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Resolving the Singlet Excited State Manifold of Benzophenone by First-Principles Simulations and Ultrafast Spectroscopy
- Source :
- Journal of Chemical Theory and Computation, Journal of Chemical Theory and Computation, 2018, 14 (5), pp.2570-2585. ⟨10.1021/acs.jctc.7b01208⟩, Journal of Chemical Theory and Computation, American Chemical Society, 2018, 14 (5), pp.2570-2585. ⟨10.1021/acs.jctc.7b01208⟩
- Publication Year :
- 2018
- Publisher :
- HAL CCSD, 2018.
-
Abstract
- Accurate characterization of the high-lying excited state manifolds of organic molecules is of fundamental importance for the interpretation of the rich response detected in time-resolved nonlinear electronic spectroscopies. Here, we have characterized the singlet excited state manifold of benzophenone (BP), a versatile organic photoinitiator and a well-known DNA photosensitizer. Benchmarks of various multiconfigurational/multireference (RASSCF/PT2) and time-dependent density functional theory (TD-DFT) approaches allowed assignments of experimental linear absorption signals of BP in the ultraviolet (UV) region, with unprecedented characterization of ground state absorptions in the far UV. Experimental transient absorption spectra obtained by UV-vis pump-probe spectroscopy at very short time delays are shown to be directly comparable to theoretical estimates of excited state absorptions (from the low-lying nOπ∗ and π π∗ singlet states) in the Franck-Condon region. Multireference computations provided reliable interpretation of the PP spectra, with TD-DFT results yielding a fair agreement as long as electronic transitions featuring double excitations contributions are not involved. These results lay the groundwork for further computational studies and interpretation of experimental nonlinear electronic spectra of benzophenone in more complex systems, such as BP/DNA adducts.
- Subjects :
- 0307 Theoretical And Computational Chemistry
DNA-PHOTOSENSITIZATION
2-DIMENSIONAL ELECTRONIC SPECTROSCOPY
Physics, Atomic, Molecular & Chemical
010402 general chemistry
medicine.disease_cause
01 natural sciences
Molecular physics
ABSORPTION-SPECTRA
DENSITY-FUNCTIONAL THEORY
PHOTOEXCITED BENZOPHENONE
chemistry.chemical_compound
0103 physical sciences
Ultrafast laser spectroscopy
medicine
Benzophenone
PRIMARY PHOTOISOMERIZATION EVENT
WAVE-FUNCTIONS
Singlet state
Physics::Chemical Physics
Physical and Theoretical Chemistry
Spectroscopy
ComputingMilieux_MISCELLANEOUS
Physics
Science & Technology
Chemical Physics
010304 chemical physics
Chemistry, Physical
Computer Science Applications1707 Computer Vision and Pattern Recognition
0104 chemical sciences
Computer Science Applications
MOLECULAR-ORBITAL METHODS
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
Chemistry
chemistry
Excited state
Physical Sciences
ANO BASIS-SETS
Density functional theory
Ground state
Ultraviolet
OPTICAL SPECTROSCOPY
Subjects
Details
- Language :
- English
- ISSN :
- 15499618 and 15499626
- Database :
- OpenAIRE
- Journal :
- Journal of Chemical Theory and Computation, Journal of Chemical Theory and Computation, 2018, 14 (5), pp.2570-2585. ⟨10.1021/acs.jctc.7b01208⟩, Journal of Chemical Theory and Computation, American Chemical Society, 2018, 14 (5), pp.2570-2585. ⟨10.1021/acs.jctc.7b01208⟩
- Accession number :
- edsair.doi.dedup.....e574e37ca8d66a146379e3b15700c43c