Trans-polyacetylene Oligomers Research Articles

Substituent Effect on the Electronic Structure and UV/Vis. Spectroscopic Properties of Polyacetylene Oligomers for Photovoltaic Devices: DFT and TD-DFT based investigations

Due to their promising opto-electronic properties, donor-π-acceptor (D-π-A) organic molecules have emerged as novel class of semiconducting photovoltaic materials. In this paper, we present a systematic study of substituent effect on electronic and absorption properties of the trans-polyacetylene oligomers, H-(CH=CH)n-H (n = 1, 2,······,13), as a function of the π-conjugation length. The HOMO-LUMO gap energies and maximum absorption wavelength (λmax) values of the oligomers connected to the donor and acceptor types of the substituents with varied π-conjugation length are correlated on the basis of the DFT and TD-DFT methods respectively. A non-linear behaviour of change in λmax with and without substituent as a function of n is observed. It is believed that such study can help to design D-π-A compounds for optoelectronic applications.

Structural and electrical properties of carbon-ion-implanted ultrananocrystalline diamond films**Project supported by the National Natural Science Foundation of China (Grant Nos. 50972129 and 50602039), the International Science Technology Cooperation Program of China (Grant No. 2014DFR51160), the National Key Research and Development Program of China (Grant No. 2016YFE0133200), European Unio’s Horizon 2020 Research and Innovation Staff Exchange (RISE) Scheme (Grant No. 734578),

We investigate the structural and electrical properties of carbon-ion-implanted ultrananocrystalline diamond (UNCD) films. Impedance spectroscopy measurements show that the impedance of diamond grains is relatively stable, while that of grain boundaries (GBs) (Rb) significantly increases after the C+ implantation, and decreases with the increase in the annealing temperature (Ta) from 650 °C to 1000 °C. This implies that the C+ implantation has a more significant impact on the conductivity of GBs. Conductive atomic force microscopy demonstrates that the number of conductive sites increases in GB regions at Ta above 900 °C, owing to the formation of a nanographitic phase confirmed by high-resolution transmission electronic microscopy. Visible-light Raman spectra show that resistive trans-polyacetylene oligomers desorb from GBs at Ta above 900 °C, which leads to lower Rb of samples annealed at 900 and 1000 °C. With the increase in Ta to 1000 °C, diamond grains become smaller with longer GBs modified by a more ordered nanographitic phase, supplying more conductive sites and leading to a lower Rb.

Theoretical investigation of second hyperpolarizability of trans-polyacetylene: Comparison between experimental and theoretical results for small oligomers.

The development of new conductive polymers nowadays is one of the most important technological areas in materials design. Computational investigation of desired properties in conductive polymers could save financial resources and time, but it is important to choose the methodology that produces good results comparing to experimental results. To verify the prediction of second hyperpolarizability (γ) in oligomers of Trans-Polyacetylene (TPA) by theoretical calculations, a series of semi-empirical, Hartree-Fock (HF), and Density Functional Theory (DFT) calculations were performed and analysed through linear fitting statistical analysis to investigate the accuracy of such theoretical predictions in comparison to the experimental ones. The results showed that HF and DFT methodologies do not describe γ with good accuracy, but the use of diffuse and polarizability functions in HF methodology provided better results than 3-21G and 6-31G functions. It was concluded that RM1 methodology better agrees with γ experimental results for TPA oligomers, and linear fitting statistical analysis is a useful tool to compare experimental and theoretical results.

Long-lived oscillatory incoherent electron dynamics in molecules: trans-polyacetylene oligomers

We identify an intriguing feature of the electron–vibrational dynamics of molecular systems via a computational examination of trans-polyacetylene oligomers. Here, via the vibronic interactions, the decay of an electron in the conduction band resonantly excites an electron in the valence band, and vice versa, leading to oscillatory exchange of electronic population between two distinct electronic states that lives for up to tens of picoseconds. The oscillatory structure is reminiscent of beating patterns between quantum states and is strongly suggestive of the presence of long-lived molecular electronic coherence. Significantly, however, a detailed analysis of the electronic coherence properties shows that the oscillatory structure arises from a purely incoherent process. These results were obtained by propagating the coupled dynamics of electronic and vibrational degrees of freedom in a mixed quantum-classical study of the Su–Schrieffer–Heeger Hamiltonian for polyacetylene. The incoherent process is shown to occur between degenerate electronic states with distinct electronic configurations that are indirectly coupled via a third auxiliary state by vibronic interactions. A discussion of how to construct electronic superposition states in molecules that are truly robust to decoherence is also presented.

Electronic coherence dynamics in trans-polyacetylene oligomers

Electronic coherence dynamics in trans-polyacetylene oligomers are considered by explicitly computing the time dependent molecular polarization from the coupled dynamics of electronic and vibrational degrees of freedom in a mean-field mixed quantum-classical approximation. The oligomers are described by the Su-Schrieffer-Heeger Hamiltonian and the effect of decoherence is incorporated by propagating an ensemble of quantum-classical trajectories with initial conditions obtained by sampling the Wigner distribution of the nuclear degrees of freedom. The electronic coherence of superpositions between the ground and excited and between pairs of excited states is examined for chains of different length, and the dynamics is discussed in terms of the nuclear overlap function that appears in the off-diagonal elements of the electronic reduced density matrix. For long oligomers the loss of coherence occurs in tens of femtoseconds. This time scale is determined by the decay of population into other electronic states through vibronic interactions, and is relatively insensitive to the type and class of superposition considered. By contrast, for smaller oligomers the decoherence time scale depends strongly on the initially selected superposition, with superpositions that can decay as fast as 50 fs and as slow as 250 fs. The long-lived superpositions are such that little population is transferred to other electronic states and for which the vibronic dynamics is relatively harmonic.

Femtosecond dynamics and laser control of charge transport in trans-polyacetylene

The induction of dc electronic transport in rigid and flexible trans-polyacetylene oligomers according to the omega versus 2omega coherent control scenario is investigated using a quantum-classical mean field approximation. The approach involves running a large ensemble of mixed quantum-classical trajectories under the influence of omega+2omega laser fields and choosing the initial conditions by sampling the ground-state Wigner distribution function for the nuclei. The vibronic couplings are shown to change the mean single-particle spectrum, introduce ultrafast decoherence, and enhance intramolecular vibrational and electronic relaxation. Nevertheless, even in the presence of significant couplings, limited coherent control of the electronic dynamics is still viable, the most promising route involving the use of femtosecond pulses with a duration that is comparable to the electronic dephasing time. The simulations offer a realistic description of the behavior of a simple coherent control scenario in a complex system and provide a detailed account of the femtosecond photoinduced vibronic dynamics of a conjugated polymer.

Laser-induced currents along molecular wire junctions

The treatment of the previous paper is extended to molecular wires. Specifically, the effect of electron-vibrational interactions on the electronic transport induced by femtosecond omega+2omega laser fields along unbiased molecular nanojunctions is investigated. For this, the photoinduced vibronic dynamics of trans-polyacetylene oligomers coupled to macroscopic metallic leads is followed in a mean-field mixed quantum-classical approximation. A reduced description of the dynamics is obtained by introducing projective lead-molecule couplings and deriving an effective Schrodinger equation satisfied by the orbitals in the molecular region. Two possible rectification mechanisms are identified and investigated. The first one relies on near-resonance photon-absorption and is shown to be fragile to the ultrafast electronic decoherence processes introduced by the wire's vibrations. The second one employs the dynamic Stark effect and is demonstrated to be highly efficient and robust to electron-vibrational interactions.

Quantization of the dipole moment and of the end charges in push-pull polymers

A theorem for end-charge quantization in quasi-one-dimensional stereoregular chains is formulated and proved. It is a direct analog of the well-known theorem for surface charges in physics. The theorem states the following: (1) Regardless of the end groups, in stereoregular oligomers with a centrosymmetric bulk, the end charges can only be a multiple of 12 and the longitudinal dipole moment per monomer p can only be a multiple of 12 times the unit length a in the limit of long chains. (2) In oligomers with a noncentrosymmetric bulk, the end charges can assume any value set by the nature of the bulk. Nonetheless, by modifying the end groups, one can only change the end charge by an integer and the dipole moment p by an integer multiple of the unit length a. (3) When the entire bulk part of the system is modified, the end charges may change in an arbitrary way; however, if upon such a modification the system remains centrosymmetric, the end charges can only change by multiples of 12 as a direct consequence of (1). The above statements imply that-in all cases-the end charges are uniquely determined, modulo an integer, by a property of the bulk alone. The theorem's origin is a robust topological phenomenon related to the Berry phase. The effects of the quantization are first demonstrated in toy LiF chains and then in a series of trans-polyacetylene oligomers with neutral and charge-transfer end groups.

Role of Charge Transfer Interaction and Conjugation Length on Electrical Polarizability of Doped trans-Polyacetylene Oligomers

The effects of charge transfer and molecular chain length on the electrical polarizability of doped trans-polyacetylene oligomers have been investigated using a series of quantum chemical methods ranging from Hartree-Fock to current density functional theory. Polarizability tensors of pristine and metal-doped trans-polyacetylene oligomers have been estimated. The nature of variations of polarizability tensor components are quite different for pristine and doped oligomers. For doped samples, distinct minima in the average static polarizabilities per acetylene unit have been observed. The results suggest that the competitive role of charge-transfer interaction and oligomer chain length are responsible for the observed minima. To simulate the ab initio results on polarizability variation, we propose a mathematical model that describes the minima quite satisfactorily.

Effective Hamiltonian for conjugated polyenes based on the ground state single-electron density matrix

A method for constructing effective Hamiltonians using the information contained in the ground state reduced single-electron density matrices for many-electron systems is proposed and applied to trans-polyacetylene oligomers C 2 n H 2 n+2 with n = 4−24. The resulting effective Hamiltonian for π electrons, expanded in the basis set of natural atomic orbitals (NAOs) with nearest neighbor transfer integrals, reproduce accurately the Hartree-Fock ground state density matrices.

Metal/conjugated polymer interfaces: A theoretical investigation of the interaction between aluminum and trans-polyacetylene oligomers

Molecular model systems are used to quantum chemically investigate the interface between aluminum and trans-polyacetylene. Modifications to the chemical and electronic structure of trans-polyacetylene oligomers upon interaction with a submonolayer of aluminum are studied at the semiempirical and ab initio Hartree–Fock levels. An aluminum atom is found to react strongly with a carbon atom of the trans-polyacetylene chain to form a heteropolar covalent bond. In this process, the binding carbon evolves from an sp2- to an sp3-hybridized electronic structure. Significant contributions from Al 3s and 3p atomic orbitals are found in the frontier molecular orbitals in aluminum/polyene complexes. This results in the fact that despite the presence of sp3 sites due to Al–C bonds, which reduces π conjugation along the chain, a large degree of delocalization in π levels is maintained. Our calculations are discussed in relation to experimental ultraviolet photoelectron spectra (UPS) taken during initial stages of aluminum deposition on oxygen-free films of trans-polyacetylene oligomers.