Bryan M. Wong

Optoelectronic and Excitonic Properties of Oligoacenes: Substantial Improvements from Range-Separated Time-Dependent Density Functional Theory

The optoelectronic and excitonic properties in a series of linear acenes (naphthalene up to heptacene) are investigated using range-separated methods within time-dependent density functional theory (TDDFT). In these rather simple systems, it is well-known that TDDFT methods using conventional hybrid functionals surprisingly fail in describing the low-lying La and Lb valence states, resulting in large, growing errors for the La state and an incorrect energetic ordering as a function of molecular size. In this work, we demonstrate that the range-separated formalism largely eliminates both of these errors and also provides a consistent description of excitonic properties in these systems. We further demonstrate that reoptimizing the percentage of Hartree−Fock exchange in conventional hybrids to match wave function-based benchmark calculations still yields serious errors, and a full 100% Hartree−Fock range separation is essential for simultaneously describing both of the La and Lb transitions. From an analysis of electron−hole transition density matrices, we finally show that conventional hybrid functionals over-delocalize excitons and underestimate quasiparticle energy gaps in the acene systems. The results of our present study emphasize the importance of both a range-separated and asymptotically correct contribution of exchange in TDDFT for investigating optoelectronic and excitonic properties, even for these simple valence excitations.

Coumarin dyes for dye-sensitized solar cells: A long-range-corrected density functional study

The excited-state properties in a series of coumarin solar cell dyes are investigated with a long-range-corrected (LC) functional which asymptotically incorporates Hartree-Fock exchange. Using time-dependent density functional theory (TDDFT), we calculate excitation energies, oscillator strengths, and excited-state dipole moments in each of the dyes as a function of the range-separation parameter mu. To investigate the acceptable range of mu and to assess the quality of the LC-TDDFT formalism, an extensive comparison is made between LC-BLYP excitation energies and approximate coupled-cluster singles and doubles calculations. When using a properly optimized value of mu, we find that the LC technique provides a consistent picture of charge-transfer excitations as a function of molecular size. In contrast, we find that the widely used B3LYP hybrid functional severely overestimates excited-state dipole moments and underestimates vertical excitation energies, especially for larger dye molecules. The results of the present study emphasize the importance of long-range exchange corrections in TDDFT for investigating the excited-state properties in solar cell dyes.

Stress Sensing in Polycaprolactone Films via an Embedded Photochromic Compound

A photochromic polymer exhibiting mechanochromic behavior is prepared by means of ring-opening polymerization (ROP) of ε-caprolactone by utilizing a difunctional indolinospiropyran as an initiator. The configuration of having the photochromic initiating species within the polymer backbone leads to a mechanochromic effect with deformation of polymer films leading to ring-opening of the spiro C−O bond to form the colored merocyanine. Active stress monitoring by dynamic mechanical analysis (DMA) in tension mode was used to probe the effects of UV irradiation on polymer films held under constant strain. Irradiation with UV light induces a negative change in the polymer stress of approximately 50 kPa. Finally, a model of the mechanochromic effect was performed using density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. A sharp increase in the relative molecular energy and the absorption wavelength as well as a drastic decrease in the spiro-oxygen atom charge occurred at a molecular elongation of >39%.

Color Detection Using Chromophore-Nanotube Hybrid Devices

We present a nanoscale color detector based on a single-walled carbon nanotube functionalized with azobenzene chromophores, where the chromophores serve as photoabsorbers and the nanotube as the electronic read-out. By synthesizing chromophores with specific absorption windows in the visible spectrum and anchoring them to the nanotube surface, we demonstrate the controlled detection of visible light of low intensity in narrow ranges of wavelengths. Our measurements suggest that upon photoabsorption, the chromophores isomerize from the ground state trans configuration to the excited state cis configuration, accompanied by a large change in dipole moment, changing the electrostatic environment of the nanotube. All-electron ab initio calculations are used to study the chromophore-nanotube hybrids and show that the chromophores bind strongly to the nanotubes without disturbing the electronic structure of either species. Calculated values of the dipole moments support the notion of dipole changes as the optical detection mechanism.

Optoelectronic Properties of Carbon Nanorings: Excitonic Effects from Time-Dependent Density Functional Theory

The electronic structure and size-scaling of optoelectronic properties in cycloparaphenylene carbon nanorings are investigated using time-dependent density functional theory (TDDFT). The TDDFT calculations on these molecular nanostructures indicate that the lowest excitation energy surprisingly becomes larger as the carbon nanoring size is increased, in contradiction with typical quantum confinement effects. In order to understand their unusual electronic properties, I performed an extensive investigation of excitonic effects by analyzing electron-hole transition density matrices and exciton binding energies as a function of size in these nanoring systems. The transition density matrices allow a global view of electronic coherence during an electronic excitation, and the exciton binding energies give a quantitative measure of electron-hole interaction energies in the nanorings. Based on overall trends in exciton binding energies and their spatial delocalization, I find that excitonic effects play a vital role in understanding the unique photoinduced dynamics in these carbon nanoring systems.

Electronically excited states of vitamin B12: benchmark calculations including time-dependent density functional theory and correlated ab initio methods.

Time-dependent density functional theory (TD-DFT) and correlated ab initio methods have been applied to explore the electronically excited states of vitamin B(12) (cyanocobalamin or CNCbl). Different experimental techniques have been used to probe the excited states of CNCbl, revealing many issues that remain poorly understood from an electronic structure point of view. Due to its efficient scaling with size, TD-DFT emerges as one of the most practical tools that can be used to study the electronic properties of these fairly complex molecules. However, the description of excited states is strongly dependent on the type of functional used in the calculations. In the present contribution, the choice of a proper functional for vitamin B(12) was evaluated in terms of its agreement with both experimental results and correlated ab initio calculations. Three different functionals, i.e., B3LYP, BP86, and LC-BLYP, were tested. In addition, the effect of the relative contributions of DFT and HF to the exchange-correlation functional was investigated as a function of the range-separation parameter, μ. The issues related to the underestimation of charge-transfer excitation energies by TD-DFT were validated by the Λ diagnostic, which measures the spatial overlap between occupied and virtual orbitals involved in the particular excitation. The nature of the low-lying excited states was also analyzed based on a comparison of TD-DFT and ab initio results. Based on an extensive comparison with experimental results and ab initio benchmark calculations, the BP86 functional was found to be the most appropriate in describing the electronic properties of CNCbl. Finally, an analysis of electronic transitions and reassignment of some excitations were discussed.

Synthesis, Characterization, and Computational Studies of Cycloparaphenylene Dimers

Two novel arene-bridged cycloparaphenylene dimers (1 and 2) were prepared using a functionalized precursor, bromo-substituted macrocycle 7. The preferred conformations of these dimeric structures were evaluated computationally in the solid state, as well as in the gas and solution phases. In the solid state, the trans configuration of 1 is preferred by 34 kcal/mol due to the denser crystal packing structure that is achieved. In contrast, in the gas phase and in solution, the cis conformation is favored by 7 kcal/mol (dimer 1) and 10 kcal/mol (dimer 2), with a cis to trans activation barrier of 20 kcal/mol. The stabilization seen in the cis conformations is attributed to the increased van der Waals interactions between the two cycloparaphenylene rings. These calculations indicate that the cis conformation is accessible in solution, which is promising for future efforts toward the synthesis of short carbon nanotubes (CNTs) via cycloparaphenylene monomers. In addition, the optoelectronic properties of these dimeric cycloparaphenylenes were characterized both experimentally and computationally for the first time.

Novel metal–organic framework linkers for light harvesting applications

Metal–organic frameworks (MOFs) are composed of organic linkers and coordinating metals that self-assemble to form a crystalline material with tunable nanoporosity. Their synthetic modularity and inherent long-range order create opportunities for use as new functional electronic materials. Using quantum mechanical computational methodologies we propose novel conjugated organic linkers that are capable of forming the same one-dimensional infinite metal-oxide secondary building units (SBUs) as the well-known IRMOF-74. This structural arrangement allows for the formation of a continuous π–π stacking network that should enable charge transport in fashion analogous to organic semiconductors. The structural and electronic properties (fundamental and optical gaps) of the isolated proposed linkers were modeled using a non-empirically tuned long-range corrected functional that leads to significantly improved results compared with experimental benchmarks. In addition, periodic hybrid density functional calculations were employed to model the extended MOF systems. Our results demonstrate how the electronic properties of MOFs can be readily modified to have favorable orbital alignments with known electron acceptors that should facilitate charge transfer. The predicted properties are in good agreement with experiment (i.e. UV-Vis absorption spectra), demonstrating the power of this computational approach for MOF design.

Nanoscale Effects on Heterojunction Electron Gases in GaN/AlGaN Core/Shell Nanowires

The electronic properties of heterojunction electron gases formed in GaN/AlGaN core/shell nanowires with hexagonal and triangular cross sections are studied theoretically. We show that at nanoscale dimensions, the nonpolar hexagonal system exhibits degenerate quasi-one-dimensional electron gases at the hexagon corners, which transition to a core-centered electron gas at lower doping. In contrast, polar triangular core/shell nanowires show either a nondegenerate electron gas on the polar face or a single quasi-one-dimensional electron gas at the corner opposite the polar face, depending on the termination of the polar face. More generally, our results indicate that electron gases in closed nanoscale systems are qualitatively different from their bulk counterparts.

Optical, Structural, and Numerical Investigations of GaAs/AlGaAs Core–Multishell Nanowire Quantum Well Tubes

The electronic properties of thin, nanometer scale GaAs quantum well tubes embedded inside the AlGaAs shell of a GaAs core-multishell nanowire are investigated using optical spectroscopies. Using numerical simulations to model cylindrically and hexagonally symmetric systems, we correlate these electronic properties with structural characterization by aberration-corrected scanning transmission electron microscopy of nanowire cross sections. These tubular quantum wells exhibit extremely high quantum efficiency and intense emission for extremely low submicrowatt excitation powers in both photoluminescence and photoluminescence excitation measurements. Numerical calculations of the confined eigenstates suggest that the electrons and holes in their ground states are confined to extremely localized one-dimensional filaments at the corners of the hexagonal structure which extend along the length of the nanowire.