reactionsmentioning

confidence: 99%

Sunlight initiated atmospheric photochemical reactions

Vaida

2005

International Journal of Photoenergy

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The Sun is the light source driving atmospheric chemistry. The wavelengths dependent photon flux is controlled by solar emission modulated by absorption of atmospheric gases, aerosols and clouds. The factors determining the characteristics of this light source, its altitude, latitude and zenith angle dependence are discussed to explain the effectiveness of the Sun in driving chemical reactions. Examples of chemical reactions occurring on the excited and the ground electronic state potential energy surfaces of molecules and radicals are used to illustrate the complexity of atmospheric photochemistry. Specifically, the near ultraviolet (UV) photochemistry of chlorine dioxide is used to exemplify electronic state reactions occurring in the atmosphere. The near infrared (IR) photochemistry of nitric and sulfuric acids are discussed to illustrate reactions important in the atmosphere which occur with solar pumping of vibrational overtone transitions in the ground electronic state of these molecules.

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Understanding the Phase-Dependent Reactivity of Chlorine Dioxide Using Resonance Raman Spectroscopy

Cited by 33 publications

References 48 publications

Molecular Photofragmentation Dynamics in the Gas and Condensed Phases

Molecular Photofragmentation Dynamics in the Gas and Condensed Phases

The Phase‐dependent Photochemical Reaction Dynamics of Halooxides and Nitrosyl Halides^¶

Sunlight initiated atmospheric photochemical reactions

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Understanding the Phase-Dependent Reactivity of Chlorine Dioxide Using Resonance Raman Spectroscopy

Cited by 33 publications

References 48 publications

Molecular Photofragmentation Dynamics in the Gas and Condensed Phases

Molecular Photofragmentation Dynamics in the Gas and Condensed Phases

The Phase‐dependent Photochemical Reaction Dynamics of Halooxides and Nitrosyl Halides¶

Sunlight initiated atmospheric photochemical reactions

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Product

Resources

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The Phase‐dependent Photochemical Reaction Dynamics of Halooxides and Nitrosyl Halides^¶