Optical Excitation Energy Research Articles

Tight-binding model predicts exciton energetics and structure for photovoltaic molecules.

Conjugated molecules and polymers are being designed as acceptor and donor materials for organic photovoltaic (OPV) cells. OPV performance depends on generation of free charge carriers through dissociation of excitons, which are electron-hole pairs created when a photon is absorbed. Here, we develop a tight-binding model to describe excitons on homo-oligomers, alternating co-oligomers, and a non-fullerene acceptor - IDTBR. We parameterize our model using density functional theory (DFT) energies of neutral, anion, cation, and excited states of constituent moieties. A symmetric molecule like IDTBR has two ends where an exciton can sit; but the product wavefunction approximation for the exciton breaks symmetry. So, we introduce a tight-binding model with full correlation between electron and hole, which allows the exciton to coherently explore both ends of the molecule. Our approach predicts optical singlet excitation energies for oligomers of varying length as well as IDTBR in good agreement with time-dependent DFT and spectroscopic results.

Rutile, anatase, brookite and titania thin film from Hubbard corrected and hybrid DFT

As a benchmark, the structural, electronic and optical properties of the three main phases of TiO2 crystals have been calculated using Hubbard U correction and hybrid functional methods in density-functional theory. These calculations are compared concerning the available experimental observations on pristine TiO2 crystals. Modified hybrid functionals, particularly the PBE0 functional with 11.4% fraction of exact exchange, are shown to provide highly accurate atomic structures and also accurate electronic structure data, including optical excitation energies. With DFT + U, accurate optical spectra are also possible, but only if the Hubbard U is applied on the O 2p electrons exclusively. Furthermore, both methods, the 11.4%-PBE0 hybrid functional and the DFT + U p scheme have been used to study TiO2 amorphous ultra-thin films, confirming the agreement of the two methods even with respect to small details of the optical spectra. Our results show that the proposed DFT + U p methodology is computationally efficient, but still accurate. It can be applied to well-ordered TiO2 polymorphs as well as to amorphous TiO2 and will allow for the calculations of complex titania-based structures.

Effect of environmental screening and strain on optoelectronic properties of two-dimensional quantum defects

Point defects in hexagonal boron nitride (hBN) are promising candidates as single-photon emitters (SPEs) in nanophotonics and quantum information applications. The precise control of SPEs requires in-depth understanding of their optoelectronic properties. However, how the surrounding environment of host materials, including the number of layers, substrates, and strain, influences SPEs has not been fully understood. In this work, we study the dielectric screening effect due to the number of layers and substrates, and the strain effect on the optical properties of carbon dimer and nitrogen vacancy defects in hBN from first-principles many-body perturbation theory. We report that environmental screening causes a lowering of the quasiparticle gap and exciton binding energy, leading to nearly constant optical excitation energy and exciton radiative lifetime. We explain the results with an analytical model starting from the Bethe–Salpeter equation Hamiltonian with Wannier basis. We also show that optical properties of quantum defects are largely tunable by strain with highly anisotropic response, in good agreement with experimental measurements. Our work clarifies the effect of environmental screening and strain on optoelectronic properties of quantum defects in two-dimensional insulators, facilitating future applications of SPEs and spin qubits in low-dimensional systems.

Anti-Stokes Photoluminescence in Halide Perovskite Nanocrystals: From Understanding the Mechanism towards Application in Fully Solid-State Optical Cooling.

Anti-Stokes photoluminescence (ASPL) is an up-conversion phonon-assisted process of radiative recombination of photoexcited charge carriers when the ASPL photon energy is above the excitation one. This process can be very efficient in nanocrystals (NCs) of metalorganic and inorganic semiconductors with perovskite (Pe) crystal structure. In this review, we present an analysis of the basic mechanisms of ASPL and discuss its efficiency depending on the size distribution and surface passivation of Pe-NCs as well as the optical excitation energy and temperature. When the ASPL process is sufficiently efficient, it can result in an escape of most of the optical excitation together with the phonon energy from the Pe-NCs. It can be used in optical fully solid-state cooling or optical refrigeration.

A global prediction of the Kataura plot for chiral carbon nanotubes: Topological family effect revealed in the natural helical crystal lattice scheme

The optical transition energies of chiral carbon nanotubes (CNTs) are intimately related to their geometrical structures, and are frequently applied in the recognition and isolation of single nanotubes. Conventional translational crystal lattice (TCL) scheme failed to offer an accurate description of the optical properties of the chiral CNTs due to the formidable unit cell size constraint as well as the complexity of the band structures. Most fitting equations for the Kataura plot, usually based on the empirical correlations with the chiral indices of the CNTs, lack a clear physical interpretation. In this study, we apply the natural helical crystal lattice (NHCL) scheme to systematically analyze the band gap variation of arbitrary chiral CNTs. We derive a global analytical formula that takes into account the comprehensive geometrical connection topologies for the band gap of all (n, m)-CNTs with a diameter larger than 1.2 nm. With the inclusion of the many-body effect, we are able to provide a global Kataura plot prediction with a minimal set of only two fitting parameters, and the results are consistent with the experimental Kataura plot within 0.67% deviation for over 1300 data points. Our formula precisely captures the observed experimental branching features and presents a clear physical rationalization for the topological family effect on the optical excitation energies of chiral CNTs.

The Marcus dimension: identifying the nuclear coordinate for electron transfer from ab initio calculations.

The Marcus model forms the foundation for all modern discussion of electron transfer (ET). In this model, ET results in a change in diabatic potential energy surfaces, separated along an ET nuclear coordinate. This coordinate accounts for all nuclear motion that promotes electron transfer. It is usually assumed to be dominated by a collective asymmetric vibrational motion of the redox sites involved in the ET. However, this coordinate is rarely quantitatively specified. Instead, it remains a nebulous concept, rather than a tool for gaining true insight into the ET pathway. Herein, we describe an ab initio approach for quantifying the ET coordinate and demonstrate it for a series of dinitroradical anions. Using sampling methods at finite temperature combined with density functional theory calculations, we find that the electron transfer can be followed using the energy separation between potential energy surfaces and the extent of electron localization. The precise nuclear motion that leads to electron transfer is then obtained as a linear combination of normal modes. Once the coordinate is identified, we find that evolution along it results in a change in diabatic state and optical excitation energy, as predicted by the Marcus model. Thus, we conclude that a single dimension of the electron transfer described in Marcus-Hush theory can be described as a well-defined nuclear motion. Importantly, our approach allows the separation of the intrinsic electron transfer coordinate from other structural relaxations and environmental influences. Furthermore, the barrier separating the adiabatic minima was found to be sufficiently thin to enable heavy-atom tunneling in the ET process.

Electronic, redox, and optical property prediction of organic π-conjugated molecules through a hierarchy of machine learning approaches.

Accelerating the development of π-conjugated molecules for applications such as energy generation and storage, catalysis, sensing, pharmaceuticals, and (semi)conducting technologies requires rapid and accurate evaluation of the electronic, redox, or optical properties. While high-throughput computational screening has proven to be a tremendous aid in this regard, machine learning (ML) and other data-driven methods can further enable orders of magnitude reduction in time while at the same time providing dramatic increases in the chemical space that is explored. However, the lack of benchmark datasets containing the electronic, redox, and optical properties that characterize the diverse, known chemical space of organic π-conjugated molecules limits ML model development. Here, we present a curated dataset containing 25k molecules with density functional theory (DFT) and time-dependent DFT (TDDFT) evaluated properties that include frontier molecular orbitals, ionization energies, relaxation energies, and low-lying optical excitation energies. Using the dataset, we train a hierarchy of ML models, ranging from classical models such as ridge regression to sophisticated graph neural networks, with molecular SMILES representation as input. We observe that graph neural networks augmented with contextual information allow for significantly better predictions across a wide array of properties. Our best-performing models also provide an uncertainty quantification for the predictions. To democratize access to the data and trained models, an interactive web platform has been developed and deployed.

Valley dynamics of different excitonic states in monolayer WSe2 grown by molecular beam epitaxy

Monolayer transition-metal dichalcogenides possess rich excitonic physics and unique valley-contrasting optical selection rule, and offer a great platform for long spin/valley lifetime engineering and the associated spin/valleytronics exploration. Using two-color time-resolved Kerr rotation and time-resolved reflectivity spectroscopy, we investigate the spin/valley dynamics of different excitonic states in monolayer WSe2 grown by molecular beam epitaxy. With fine tuning of the photon energy of both pump and probe beams, the valley relaxation process for the neutral excitons and trions is found to be remarkably different—their characteristic spin/valley lifetimes vary from picoseconds to nanoseconds, respectively. The observed long trion spin lifetime of > 2.0 ns is discussed to be associated with the dark trion states, which is evidenced by the photon-energy dependent valley polarization relaxation. Our results also reveal that valley depolarization for these different excitonic states is intimately connected with the strong Coulomb interaction when the optical excitation energy is above the exciton resonance.

Photoexcited carrier dynamics in a GaAs photoconductive switch under nJ excitation

In this article, the bunched transport of photoexcited carriers in a GaAs photoconductive semiconductor switch (PCSS) with interdigitated electrodes is investigated under femtosecond laser excitation. Continuous outputs featuring high gain are obtained for single shots and at 1 kHz by varying the optical excitation energy. An ensemble three-valley Monte Carlo simulation is utilized to investigate the transient characteristics and the dynamic process of photoexcited carriers. It demonstrates that the presence of a plasma channel can be attributed to the bunching of high-density electron–hole pairs, which are transported in the form of a high-density filamentary current. The results provide a picture of the evolution of photoexcited carriers during transient switching. A photoinduced heat effect is analyzed, which reveals the related failure mechanism of GaAs PCSS at various repetition rates.

Oxygen vacancies in KTiOPO4 : Optical absorption from hybrid DFT

Density functional theory is used to calculate the optical absorption of oxygen vacancies in potassium titanyl phosphate ($\mathrm{K}\mathrm{Ti}\mathrm{O}\mathrm{P}{\mathrm{O}}_{4}$, KTP) crystals. A modified hybrid functional is used for the description of the midgap defect states and the optical excitation energies. Oxygen vacancies in the $+2$ charge state lead to rather minor modification of the bulk KTP optical response, while the $+1$ and neutral charge states give rise to characteristic midgap optical absorption covering the whole near-infrared and visible spectrum. Its intensity is strongly polarization dependent and strongest for light polarized parallel to the $z$ axis. The modification of the KTP optical absorption by oxygen vacancies predicted here corroborates the picture that the gray-track formation in KTP, i.e., its photochromic damage, is related to a successive charging of oxygen vacancies.

Is charge-transfer excitation through a polyalkane single-bond chain an intramolecular charge-transfer?: EOM-CCSD and LC-BOP study

We performed intra- and intermolecular charge-transfer (CT) excitation calculations of (a) H2N–(CH2–CH2)n–NO2 and (b) its equidistant H2N-H……H-NO2 using EOM-CCSD (n = 1 ∼ 5) and time-dependent long-range corrected density functional theory (n = 1 ∼ 10). The calculation results show that polyalkane [polyethylene oligomer] chain has almost no effect on CT excitation energy between donor and acceptor. That is, CT excitation energy through the polyalkane chain behaves closely to intermolecular CT excitation. Decomposition of the optical excitation energies of (a) and (b) into HOMO-LUMO gap and excitonic binding energy revealed that alkane chain does not affect HOMO-LUMO gaps, while conjugated polyene [polyethylene oligomer] chain medium reduces HOMO-LUMO gaps by delocalization.

The Appeal of Small Molecules for Practical Nonlinear Optics.

Small organic molecules with a π-conjugated system that consists of only a few double or triple bonds can have significantly smaller optical excitation energies when equipped with donor and acceptor groups, which raises the quantum limits to the molecular polarizabilities. As a consequence, third-order nonlinear optical polarizabilities become orders of magnitude larger than those of molecules of similar size without donor-acceptor substitution. This enables strong third-order nonlinear optical effects (as high as 1000 times those of silica glass) in dense, amorphous monolithic assemblies. These properties, accompanied by the possibility of deposition from the vapor phase and of electric-field poling at higher temperatures, make the resulting materials competitive towards adding an active nonlinear optical or electro-optic functionality to state-of-the-art integrated photonics platforms.

First-principles study of the Li(Y/Lu)SiO4:Ce3+,Sm3+ storage phosphor

First-principles calculations are carried out to study the native point defects and dopants (Ce3+, Sm3+) in Li(Y/Lu)SiO4 for revealing the mechanism of the optical excitation energy storage properties. The calculated excitation and emission energies, the Stokes shifts as well as the positions of 4f and 5d levels of Ce3+ relative to host band edges show great consistent with the experimental results. The calculated formation energies reveal that the Li vacancies (VLi) and the antisite defects LiY and YLi (or LiLu and LuLi) are always much more energetically favorable than Y or Lu vacancies (VY or VLu) and O vacancies (VO) in Li(Y/Lu)SiO4 under reductive atmospheres. Moreover, according to the calculated charge transition levels of the native point defects and the dopants, the antisite defects YLi (or LuLi) and the dopants Sm3+ (SmY or SmLu) are deemed as electron traps that provide suitable charge transition levels for information storage in Li(Y/Lu)SiO4. Based on our calculations, a mechanism diagram of charge carrier storage and recombination during irradiation and thermal or optical readout is constructed for the storage phosphors Li(Y/Lu)SiO4:Ce3+,Sm3+.

Probing the Formation and Conformational Relaxation of Previtamin D3 and Analogues in Solution and in Lipid Bilayers.

The photosynthesis of vitamin D3 in mammalian skin results from UV-B irradiation of provitamin D3 (7-dehydrocholesterol, DHC) at ca. 290 nm. Upon return to the ground state, the hexatriene product, previtamin D3, undergoes a conformational equilibration between helical gZg and more planar tZg and tZt forms. The helical gZg forms provide a pathway for the formation of vitamin D3 via a [1,7]-sigmatropic hydrogen shift. Steady state photolysis and UV transient absorption spectroscopy are combined to explore the conformational relaxation of previtamin D3 formed from DHC in isotropic solution and confined to lipid bilayers chosen to model the biological cell membrane. The results are compared with measurements for two analogues: previtamin D2 formed from ergosterol (provitamin D2) and previtamin D3 acetate formed from DHC acetate. The resulting spectral dynamics are interpreted in the context of simulations of optical excitation energy and oscillator strength as a function of conformation. In solution, the relaxation dynamics and steady state product distributions of the three compounds are nearly identical, favoring tZg forms. When confined to lipid bilayers, the heterogeneity and packing forces alter the conformational distributions and enhance the population of a gZg conformer capable of vitamin D formation.

Accurate prediction of the properties of materials using the CAM-B3LYP density functional.

Density functionals with asymptotic corrections to the long-range potential provide entry-level methods for calculations on molecules that can sustain charge transfer, but similar applications in materials science are rare. We describe an implementation of the CAM-B3LYP range-separated functional within the Vienna Ab-initio Simulation Package (VASP) framework, together with its analytical functional derivatives. Results obtained for eight representative materials: aluminum, diamond, graphene, silicon, NaCl, MgO, 2D h-BN, and 3D h-BN, indicate that CAM-B3LYP predictions embody mean-absolute deviations (MAD) compared to HSE06 that are reduced by a factor of six for lattice parameters, four for quasiparticle band gaps, three for the lowest optical excitation energies, and six for exciton binding energies. Further, CAM-B3LYP appears competitive compared to ab initio G0 W0 and Bethe-Salpeter equation approaches. The CAM-B3LYP implementation in VASP was verified by comparison of optimized geometries and reaction energies for isolated molecules taken from the ACCDB database, evaluated in large periodic unit cells, to analogous results obtained using Gaussian basis sets. Using standard GW pseudopotentials and energy cutoffs for the plane-wave calculations and the aug-cc-pV5Z basis set for the atomic-basis ones, the MAD in energy for 1738 chemical reactions was 0.34 kcal mol-1 , while for 480 unique bond lengths this was 0.0036 Å; these values reduced to 0.28 kcal mol-1 (largest error 0.94 kcal mol-1 ) and 0.0009 Å by increasing the plane-wave cutoff energy to 850 eV.

Electronic Structure of Metallophthalocyanines, MPc (M = Fe, Co, Ni, Cu, Zn, Mg) and Fluorinated MPc.

We compute the electronic structure and optical excitation energies of metal-free and transition-metal phthalocyanines (H2Pc and MPc for M = Fe, Co, Ni, Cu, Zn, Mg) using density functional theory with optimally tuned range-separated hybrid functionals (OT-RSH). We show that the OT-RSH approach provides photoemission spectra in quantitative agreement with experiments as well as optical band gaps within 10% of their experimental values, capturing the interplay of localized d-states and delocalized π-π* states for these organometallic compounds. We examine the tunability of MPcs and H2Pc through fluorination, resulting in quasi-rigid shifts of the molecular orbital energies by up to 0.7 eV. Our comprehensive data set provides a new computational benchmark for gas-phase phthalocyanines, significantly improving upon other density-functional-theory-based approaches.

Switching resonance character within merocyanine stacks and its impact on excited-state dynamics

Summary In this study, the optical properties and excited-state dynamics of the unique self-assembled donor-acceptor (DA) merocyanine dye stacks from dimer up to octamer, prepared via dipole-dipole interactions, are reported in terms of coherent exciton dynamics and formation of an excimer-like state. Our findings are based on the steady-state absorption/emission, time-resolved fluorescence, and transient absorption (anisotropy) measurements, including wavepacket analysis and quantum mechanical calculations. Coherent exciton of torsional motions-restricted dye stacks rapidly localizes into the weakly emissive excimer-like state, by shortening the inter-moiety distance and changing the bond-length alternation pattern. The inner merocyanine moiety, having two neighboring units, has a reversed resonance character (non-polar (N) Z) in the ground state. This difference has led to two conclusions: (1) tetramers and octamers exhibit different features of excimer-like state than the dimer, and (2) octamers exhibit slower localization dynamics due to the enhanced homogeneity (six inner-moieties) compared with tetramers (two inner moieties).

Dynamical correction to the Bethe-Salpeter equation beyond the plasmon-pole approximation.

The Bethe-Salpeter equation (BSE) formalism is a computationally affordable method for the calculation of accurate optical excitation energies in molecular systems. Similar to the ubiquitous adiabatic approximation of time-dependent density-functional theory, the static approximation, which substitutes a dynamical (i.e., frequency-dependent) kernel by its static limit, is usually enforced in most implementations of the BSE formalism. Here, going beyond the static approximation, we compute the dynamical correction of the electron-hole screening for molecular excitation energies, thanks to a renormalized first-order perturbative correction to the static BSE excitation energies. The present dynamical correction goes beyond the plasmon-pole approximation as the dynamical screening of the Coulomb interaction is computed exactly within the random-phase approximation. Our calculations are benchmarked against high-level (coupled-cluster) calculations, allowing one to assess the clear improvement brought by the dynamical correction for both singlet and triplet optical transitions.

A theoretical study of carbazole dimers: Does carbazole form an excimer that undermines the performance of organic light emitting diodes?

AbstractCarbazole (Cz) dimers in various cofacial conformations, including staggered (Stg), anti, and syn, were explored by means of ab initio calculations at scaled opposite‐spin (SOS)‐MP2, SOS‐CIS(D0), and additional coupled cluster calculation levels. Similar to other π‐conjugated molecules, strong Cz excimers form in the syn conformation in both S1 and T1 states, leading to significantly reduced optical excitation energies. Upon excitation, the dimers in the Stg and anti‐conformations remain simple excited dimers, exhibiting similar optical energy gaps to those of the monomer. Being far more stable in the ground state, however, the Stg dimer is nearly isoenergetic to the syn dimer in the S1 state and even more stable in the T1 state. Given that the intermolecular interactions in the ground state are expected to govern the dimer conformations of Cz‐based materials in the solid‐state films of organic electronics, our results strongly demonstrate that the electronic excitation of Cz dimers do not necessarily lead to the strong excimer formation unless Cz molecules are forced to be arranged in the syn conformation.

Impact of excitation energy on the excitonic luminescence of cesium lead bromide perovskite nanosheets.

An excitation-energy-dependent luminescence phenomenon is reported in cesium lead bromide (CsPbBr3) perovskite nanosheets. At 10 K, the relative integrated luminescence intensity between the trapped exciton (TX) emission and the free exciton (FX) emission shows an interesting tendency with increasing the optical excitation energy from 2.431 eV (510 nm) to 3.758 eV (330 nm). To interpret such phenomenon, we develop a quantitative model on the basis of the biological population growth theory. A good agreement between experiment and theory is obtained. It is thus revealed that the lower capture coefficient of the TX level to the excited excitons via multiphonon emission relative to the FX level shall be the major cause of the observed phenomenon. These findings may help to deepen the current understanding of the complex luminescence mechanisms of these emerging light-emitting materials.