Absorption Spectrum of Hydroperoxymethyl Thioformate: A Computational Chemistry Study
Hydroperoxymethyl thioformate (or HPMTF) is a compound relevant to the chemistry of sulfur in the marine atmosphere. The chemical cycling of this molecule in the atmosphere is still uncertain due in part to the lack of accurate knowledge of its photolytic behavior. Only approximations based on the p...
Saved in:
| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2025-01-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/30/2/338 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1832587847590215680 |
|---|---|
| author | David Catalán-Fenollosa Javier Carmona-García Ana Borrego-Sánchez Alfonso Saiz-Lopez Daniel Roca-Sanjuán |
| author_facet | David Catalán-Fenollosa Javier Carmona-García Ana Borrego-Sánchez Alfonso Saiz-Lopez Daniel Roca-Sanjuán |
| author_sort | David Catalán-Fenollosa |
| collection | DOAJ |
| description | Hydroperoxymethyl thioformate (or HPMTF) is a compound relevant to the chemistry of sulfur in the marine atmosphere. The chemical cycling of this molecule in the atmosphere is still uncertain due in part to the lack of accurate knowledge of its photolytic behavior. Only approximations based on the properties of its chromophores are used in previous studies. In this work, we calculated the absorption spectra of the molecule in gas and aqueous phases using the Nuclear Ensemble Approach (NEA) and the CASPT2 method. Furthermore, we used such information to obtain relative photolysis rates. We found that the chromophore approximation overestimates the photolysis rates in the gas phase by twice the value obtained with the NEA-CASPT2 protocol. Furthermore, for the aqueous phase, we predict a lower role of photolysis as compared to the gas phase. |
| format | Article |
| id | doaj-art-4e3a170b747f4bdcbff72b27954c9474 |
| institution | Kabale University |
| issn | 1420-3049 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj-art-4e3a170b747f4bdcbff72b27954c94742025-01-24T13:43:40ZengMDPI AGMolecules1420-30492025-01-0130233810.3390/molecules30020338Absorption Spectrum of Hydroperoxymethyl Thioformate: A Computational Chemistry StudyDavid Catalán-Fenollosa0Javier Carmona-García1Ana Borrego-Sánchez2Alfonso Saiz-Lopez3Daniel Roca-Sanjuán4Instituto de Ciencia Molecular, Universitat de València, Apartado 22085, 46071 Valencia, SpainInstituto de Ciencia Molecular, Universitat de València, Apartado 22085, 46071 Valencia, SpainInstituto de Ciencia Molecular, Universitat de València, Apartado 22085, 46071 Valencia, SpainDepartment of Atmospheric Chemistry and Climate, Institute of Physical Chemistry Blas Cabrera, Consejo Superior de Investigaciones Científicas, 28006 Madrid, SpainInstituto de Ciencia Molecular, Universitat de València, Apartado 22085, 46071 Valencia, SpainHydroperoxymethyl thioformate (or HPMTF) is a compound relevant to the chemistry of sulfur in the marine atmosphere. The chemical cycling of this molecule in the atmosphere is still uncertain due in part to the lack of accurate knowledge of its photolytic behavior. Only approximations based on the properties of its chromophores are used in previous studies. In this work, we calculated the absorption spectra of the molecule in gas and aqueous phases using the Nuclear Ensemble Approach (NEA) and the CASPT2 method. Furthermore, we used such information to obtain relative photolysis rates. We found that the chromophore approximation overestimates the photolysis rates in the gas phase by twice the value obtained with the NEA-CASPT2 protocol. Furthermore, for the aqueous phase, we predict a lower role of photolysis as compared to the gas phase.https://www.mdpi.com/1420-3049/30/2/338hydroperoxymethyl thioformateexcited statesabsorption spectrumphotolysisNuclear Ensemble ApproachCASPT2 |
| spellingShingle | David Catalán-Fenollosa Javier Carmona-García Ana Borrego-Sánchez Alfonso Saiz-Lopez Daniel Roca-Sanjuán Absorption Spectrum of Hydroperoxymethyl Thioformate: A Computational Chemistry Study Molecules hydroperoxymethyl thioformate excited states absorption spectrum photolysis Nuclear Ensemble Approach CASPT2 |
| title | Absorption Spectrum of Hydroperoxymethyl Thioformate: A Computational Chemistry Study |
| title_full | Absorption Spectrum of Hydroperoxymethyl Thioformate: A Computational Chemistry Study |
| title_fullStr | Absorption Spectrum of Hydroperoxymethyl Thioformate: A Computational Chemistry Study |
| title_full_unstemmed | Absorption Spectrum of Hydroperoxymethyl Thioformate: A Computational Chemistry Study |
| title_short | Absorption Spectrum of Hydroperoxymethyl Thioformate: A Computational Chemistry Study |
| title_sort | absorption spectrum of hydroperoxymethyl thioformate a computational chemistry study |
| topic | hydroperoxymethyl thioformate excited states absorption spectrum photolysis Nuclear Ensemble Approach CASPT2 |
| url | https://www.mdpi.com/1420-3049/30/2/338 |
| work_keys_str_mv | AT davidcatalanfenollosa absorptionspectrumofhydroperoxymethylthioformateacomputationalchemistrystudy AT javiercarmonagarcia absorptionspectrumofhydroperoxymethylthioformateacomputationalchemistrystudy AT anaborregosanchez absorptionspectrumofhydroperoxymethylthioformateacomputationalchemistrystudy AT alfonsosaizlopez absorptionspectrumofhydroperoxymethylthioformateacomputationalchemistrystudy AT danielrocasanjuan absorptionspectrumofhydroperoxymethylthioformateacomputationalchemistrystudy |