Computational Study of the 1,3-Dipolar Cycloaddition between Criegee Intermediates and Linalool: Atmospheric
Rocío Durán1, César Barrales-Martínez2,3, Jocelyn Solorza3
1Departamento de Química Ambiental, Facultad de Ciencias, Universidad Católica de la Santísima Concepción, Concepción 4090541, Chile.
Biogenic volatile organic compounds like linalool play a key role in atmospheric chemistry. This study reveals specific reaction pathways and their impact on tropospheric ozone and aerosol formation.
Area of Science:
- Atmospheric Chemistry
- Climate Dynamics
- Biogenic Emissions
Background:
- Biogenic volatile organic compounds (BVOCs) emissions regulate atmospheric chemistry and climate.
- Linalool ozonolysis and secondary organic aerosol (SOA) formation are critical processes.
Purpose of the Study:
- Investigate the role of linalool ozonolysis in atmospheric processes.
- Elucidate the mechanisms of 1,3-dipolar cycloadditions involving Criegee intermediates.
Main Methods:
- Density functional theory (DFT) calculations.
- Molecular dynamics (MD) simulations.
- Conceptual DFT reactivity indices and activation strain model.
Main Results:
- Identified four key reactions with high rate constants for linalool ozonolysis byproducts.
- Determined electron flux from linalool to Criegee intermediates.
- Showed favorable water molecule adsorption by cycloaddition adducts.
Conclusions:
- Linalool's reactivity influences tropospheric ozone and SOA formation.
- Computational methods provide mechanistic insights into atmospheric reactions.
- Adducts formed can impact atmospheric water interactions.
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