التفاصيل البيبلوغرافية
| العنوان: |
Ultrafast CO 2 photodissociation in the energy region of the lowest Rydberg series. |
| المؤلفون: |
Triana JF; Department of Physics, Universidad de Santiago de Chile, Av. Victor Jara 3493, Estación Central, Chile. johan.triana@usach.cl., Peláez D; Institut des Sciences Moléculaires d'Orsay (ISMO), Université Paris-Saclay, Orsay, France. daniel.pelaez-ruiz@universite-paris-saclay.fr., Hochlaf M; Université Gustave Eiffel, COSYS/LISIS, 5 Bd Descartes 77454, Champs-sur-Marne, France. majdi.hochlaf@univ-eiffel.fr., Sanz-Vicario JL; Grupo de Física Atómica y Molecular, Instituto de Física, Universidad de Antioquia, Medellín, Colombia. jose.sanz@udea.edu.co. |
| المصدر: |
Physical chemistry chemical physics : PCCP [Phys Chem Chem Phys] 2022 Jun 08; Vol. 24 (22), pp. 14072-14084. Date of Electronic Publication: 2022 Jun 08. |
| نوع المنشور: |
Journal Article |
| اللغة: |
English |
| بيانات الدورية: |
Publisher: Royal Society of Chemistry Country of Publication: England NLM ID: 100888160 Publication Model: Electronic Cited Medium: Internet ISSN: 1463-9084 (Electronic) Linking ISSN: 14639076 NLM ISO Abbreviation: Phys Chem Chem Phys Subsets: PubMed not MEDLINE; MEDLINE |
| أسماء مطبوعة: |
Original Publication: Cambridge [England] : Royal Society of Chemistry, c1999- |
| مستخلص: |
We present a detailed theoretical survey of the electronic structure of excited states of the CO 2 molecule, with the aim of providing a well-defined theoretical framework for the quantum dynamical studies at energies beyond 12 eV from the ground state. One of the major goals of our work is to emphasize the need for dealing with the presence of both molecular valence and Rydberg states. Although a CASSCF/MRCI approach can be used to appropriately describe the lowest-lying valence states, it becomes incapable of describing the upper electronic states due to the exceedingly large number of electronic excitations required. To circumvent this we employ instead the EOM-CCSD monoconfigurational method to describe the manifold of both valence and Rydberg states in the Franck-Condon region and then a matching procedure to connect these EOM-CCSD eigensolutions with those obtained from CASSCF/MRCI in the outer region, thus ensuring the correct asymptotic behavior. Within this hybrid level of theory, we then analyze the role of valence and Rydberg states in the dynamical mechanism of the photodissociation of quasi-linear CO 2 into CO + O fragments, by considering a simple but effective 1D multistate non-adiabatic model for the ultrafast C-O bond break up. We show evidence that the metastability of the Rydberg states must be accounted for in the ultrafast dynamics since they produce changes in the photodissociation yields within the first tens of fs. |
| تواريخ الأحداث: |
Date Created: 20220531 Latest Revision: 20220609 |
| رمز التحديث: |
20221213 |
| DOI: |
10.1039/d2cp01017h |
| PMID: |
35640548 |
| قاعدة البيانات: |
MEDLINE |
