An official website of the United States government
ABSTRACT Criegee intermediates make up a class of molecules that are of significant atmospheric importance. Understanding their electronically excited states guides experimental detection and provides insight into whether solar photolysis plays a role in their removal from the troposphere. The latter is particularly important for large and functionalized Criegee intermediates. In this study, the excited state chemistry of two small Criegee intermediates, formaldehyde oxide (CH2OO) and acetaldehyde oxide (CH3CHOO), was modeled to compare their specific dynamics and mechanisms following excitation to the bright ππ* state and to assess the involvement of triplet states to the excited state decay process. Following excitation to the bright ππ* state, the photoexcited population exclusively evolves to form oxygen plus aldehyde products without the involvement of triplet states. This occurs despite the presence of a more thermodynamically stable triplet path and several singlet/triplet energy crossings at the Franck‐Condon geometry and contrasts with the photodynamics of related systems such as acetaldehyde and acetone. This work sets the foundations to study Criegee intermediates with greater molecular complexity, wherein a bathochromic shift in the electron absorption profiles may ensure greater removalviasolar photolysis.
more »
« less
This content will become publicly available on August 31, 2026
Thermal and photoinduced chemistry of the aromatic Criegee intermediate, benzaldehyde oxide: Implications for indoor air quality
Abstract Essential oils contain a complex mixture of volatile organic compounds, ranging from terpenes to aromatics. When released into the indoor air environment or into the atmosphere, they may undergo oxidation to generate complex reactive intermediates that affect indoor air quality. Cinnamaldehyde is one such aromatic molecule that is abundant in essential oils. When released into the indoor air environment, it may undergo oxidation to form a carbonyl oxide (Criegee intermediate) with an aromatic substituent: benzaldehyde oxide. In this manuscript, we present a high‐level quantum chemical study that shows that, unlike smaller atmospherically relevant Criegee intermediates, benzaldehyde oxide is expected to undergo solar photolysis on timescales that are competitive with its ground state unimolecular and bimolecular chemistry. We show that aromatic substitution leads to a drastic bathochromic shift in the spectroscopically relevant excited states, revealing that photolysis in the indoor or outdoor environment should not be neglected when modeling the climate and air quality implications of Criegee intermediates with extended conjugation. We predict a range of products that may be important for forming lower volatility compounds via tropospherically relevant photochemistry. To motivate future experimental validation of our results, we propose a viable synthetic procedure of the relevant precursor for generating and stabilizing benzaldehyde oxide.
more »
« less
- Award ID(s):
- 2003422
- PAR ID:
- 10633457
- Publisher / Repository:
- Wiley
- Date Published:
- Journal Name:
- Photochemistry and Photobiology
- ISSN:
- 0031-8655
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Biogenic hydrocarbons are emitted into the Earth's atmosphere by terrestrial vegetation as by‐products of photosynthesis. Isoprene is one such hydrocarbon and is the second most abundant volatile organic compound emitted into the atmosphere (after methane). Reaction with ozone represents an important atmospheric sink for isoprene removal, forming carbonyl oxides (Criegee intermediates) with extended conjugation. In this manuscript, we argue that the extended conjugation of these Criegee intermediates enables electronic excitation of these compounds, on timescales that are competitive with their slow unimolecular decay and bimolecular chemistry. We show that the complexation of methacrolein oxide with water enhances the absorption cross section of the otherwise dark S1state, potentially revealing a new avenue for forming lower volatility compounds via tropospherically relevant photochemistry.more » « less
-
The composition of air-exposed surfaces can have a strong impact on air quality and chemical exposure in the indoor environment. Third hand smoke (THS), which includes surface-deposited cigarette smoke residue along with the collection of gases evolved from such residues, is becoming increasingly recognized as an important source of long-term tobacco smoke exposure. While studies have described gas/surface partitioning behaviour and some multiphase reaction systems involving THS, the possibility of time-dependent changes in chemical composition due to chemical reactivity that is endogenous to the deposited film has yet to be investigated. In this study, sidestream cigarette smoke was allowed to deposit on glass surfaces that were either clean or pre-coated with chemicals that may be oxidized by reactive oxygen species found in the smoke. Surface films included a low volatility antioxidant, tris(2-carboxyethyl)phosphine (TCEP), and two compounds relevant to surface films found within buildings, oleic acid (OA) and squalene (SQ). Upon deposition, oxidation products of nicotine, TCEP, OA, and SQ were formed over time periods of hours to weeks. The inherent oxidative potential of cigarette smoke deposited as a THS film can therefore initiate and sustain oxidation chemistry, transforming the chemical composition of surface films over long periods of time after initial smoke deposition. An interpretation of the THS oxidation results is provided in the context of other types of deposited particulate air pollutants with known oxidative potential that may be introduced to indoor environments. Continued study of THS and deposited surface films found indoors should consider the concept that chemical reservoirs found on surfaces may be reactive, that the chemical composition of indoor surface films may be time-dependent, and that the deposition of aerosol particles can act as a mechanism to initiate oxidation in surface films.more » « less
-
Criegee intermediates (CIs) are of great significance to Earth’s troposphere – implicated in altering the tropospheric oxidation cycle and in forming low volatility products that typically condense to form secondary organic aerosols (SOAs). As such, their chemistry has attracted vast attention in recent years. In particular, the unimolecular decay of thermal and vibrationally-excited CIs has been the focus of several experimental and computational studies, and it now recognized that CIs undergo unimolecular decay to form OH radicals. In this contribution we reveal insight into the chemistry of CIs by highlighting the hitherto neglected multi-state contribution to the ground state unimolecular decay dynamics of the Criegee intermediate products. The two key intermediates of present focus are dioxirane and vinylhydroperoxide – known to be active intermediates that mediate the unimolecular decay of CH2OO and CH3CHOO, respectively. In both cases the unimolecular decay path encounters conical intersections, which may play a pivotal role in the ensuing dynamics. This hitherto unrecognized phenomenon may be vital in the way in which the reactivity of CIs are modelled and is likely to affect the ensuing dynamics associated with the unimolecular decay of a given CI.more » « less
-
Isostructural Cr and Fe nanoporous MIL-101, synthesized without mineralizing agents, are investigated for styrene oxidation utilizing aqueous hydrogen peroxide to yield valuable oxygenates for chemical synthesis applications. Styrene conversion rates and oxygenate product distributions both depend on metal identity, as MIL-101(Fe) is more reactive for total styrene oxidation and is more pathway selective, preferring aldehyde (benzaldehyde) formation at the α-carbon to the aromatic ring, where MIL-101(Cr) sustains epoxide (styrene oxide) production at the same α-carbon. These pathways often involve hydrogen peroxide derived radical intermediates (O, –HOO˙, –HO − ˙) and metallocycle transition states. We postulate that the higher reactivity of one of these surface intermediates, Fe( iv )O relative to Cr( iv )O, leads to higher styrene oxidation rates for MIL-101(Fe), while higher electrophilicity of Cr( iii )–OOH intermediates translates to the higher styrene oxide selectivity observed for MIL-101(Cr). Secondary styrene oxide and benzaldehyde conversions are observed over both analogs, but the former is more prevalent over MIL-101(Fe) due to higher Lewis/Brønsted acid site density and strength compared to MIL-101(Cr). Recyclability experiments combined with characterization via XRD, SEM/EDXS, and FT-IR and UV-vis spectroscopies show that the nature of MIL-101(Fe) sites does not change significantly with each cycle, whereas MIL-101(Cr) suffers from metal leaching, which impacts styrene conversion rates and product distribution. Both catalysts require active site regeneration, though MIL-101(Fe) sites are more susceptible to reactivation, even under mild conditions. Finally, examination of styrene conversion for three unique synthesized phases of MIL-101(Cr) rationalizes that nodal defects are largely responsible for observed reactivity and selectivity but predispose the framework to metal leaching as a predominant deactivation mechanism.more » « less
