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A SA-CASSCF and MS-CASPT2 study on the electronic structure of nitrosobenzene and its relation to its dissociation dynamics
- Source :
- Journal of Chemical Physics, Journal of Chemical Physics, American Institute of Physics, 2021, 154 (4), pp.044307. ⟨10.1063/5.0033181⟩
- Publication Year :
- 2021
- Publisher :
- HAL CCSD, 2021.
-
Abstract
- The photodissociation channels of nitrosobenzene (PhNO) induced by a 255 nm photolytic wavelength have been studied using the complete active space self-consistent method and the multistate second-order multiconfigurational perturbation theory. It is found that there exists a triplet route for photodissociation of the molecule. The reaction mechanism consists of a complex cascade of nonadiabatic electronic transitions involving triple and double conical intersections as well as intersystem crossing. Several of the relevant states (S2, S4, and S5 states) correspond to double excitations. It is worth noting that the last step of the photodissociation implies an internal conversion process. The experimentally observed velocity pattern of the NO fragment is a signature of such a conical intersection.
- Subjects :
- Physics
010304 chemical physics
Photodissociation
General Physics and Astronomy
Electronic structure
Conical intersection
010402 general chemistry
Internal conversion (chemistry)
01 natural sciences
Molecular physics
Dissociation (psychology)
0104 chemical sciences
Nitrosobenzene
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
chemistry.chemical_compound
Intersystem crossing
chemistry
0103 physical sciences
medicine
Complete active space
Physics::Chemical Physics
Physical and Theoretical Chemistry
medicine.symptom
ComputingMilieux_MISCELLANEOUS
Subjects
Details
- Language :
- English
- ISSN :
- 00219606 and 10897690
- Database :
- OpenAIRE
- Journal :
- Journal of Chemical Physics, Journal of Chemical Physics, American Institute of Physics, 2021, 154 (4), pp.044307. ⟨10.1063/5.0033181⟩
- Accession number :
- edsair.doi.dedup.....ab64e515ea0dd760db2aedec60f905f6