Nitrous oxide (N 2 O) plays an important role in greenhouse warming and ozone depletion. Yung and Miller's zero point energy (ZPE) model for the photolysis of N 2 O isotopomers was able to explain atmospheric isotopomer distributions without invoking in situ chemical sources. Subsequent experiments showed enrichment factors twice those predicted by the ZPE model. In this article we calculate the UV spectrum of the key N 2 O isotopomers to quantify the influence of factors not included in the ZPE model, namely, the transition dipole surface, bending vibrational excitation, dynamics on the excited state potential surface, and factors related to isotopic substitution itself. The relative cross-sections are calculated as the Fourier transform of the correlation function of the initial vibrational wave function and the time-propagated wave function, using a Hermite expansion of the time evolution operator. The model uses the electronic structure data recently published by Balint-Kurti and co-workers and makes several predictions. (a) The absolute values of the enrichment factors decrease with increasing temperature. (b) Photolysis of N 2 O will produce "mass-independent" enrichment in the remaining sample. (c) Much of the enrichment is due to decreased heavy isotopomer cross-section over the entire absorption band, in contrast to the wavelength shift predicted by the ZPE model. Consequently, to within the error of the calculation, we predict only minor enrichments at λ < 182 nm. The smaller bending excursion of heavy isotopomers combines with the transition dipole surface to produce a smaller integrated cross-section. This effect is partially countered by the larger fraction of heavy isotopomers in excited bending states; the first three bending states have an integrated intensity ratio of ca. 1:3:6. The model agrees with available experimental enrichment factors and stratospheric balloon infrared remote sensing data to within the estimated error.
A series of new branched hole transporting materials (HTMs) containing two diphenylamine‐substituted carbazole fragments linked by a nonconjugated methylenebenzene unit is synthesized and tested in perovskite solar cells. Synthesis of the investigated materials is performed by a simple two‐step synthetic procedure providing a target product in high yield. The isolated materials demonstrate good thermal stability and majority of the investigated compounds exist in an amorphous state, which is advantageous as there is no risk of crystallization directly in the film. The highest charge drift mobility of µ0 = 4 × 10−4 cm2 V−1 s−1, measured at weak electric fields, is by ca. one order of magnitude higher than that of Spiro‐OMeTAD under identical conditions. From the perovskite solar cell testing results, it can be seen that performance of two new HTMs (V885 and V911) is on a par with Spiro‐OMeTAD. Due to the ease of synthesis, good thermal, optical and photophysical properties, this type of molecules hold great promise for practical application in commercial perovskite solar cells.
Realization of efficient deep-blue anthracene-based emitters with superior film-forming and charge transport properties is challenging. A series of non-symmetric 9,10-diphenylanthracenes (DPA) with phenyl and pentyl moieties at the 2nd position and alkyl groups at para positions of the 9,10-phenyls were synthesized and investigated. The non-symmetric substitution at the 2nd position enabled to improve film forming properties as compared to those of the unsubstituted DPA and resulted in glass transition temperatures of up to 92 °C. Small-sized and poorly conjugated substituents allowed to preserve emission in the deep blue range (<450 nm). Substitution at the 2nd position enabled to achieve high fluorescence quantum yields (up to 0.7 in solution, and up to 0.9 in the polymer host), although it caused an up to 10-fold increase in the intersystem crossing rate as compared to that of the unsubstituted DPA. Further optimization of the film forming properties achieved by varying the length of the alkyl groups attached at the 9,10-phenyls enabled to attain very high hole drift mobilities (∼5 × 10(-3)-1 × 10(-2) cm(2) V(-1) s(-1)) in the solution-processed amorphous films of the DPA compounds.
Synthesis and properties of new glass-forming 2-, 2,7-substituted carbazole dimers and trimers exhibiting ambipolar charge carrier transport are reported. The results of thorough evaluation of thermal, optical, and photoelectrical properties of the carbazole derivatives are presented. Additionally, a comparative experimental and theoretical analysis of the 2,7-substituted carbazole trimer with the 3,6-substituted analogue is performed. 2,7-Di(9-carbazolyl)-9-(2-ethylhexyl)carbazole was found to show very high electron mobility (μ e = 2 Â 10 -3 cm 2 V -1 s -1 at an electric field of 1.8 Â 10 5 V/cm) and reasonably high hole mobility (μ h = 8 Â 10 -4 cm 2 V -1 s -1 at an electric field of 1.8 Â 10 5 V/cm). 2-Substituted carbazole dimers also demonstrate bipolar conductive properties although with significantly lower charge carrier mobility values. The obtained carrier mobility values for the 2,7-substituted carbazole compound were found to be nearly 2 orders of magnitude higher than those for 3,6-substituted carbazole counterpart. The pronounced differences in carrier mobility are justified by DFT calculations indicating extended π-conjugation and a twice as large transition dipole moment in the 2,7-disubstituted carbazole derivative. This is also supported by the optical properties of the 2,7-disubstituted carbazole compound showing up to 5 times larger radiative relaxation rates, 3-fold increase in the fluorescence quantum yield and absorbance, as well as the reduced electron-vibronic system coupling as compared to the 3,6-substituted analogue. The prolonged molecular geometry and extended π-conjugation of the 2,7-substituted carbazole derivative facilitate more ordered and dense molecular packing and thus enhance intermolecular coupling in the solid films contributing to more efficient carrier hopping.
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