An sp-hybridized all-carboatomic ring, cyclo[18]carbon: Electronic structure, electronic spectrum, and optical nonlinearity

Liu, Zeyu; Tian, Laijin; Chen, Qinxue

doi:10.1016/j.carbon.2020.05.023

Cited by 886 publications

(649 citation statements)

References 37 publications

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“…The overlap function between the hole and electron distribution of the lowest two transitions (S 0 →S 1 , S 0 →S 2 ) was more than 60%, and both transitions were local excitation (LE) characters. For the convenience of readers, positions and oscillator strength, the excited-state analysis-based values, natural transition orbital pairs [ 29 ], the overlap of electron-hole isosurface density maps [ 30 ] of the 10 lowest-energy electronic transitions, and selected electron density contours of selected molecular orbitals were calculated by a multifunctional wavefunction analyzer (Multiwfn) version 3.7 [ 31 ] and shown in Supporting information (S2:TD-DFT with B3LYP/Def2-TZVPP, S3: TD-DFT with B3LYP/6-31G*, Figures S1–S10, Tables S1–S5 ). We found that the experimental measured PL was similar to the simulated fluoresce from S 1 , suggesting the experimental observed PL origin from the lowest exited state S 1 .…”

Section: Resultsmentioning

confidence: 99%

An Insight into the Excitation States of Small Molecular Semiconductor Y6

Zou

Wen

et al. 2020

Molecules

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Y6 is a new type of non-fullerene acceptor, which has led to power conversion efficiencies of single-junction polymer solar cells over 17% when combined with a careful choice of polymeric donors. However, the excited state characteristics of Y6, which is closely correlated with its opto-electronic applications, are not clear yet. In this work, we studied the excited state properties of the Y6 solution and Y6 film, by using steady-state and time-resolved spectroscopies as well as time-dependent density functional theory (TD-DFT) calculations. UV-Vis absorption and fluorescence simulation, natural transition orbitals (NTOs) and hole-electron distribution analysis of Y6 solution were performed for understanding the excitation properties of Y6 by using TD-DFT calculations. The lifetimes of the lowest singlet excited state in Y6 solution and film were estimated to be 0.98 and 0.8 ns, respectively. Combining the exciton lifetime and photoluminescence (PL) quantum yield, the intrinsic radiative decay lifetimes of Y6 in the solution and film were estimated, which were 1.3 and 10.5 ns for the Y6 solution and film, respectively. Long exciton lifetime (~0.8 ns) and intrinsic radiative decay lifetime (~10.5 ns) of Y6 film enable Y6 to be a good acceptor material for the application of polymer solar cells.

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Section: Resultsmentioning

confidence: 99%

An Insight into the Excitation States of Small Molecular Semiconductor Y6

Zou

Wen

et al. 2020

Molecules

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“…Moreover, the variation tendencies of the electron distribution, orbital energies and absorption spectrum with the nitro rotation were also presented by utilizing the single-point calculation based on rotation-distorted configurations. The electronic excitation types were confirmed from the hole-electron distributions drawn by the Multiwfn program (Liu Z. Y. et al, 2020). The C hole -C ele diagram is employed to smooth out the complex isosurfaces of hole and electron distribution.…”

Section: Computational Detailsmentioning

confidence: 99%

Proton Transfer and Nitro Rotation Tuned Photoisomerization of Artificial Base Pair-ZP

Cui

Zhao

et al. 2020

Front. Chem.

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Recently, the successful incorporation of artificial base pairs in genetics has made a significant progress in synthetic biology. The present work reports the proton transfer and photoisomerization of unnatural base pair ZP, which is synthesized from the pyrimidine analog 6-amino-5-nitro-3-(1-β-D-2′-deoxyribo-furanosyl)-2 (1H)-pyridone (Z) and paired with its Watson-Crick complement, the purine analog 2-amino-8-(1′-β-D-2′- deoxyribofuranosyl)-imidazo[1,2-a]-1,3,5-triazin-4(8H)-one (P). To explain the mechanism of proton transfer process, we constructed the relaxed potential energy surfaces (PESs) linking the different tautomers in both gas phase and solution. Our results show that the double proton transfer in the gas phase occurs in a concerted way both in S0 and S1 states, while the stepwise mechanism becomes more favorable in solution. The solvent effect can promote the single proton transfer, which undergoes a lower energy barrier in S1 state due to the strengthened hydrogen bond. In contrast to the excited state ultrafast deactivation process of the natural bases, there is no conical intersection between S0 and S1 states along the proton transfer coordinate to activate the decay mechanism in ZP. Of particular relevance to the photophysical properties, charge-transfer character is obviously related to the nitro rotation in S1 state. We characterized the molecular vibration effect on the electronic properties, which reveals the electronic excitation can be tuned by the rotation-induced structural distortion accompanied with the electron localization on nitro group.

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“…In Ref. [12] we have showed that the cyclo [18]carbon does not have absorption in the visible light region but has an extremely strong absorption peak in the ultraviolet region, is this still true when EEF is present? To investigate this point, we calculated excitation energies and oscillator strengths for the excited states of the cyclo [18]carbon under different EEF strengths using timedependent density functional theory (TDDFT), and then simulated electronic absorption spectrum using Gaussian broadening function with full width at half maximum of 2/3 eV, the resulting spectra are collectively shown in Fig.…”

Section: Electric Field Regulation On Homo-lumo Gap and Optical Absormentioning

confidence: 99%

“…[1][2][3] Significant theoretical efforts have been devoted to explore its characteristics and potential applications, [4][5][6][7][8][9][10] and recently we have comprehensively investigated its properties from different aspects, including bonding nature, aromaticity, electronic and vibrational spectra, non-linear optical property, intermolecular interaction, dynamic behavior and so on. [11][12][13][14] It is well known that external electric field (EEF) often has a great influence on chemical systems, and this has always been a hot research field. [15][16][17][18][19][20][21][22] The influence of EEF on pure carbon system, including fullerene, graphite, nanotube and their derivatives has been studied in many articles.…”

Section: Introductionmentioning

confidence: 99%

Ultrastrong Regulation Effect of Electric Field on Cyclo[18]carbon: Phenomenon and Essence

Tian¹,

Chen²

2020

Preprint

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Cyclo[18]carbon has a very unique geometry and electronic structure. Based on quantum chemistry calculations, we found that external electric field (EEF) has ultrastrong regulation effect on various aspects of the cyclo[18]carbon. The main findings are as follows: (1) The EEF evidently affects geometric structure of the cyclo[18]carbon, and the ring is greatly elongated when EEF exceeds 0.02 a.u. (2) The EEF causes a huge polarization in the charge distribution of the system, and large EEF can even make some in-plane  electrons nearly detached from the system (3) Presence of EEF significantly reduces HOMO-LUMO gap (4) The EEF not only greatly changes the position and intensity of the original absorption peak of the cyclo[18]carbon in the ultraviolet region, but large EEF also leads to a new absorption band in the visible light range and thus makes the cyclo[18]carbon show color. We made an in-depth explanation and discussion of the above phenomena from the aspects of energy, electronic structure, and atomic force. This work is not only of scientific interest in the interplay between the EEF and the cyclo[18]carbon, but may also open a novel path to explore different applications of this unusual molecule.

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An sp-hybridized all-carboatomic ring, cyclo[18]carbon: Electronic structure, electronic spectrum, and optical nonlinearity

Cited by 886 publications

References 37 publications

An Insight into the Excitation States of Small Molecular Semiconductor Y6

An Insight into the Excitation States of Small Molecular Semiconductor Y6

Proton Transfer and Nitro Rotation Tuned Photoisomerization of Artificial Base Pair-ZP

Ultrastrong Regulation Effect of Electric Field on Cyclo[18]carbon: Phenomenon and Essence

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