Photodissociation of Cr(CO)4bpy$$ \mathrm{Cr}{\left(\mathrm{CO}\right)}_4\mathrm{bpy} $$: A Non‐Adiabatic Dynamics Investigation
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| Format: | Artículo Open Access |
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Wiley
2025
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| _version_ | 1867010975397314561 |
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| author | Bartosz Ciborowski Morgane Vacher |
| author_facet | Bartosz Ciborowski Morgane Vacher Bartosz Ciborowski Morgane Vacher |
| collection | Wiley Open Access |
| contents | Photodissociation of Cr(CO)4bpy$$ \mathrm{Cr}{\left(\mathrm{CO}\right)}_4\mathrm{bpy} $$: A Non‐Adiabatic Dynamics Investigation Bartosz Ciborowski Morgane Vacher Journal of Computational Chemistry ABSTRACT Carbonyl complexes of metals with an α‐diimine ligand exhibit both emission and ligand‐selective photodissociation from MLCT states. Studying this photodissociative mechanism is challenging for experimental approaches due to an ultrafast femtosecond timescale and spectral overlap of multiple photoproducts. The photochemistry of a prototypical system is investigated with non‐adiabatic dynamic simulations. Obtained 86 fs lifetime of the bright state and 13% quantum yield are in good agreement with experimental data. The present simulations suggest a ballistic mechanism of photodissociation, which is irrespective of the occupied electronic state. This is in contrast to the previously established mechanism of competitive intersystem crossing and dissociation. Selectivity of axial photodissociation is shown to be caused by the absence of an avoided crossing in the equatorial direction. 10.1002/jcc.70021 http://creativecommons.org/licenses/by/4.0/ |
| doi_str_mv | 10.1002/jcc.70021 |
| format | Artículo Open Access |
| id | wiley_oa_10_1002_jcc_70021 |
| institution | Wiley Open Access |
| license_str_mv | http://creativecommons.org/licenses/by/4.0/ |
| publishDate | 2025 |
| publisher | Wiley |
| record_format | wiley_oa |
| spellingShingle | Photodissociation of Cr(CO)4bpy$$ \mathrm{Cr}{\left(\mathrm{CO}\right)}_4\mathrm{bpy} $$: A Non‐Adiabatic Dynamics Investigation Bartosz Ciborowski Morgane Vacher Journal of Computational Chemistry Photodissociation of Cr(CO)4bpy$$ \mathrm{Cr}{\left(\mathrm{CO}\right)}_4\mathrm{bpy} $$: A Non‐Adiabatic Dynamics Investigation Bartosz Ciborowski Morgane Vacher Journal of Computational Chemistry ABSTRACT Carbonyl complexes of metals with an α‐diimine ligand exhibit both emission and ligand‐selective photodissociation from MLCT states. Studying this photodissociative mechanism is challenging for experimental approaches due to an ultrafast femtosecond timescale and spectral overlap of multiple photoproducts. The photochemistry of a prototypical system is investigated with non‐adiabatic dynamic simulations. Obtained 86 fs lifetime of the bright state and 13% quantum yield are in good agreement with experimental data. The present simulations suggest a ballistic mechanism of photodissociation, which is irrespective of the occupied electronic state. This is in contrast to the previously established mechanism of competitive intersystem crossing and dissociation. Selectivity of axial photodissociation is shown to be caused by the absence of an avoided crossing in the equatorial direction. 10.1002/jcc.70021 http://creativecommons.org/licenses/by/4.0/ |
| title | Photodissociation of Cr(CO)4bpy$$ \mathrm{Cr}{\left(\mathrm{CO}\right)}_4\mathrm{bpy} $$: A Non‐Adiabatic Dynamics Investigation |
| topic | Journal of Computational Chemistry |
| url | https://onlinelibrary.wiley.com/doi/10.1002/jcc.70021 |