Factors governing $${\rm H}_{3}^{+}$$ H 3 + formation from methyl halogens and pseudohalogens
Abstract The formation of $${\rm H}_{3}^{+}$$ H 3 + following the double ionization of small organic compounds via a roaming mechanism, which involves the generation of H2 and subsequent proton abstraction, has recently garnered significant attention. Nonetheless, a cohesive model explaining trends...
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Nature Portfolio
2025-01-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-55065-5 |
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| author | Jacob Stamm Swati S. Priyadarsini Shawn Sandhu Arnab Chakraborty Jun Shen Sung Kwon Jesse Sandhu Clayton Wicka Arshad Mehmood Benjamin G. Levine Piotr Piecuch Marcos Dantus |
| author_facet | Jacob Stamm Swati S. Priyadarsini Shawn Sandhu Arnab Chakraborty Jun Shen Sung Kwon Jesse Sandhu Clayton Wicka Arshad Mehmood Benjamin G. Levine Piotr Piecuch Marcos Dantus |
| author_sort | Jacob Stamm |
| collection | DOAJ |
| description | Abstract The formation of $${\rm H}_{3}^{+}$$ H 3 + following the double ionization of small organic compounds via a roaming mechanism, which involves the generation of H2 and subsequent proton abstraction, has recently garnered significant attention. Nonetheless, a cohesive model explaining trends in the yield of $${\rm H}_{3}^{+}$$ H 3 + characterizing these unimolecular reactions is yet to be established. We report yield and femtosecond time-resolved measurements following the strong-field double ionization of CH3X molecules, where X = OD, Cl, NCS, CN, SCN, and I. These measurements, combined with double-ionization-potential equation-of-motion coupled-cluster ab initio calculations used to determine the geometries and energetics of CH3X2+ dications, are employed to identify the key factors governing the formation of $${\rm H}_{3}^{+}$$ H 3 + in certain doubly ionized CH3X species and its absence in others. We also carry out ab initio molecular dynamics simulations to obtain detailed microscopic insights into the mechanism, yields, and timescales of $${\rm H}_{3}^{+}$$ H 3 + production. We find that the excess relaxation energy released after double ionization of CH3X molecules combined with substantial geometrical distortion that favors H2 formation prior to proton abstraction boost the generation of $${\rm H}_{3}^{+}$$ H 3 + . Our study provides useful guidelines for examining alternative sources of $${\rm H}_{3}^{+}$$ H 3 + in the universe. |
| format | Article |
| id | doaj-art-643e7c1645ee4213ad5adf874e08e091 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-643e7c1645ee4213ad5adf874e08e0912025-01-12T12:30:10ZengNature PortfolioNature Communications2041-17232025-01-0116111410.1038/s41467-024-55065-5Factors governing $${\rm H}_{3}^{+}$$ H 3 + formation from methyl halogens and pseudohalogensJacob Stamm0Swati S. Priyadarsini1Shawn Sandhu2Arnab Chakraborty3Jun Shen4Sung Kwon5Jesse Sandhu6Clayton Wicka7Arshad Mehmood8Benjamin G. Levine9Piotr Piecuch10Marcos Dantus11Department of Chemistry, Michigan State UniversityDepartment of Chemistry, Michigan State UniversityDepartment of Chemistry, Michigan State UniversityDepartment of Chemistry, Michigan State UniversityDepartment of Chemistry, Michigan State UniversityDepartment of Chemistry, Michigan State UniversityDepartment of Chemistry, Michigan State UniversityDepartment of Chemistry, Michigan State UniversityDepartment of Chemistry, Stony Brook UniversityDepartment of Chemistry, Stony Brook UniversityDepartment of Chemistry, Michigan State UniversityDepartment of Chemistry, Michigan State UniversityAbstract The formation of $${\rm H}_{3}^{+}$$ H 3 + following the double ionization of small organic compounds via a roaming mechanism, which involves the generation of H2 and subsequent proton abstraction, has recently garnered significant attention. Nonetheless, a cohesive model explaining trends in the yield of $${\rm H}_{3}^{+}$$ H 3 + characterizing these unimolecular reactions is yet to be established. We report yield and femtosecond time-resolved measurements following the strong-field double ionization of CH3X molecules, where X = OD, Cl, NCS, CN, SCN, and I. These measurements, combined with double-ionization-potential equation-of-motion coupled-cluster ab initio calculations used to determine the geometries and energetics of CH3X2+ dications, are employed to identify the key factors governing the formation of $${\rm H}_{3}^{+}$$ H 3 + in certain doubly ionized CH3X species and its absence in others. We also carry out ab initio molecular dynamics simulations to obtain detailed microscopic insights into the mechanism, yields, and timescales of $${\rm H}_{3}^{+}$$ H 3 + production. We find that the excess relaxation energy released after double ionization of CH3X molecules combined with substantial geometrical distortion that favors H2 formation prior to proton abstraction boost the generation of $${\rm H}_{3}^{+}$$ H 3 + . Our study provides useful guidelines for examining alternative sources of $${\rm H}_{3}^{+}$$ H 3 + in the universe.https://doi.org/10.1038/s41467-024-55065-5 |
| spellingShingle | Jacob Stamm Swati S. Priyadarsini Shawn Sandhu Arnab Chakraborty Jun Shen Sung Kwon Jesse Sandhu Clayton Wicka Arshad Mehmood Benjamin G. Levine Piotr Piecuch Marcos Dantus Factors governing $${\rm H}_{3}^{+}$$ H 3 + formation from methyl halogens and pseudohalogens Nature Communications |
| title | Factors governing $${\rm H}_{3}^{+}$$ H 3 + formation from methyl halogens and pseudohalogens |
| title_full | Factors governing $${\rm H}_{3}^{+}$$ H 3 + formation from methyl halogens and pseudohalogens |
| title_fullStr | Factors governing $${\rm H}_{3}^{+}$$ H 3 + formation from methyl halogens and pseudohalogens |
| title_full_unstemmed | Factors governing $${\rm H}_{3}^{+}$$ H 3 + formation from methyl halogens and pseudohalogens |
| title_short | Factors governing $${\rm H}_{3}^{+}$$ H 3 + formation from methyl halogens and pseudohalogens |
| title_sort | factors governing rm h 3 h 3 formation from methyl halogens and pseudohalogens |
| url | https://doi.org/10.1038/s41467-024-55065-5 |
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