Two pathways and an isotope effect in H3+ formation following double ionization of methanol
Abstract The trihydrogen ion has a central role in creating complex molecules in the interstellar medium. Therefore, its formation and destruction mechanisms in high photon energy environments involving organic molecules are drawing significant experimental and theoretical attention. Here, we employ...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
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Wiley-VCH
2021-10-01
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| Series: | Natural Sciences |
| Subjects: | |
| Online Access: | https://doi.org/10.1002/ntls.10022 |
| _version_ | 1819240800486162432 |
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| author | Krishnendu Gope Ester Livshits Dror M. Bittner Roi Baer Daniel Strasser |
| author_facet | Krishnendu Gope Ester Livshits Dror M. Bittner Roi Baer Daniel Strasser |
| author_sort | Krishnendu Gope |
| collection | DOAJ |
| description | Abstract The trihydrogen ion has a central role in creating complex molecules in the interstellar medium. Therefore, its formation and destruction mechanisms in high photon energy environments involving organic molecules are drawing significant experimental and theoretical attention. Here, we employ a combination of time‐resolved ultrafast extreme‐ultraviolet pump and near‐infrared probe spectroscopy applied to the deuterated CH3OD methanol molecule. Similar to other double‐ionization studies, the isotopic labeling reveals two competing pathways for forming trihydrogen: A) H3++COH+ and B) H3++HCO+. We validate our high‐level ab initio nonadiabatic molecular dynamic simulations by showing that it closely reproduces the essential features of the measured kinetic energy release distribution and branching ratios of the two pathways of the deuterated system. The success of ab initio simulation in describing single photon double‐ionization allows for an unprecedented peek into the formation pathways for the undeuterated species, beyond present experimental reach. For this case, we find that the kinetic energy release of pathway B shifts to lower energies by more than 0.6 eV due to a dynamical isotope effect. We also determine the mechanism for trihydrogen formation from excited states of the dication and elucidate the isotope effect's role in the observed dynamics. |
| first_indexed | 2024-12-23T14:13:46Z |
| format | Article |
| id | doaj.art-33a9e599c4434829b56e14da399ce119 |
| institution | Directory Open Access Journal |
| issn | 2698-6248 |
| language | English |
| last_indexed | 2024-12-23T14:13:46Z |
| publishDate | 2021-10-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | Natural Sciences |
| spelling | doaj.art-33a9e599c4434829b56e14da399ce1192022-12-21T17:43:59ZengWiley-VCHNatural Sciences2698-62482021-10-0112n/an/a10.1002/ntls.10022Two pathways and an isotope effect in H3+ formation following double ionization of methanolKrishnendu Gope0Ester Livshits1Dror M. Bittner2Roi Baer3Daniel Strasser4Institute of Chemistry The Hebrew University of Jerusalem Jerusalem IsraelFritz Haber Research Center for Molecular Dynamics and the Institute of Chemistry The Hebrew University of Jerusalem Jerusalem IsraelInstitute of Chemistry The Hebrew University of Jerusalem Jerusalem IsraelFritz Haber Research Center for Molecular Dynamics and the Institute of Chemistry The Hebrew University of Jerusalem Jerusalem IsraelInstitute of Chemistry The Hebrew University of Jerusalem Jerusalem IsraelAbstract The trihydrogen ion has a central role in creating complex molecules in the interstellar medium. Therefore, its formation and destruction mechanisms in high photon energy environments involving organic molecules are drawing significant experimental and theoretical attention. Here, we employ a combination of time‐resolved ultrafast extreme‐ultraviolet pump and near‐infrared probe spectroscopy applied to the deuterated CH3OD methanol molecule. Similar to other double‐ionization studies, the isotopic labeling reveals two competing pathways for forming trihydrogen: A) H3++COH+ and B) H3++HCO+. We validate our high‐level ab initio nonadiabatic molecular dynamic simulations by showing that it closely reproduces the essential features of the measured kinetic energy release distribution and branching ratios of the two pathways of the deuterated system. The success of ab initio simulation in describing single photon double‐ionization allows for an unprecedented peek into the formation pathways for the undeuterated species, beyond present experimental reach. For this case, we find that the kinetic energy release of pathway B shifts to lower energies by more than 0.6 eV due to a dynamical isotope effect. We also determine the mechanism for trihydrogen formation from excited states of the dication and elucidate the isotope effect's role in the observed dynamics.https://doi.org/10.1002/ntls.10022AIMDCASPT2Coulomb explosiondouble‐ionizationdynamical isotope effectHHG |
| spellingShingle | Krishnendu Gope Ester Livshits Dror M. Bittner Roi Baer Daniel Strasser Two pathways and an isotope effect in H3+ formation following double ionization of methanol Natural Sciences AIMD CASPT2 Coulomb explosion double‐ionization dynamical isotope effect HHG |
| title | Two pathways and an isotope effect in H3+ formation following double ionization of methanol |
| title_full | Two pathways and an isotope effect in H3+ formation following double ionization of methanol |
| title_fullStr | Two pathways and an isotope effect in H3+ formation following double ionization of methanol |
| title_full_unstemmed | Two pathways and an isotope effect in H3+ formation following double ionization of methanol |
| title_short | Two pathways and an isotope effect in H3+ formation following double ionization of methanol |
| title_sort | two pathways and an isotope effect in h3 formation following double ionization of methanol |
| topic | AIMD CASPT2 Coulomb explosion double‐ionization dynamical isotope effect HHG |
| url | https://doi.org/10.1002/ntls.10022 |
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