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Abstract
The second hyperpolarizabilities (γ) of the stilbene molecular switch in its trans and cis forms have been calculated using quantum chemistry methods to address their third-order nonlinear optical contrasts, to assess the reliability of lower-cost DFT methods, and to make comparisons with experiments. First, the reference CCSD(T) method shows that trans-stilbene presents a γ‖ value twice larger than its cis isomer (its γTHS value is 2.7 times larger). Among more cost-effective methods, reliable results are obtained at MP2 as well as with DFT, provided the CAM-B3LYP or ωB97X-D XCFs are employed. Supplementary DFT calculations have investigated the relationships between the accuracy of the exchange–correlation functionals, the fulfillment of Koopmans’ theorem, and the delocalization error, and they demonstrated that satisfying Koopmans’ theorem is not the condition for the best accuracy but that functionals with small delocalization errors are generally efficient. Using the selected CAM-B3LYP, large γ enhancements by about 70% (trans-stilbene) and 50% (cis-stilbene) have been evidenced when accounting for solvent effects using an implicit solvation model (IEFPCM), even for apolar solvents. Then, the frequency dispersion of the γ responses has been described using Bishop polynomial expansions, allowing comparisons with a broad set of experimental data. To a certain extent, no systematic agreement between the calculations and the measured values was found. On the one hand, the agreement is satisfactory for the γ(−ω;ω,−ω,ω) quantities, provided that the dominant vibrational contribution is taken into account. On the other hand, the agreement is poor for the γ(−2ω;ω,ω,0) and γ(−3ω;ω,ω,ω) quantities, while some inconsistencies between experimental values are also highlighted.
Original language | English |
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Article number | 14808 |
Pages (from-to) | 14808-14824 |
Number of pages | 17 |
Journal | PCCP : Physical Chemistry Chemical Physics |
Volume | 26 |
Issue number | 20 |
DOIs | |
Publication status | Published - 25 Apr 2024 |
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CÉCI – Consortium of high performance computing centers
CHAMPAGNE, B. (PI), Lazzaroni, R. (PI), Geuzaine , C. (CoI), Chatelain, P. (CoI) & Knaepen, B. (CoI)
1/01/18 → 31/12/22
Project: Research
Equipment
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High Performance Computing Technology Platform
Champagne, B. (Manager)
Technological Platform High Performance ComputingFacility/equipment: Technological Platform
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Congress of Theoretical Chemists of Latin Expression (Chimistes Théoriciens d'Expression Latine) 2024
Kaka, K. S. (Poster)
30 Jun 2024 → 5 Jul 2024Activity: Participating in or organising an event types › Participation in conference
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On the third-order nonlinear optical responses of cis and trans stilbenes – a quantum chemistry investigation
Kaka, K. S. (Speaker)
21 May 2024Activity: Talk or presentation types › Oral presentation
Press/Media
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University of Namur Reports Findings in Science (On the third-order nonlinear optical responses of cis and trans stilbenes - a quantum chemistry investigation)
21/05/24
1 item of Media coverage
Press/Media: Expert Comment