Исследование роли конформации олигомеров политиофена на их электронные и магнитные свойства

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Abstract

Из сопоставления данных, теоретически полученных с использованием методов теории функционала плотности (ТФП) и электронного парамагнитного резонанса (ЭПР) с экспериментальными результатами установлены корреляции электронных и магнитно-резонансных параметров спиновых носителей заряда в олигомерах потитиофена с разной степенью их полимеризации и конформации.

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В. И. Криничный

Федеральный исследовательский центр проблем химической физики и медицинской химии РАН (ФИЦ ПХФ МХ РАН)

Author for correspondence.
Email: kivi@icp.ac.ru
Russian Federation, проспект академика Н.Н. Семенова, 1, Черноголовка, 142432

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2. Fig. 1. Evolution of the initial zone structure of neutral polythiophene (a) at leaving its chain of elementary charge |e|, accompanied by the formation of polarons P+* (b) or P-* (c) with the corresponding energy levels Ei in the forbidden zone.

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3. Fig. 2. Relative charge (a) and electron spin (b) densities on hydrogen and sulfur atoms in neutral (a) and oxidized (b) 12-dimensional polythiophene (PT) oligomers optimized in the framework of density functional formalism/theory (DFT), calculated by the Malliken method in the Orca package environment using the B3LYP functional in conjunction with the EPRNMR module, as well as the EPRII basis sets for 1H and 12S atoms and TZVPP for 32S. In (b), an eight-strand polaron with a quinoid/trans conformation carrying spin S = 1/2 and elementary positive charge +e is depicted. The sums of both densities on all atoms (including also 12S not shown here) are zero (a) and one (b).

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4. Fig. 3. Variation of charge (a, b, d, e, g, h) and spin (c, f, i) densities on hydrogen (circles), sulfur (triangles), and carbon (squares) nuclei along the main x-axis of neutral (unfilled dots) and oxidized (filled dots) within a 12-dimensional polythiophene oligomer (schematically shown above), optimized in the framework of the density functional formalism/theory (DFT), calculated by the Malliken method in the Orca program environment.

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5. Fig. 4. Variation of the forbidden band width from the dimensionality of polythiophene oligomers optimized in the framework of the density functional formalism/theory (DFT) defined as the difference Eg = EHOMO - ELUMO of the corresponding VZMO and NSMO energy levels calculated in the Malliken approximation in the Orca package environment. In the upper part are plots of the isosurfaces of the indicated energy levels calculated for the 7-dimensional polythiophene oligomer. The upper solid, dashed and lower solid lines show the dependences calculated from equation (1) with the coefficients a0 = 2.078 eV, b = 5.89 eV, c = 1.67, a0 = 2.070 eV, b = 5.45 eV, c = 1.59 and a0 = 3.153 eV, b = 5.03 eV, c = 3.15, respectively.

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6. Fig. 5. Dependence of the isotropic spin-spin superfine interaction constants, Aiso, and g-factor, giso, of polarons with spin S = 1/2 and elementary positive charge +e, on the chain length of the polythiophene oligomer, calculated in the Orca package environment using the B3LYP functional together with the EPRNMR module, as well as the EPRII basis sets for 1H and 12S atoms and TZVPP for 32S. The inset shows the 2-mm band EPR spectrum calculated for 12-mer oligothiophene using the EasySpin program and the corresponding data shown in Table 2. The lower and upper dependencies are calculated from Equation (1) with a0 = 0.47 MHz, b = 83.62 MHz, c = 1.17 and a0 = 2.00162, b = 8.71 ∙ 104, c = 5.31.

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