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Few atom thick, twisted bilayer graphene (tBLG) possesses a rotation angle (θ) dependent van Hove singularity (vHs). Fine-tuning vHs serves a potential method to enhance charge transfer (CT) in surface enhanced Raman spectroscopy. This study shows that tBLG having a specific θ promotes as high as a 1.7 times enhancement of the Raman signals of copper phthalocyanine (CuPc) as compared to that caused by single layer graphene (SLG). The results of a combination of reflection imaging spectroscopy and widefield Raman provide spatial and spectral information about both tBLG with θ ranging from 10.9 to 13.7° and the corresponding vHs. Comparison of Raman spectra of CuPc in presence and absence of tBLG demonstrates that a significant enhancement of certain CuPc vibrational modes occurs when the underlying tBLG possesses a θ = 12.2°, showing as high as 6.8 and 1.7 times enhancements of certain vibrational mode as compared to those of CuPc on bare and SLG substrates, respectively. Theoretical calculations indicate that a match between the energies of vHs of tBLG with those of frontier orbitals of CuPc facilitates CT from the distant SLG to CuPc.

Reversible conversion over multi-million-times in bond types between metavalent and covalent bonds becomes one of the most promising bases for universal memory. As the conversions have been found in metastable states, extended category of crystal structures from stable states via redistribution of vacancies, researches on kinetic behavior of the vacancies are highly on demand. However, they remain lacking due to difficulties with experimental analysis. Herein, the direct observation of the evolution of chemical states of vacancies clarifies the behavior by combining analysis on charge density distribution, electrical conductivity, and crystal structures. Site-switching of vacancies gradually occurs with diverged energy barriers owing to a unique activation code-the accumulation of vacancies triggers spontaneous gliding along atomic planes to relieve electrostatic repulsion. Study on the behavior can be further applied to multi-phase superlattices composed of Sb2Te3 (2D) and GeTe (3D) sublayers, which represent the superior memory performances but their operating mechanisms were still under debates due to their complexity. The site-switching is favorable (suppressed) when Te-Te bonds are formed as physisorption (chemisorption) over the interface between Sb2Te3 (2D) and GeTe (3D) sublayers driven by configurational entropic gain (electrostatic enthalpic loss). Depending on the type of interfaces between sublayers, phases of the superlattices are classified into metastable and stable states, where the conversion could be only achieved in the metastable state. From this comprehensive understanding on the operating mechanism via kinetic behaviors of vacancies and the metastability, further studies towards vacancy engineering are expected in versatile materials., Comment: 32 pages, 4 figures

Heterometal doping is a powerful method for tuning the physicochemical properties of metal nanoclusters. While the heterometals doped into such nanoclusters predominantly include transition metals with closed d-shells, the doping of open d-shell metals remains largely unexplored. Herein, we report the first synthesis of a [RhHAg24 (SPhMe2 )18 ]2- nanocluster, in which a Rh atom with open d-shells ([Kr]4d8 5s1 ) is incorporated into the Ag24 framework by forming a RhH superatom with closed d-shells ([Kr]4d10 ). Combined experimental and theoretical investigations showed that the Ag24 framework was co-doped with Rh and hydride and that the RhH dopant was a superatomic construct of a Pd atom. Additional studies demonstrated that the [RhHAg24 (SPhMe2 )18 ]2- nanocluster was isoelectronic to the [PdAg24 (SPhMe2 )18 ]2- nanocluster with the superatomic 8-electron configuration (1S2 1P6 ). This study demonstrated for the first time that a superatom could be incorporated into a cluster superatom to generate a stable superatom-in-superatom nanocluster.

Density functional simulations of condensed phase water are typically inaccurate, due to the inaccuracies of approximate functionals. A recent breakthrough showed that the SCAN approximation can yield chemical accuracy for pure water in all its phases, but only when its density is corrected. This is a crucial step toward first-principles biosimulations. However, weak dispersion forces are ubiquitous and play a key role in noncovalent interactions among biomolecules, but are not included in the new approach. Moreover, naïve inclusion of dispersion in HF-SCAN ruins its high accuracy for pure water. Here we show that systematic application of the principles of density-corrected DFT yields a functional (HF-r2SCAN-DC4) which recovers and not only improves over HF-SCAN for pure water, but also captures vital noncovalent interactions in biomolecules, making it suitable for simulations of solutions.

The two different light-matter interactions between visible and infrared light are not switchable because control mechanisms have not been elucidated so far, which restricts the effective spectral range in light-sensing devices. In this study, modulation of the effective spectral range is demonstrated using the metal-insulator transition of MoS

We investigated the association between isoflavone (ISF) intake and hereditary breast cancer (BC) risk, particularly by molecular subtype, in East-Asian BRCA1/2 mutation carriers and non-carriers at a high risk of hereditary breast cancer (i.e., family history of BC (FHBC) and early-onset BC [EOBC, age

We investigate the thermal and electrical conductivities of Cu-coated carbon fiber (Cu-CF), which is designed to reduce the weight of metal wires. The electrical and thermal properties of Cu-CF are assessed using the 3 ω method. This material is formed by depositing a thin layer of Cu, approximately 100–200 nm thick, on a core of CF with a diameter of 7 μ m. This structure grants the wire metal-like electrical properties, i.e., a positive temperature coefficient of resistance (TCR), with phonon-driven heat conduction behavior. Therefore, metal-like electrical conduction and insulator-like thermal conduction are combined in the Cu-CF wire. Electrical conduction is completely dominated by the Cu layer regardless of temperature. In contrast, heat conduction is dominated by the inner-core CF near 300 K, but the Cu layer dominates at lower temperatures. Thus, the deviation of Lorenz number L of Cu-CF from its theoretical value of Lo = 2.44 × 10−8 W Ω/K2 increases as the Cu layer becomes thinner and the temperature increases.

Despite the successful debut of gold nanoclusters (Au NCs) in solar cell applications, Au NCs, compared to dyes and quantum dots, have several drawbacks, such as lower extinction coefficients. Any modulation of the physical properties of NCs can have a significant influence on the delicate control of absorbance, energy levels, and charge separation, which are essential to ensure high power conversion efficiency. To this end, we systematically alter the optoelectronic structure of Au18(SR)14 by Ag doping and explain its influence on solar cell performance. Our in-depth spectroscopic and electrochemical characterization combined with computational study reveals that the performance-dictating factors respond in different manners to the Ag doping level, and we determine that the best compromise is the incorporation of a single Ag atom into an Au NC. This new insight highlights the unique aspect of NCs—susceptibility to atomic level doping—and helps establish a new design principle for efficient NC-based solar cells.

Density functional theory (DFT) calculations have become widespread in both chemistry and materials, because they usually provide useful accuracy at much lower computational cost than wavefunction-based methods. All practical DFT calculations require an approximation to the unknown exchange-correlation energy, which is then used self-consistently in the Kohn-Sham scheme to produce an approximate energy from an approximate density. Density-corrected DFT is simply the study of the relative contributions to the total energy error. In the vast majority of DFT calculations, the error due to the approximate density is negligible. But with certain classes of functionals applied to certain classes of problems, the density error is sufficiently large as to contribute to the energy noticeably, and its removal leads to much better results. These problems include reaction barriers, torsional barriers involving I -conjugation, halogen bonds, radicals and anions, most stretched bonds, etc. In all such cases, use of a more accurate density significantly improves performance, and often the simple expedient of using the Hartree-Fock density is enough. This Perspective explains what DC-DFT is, where it is likely to improve results, and how DC-DFT can produce more accurate functionals. We also outline challenges and prospects for the field.

Although anionic-redox-based layered oxide materials have attracted great attention as promising cathodes for Na-ion batteries because of their high practical capacities, they suffer from undesirable structural degradation, resulting in the poor electrochemical behavior. Moreover, the occurrence of stable anionic-redox reaction without the use of expensive elements such as Li, Co, and Ni is considered one of the most important issues for high-energy and low-cost Na-ion batteries. Herein, using first-principles calculation and various experimental techniques, we investigate the combination of vacancy (□) and Ti4+ cations in the transition-metal sites to enable outstanding anionic-redox-based electrochemical performance in the Na-ion battery system. The presence of vacancies in the P2-type Na0.56[Ti0.1Mn0.76□0.14]O2 structure suppresses the large structural change such as the P2–OP4 phase transition, and Ti4+ cations in the structure result in selectively oxidized oxygen ions with structural stabilization during Na+ deintercalation in the high-voltage region. The high structural stability of P2-type Na0.56[Ti0.1Mn0.76□0.14]O2 enables not only the high specific capacity of 224.92 mAh g−1 at 13 mA g−1 (1C = 264.1 mA g−1) with an average potential of ∼2.62 V (vs Na+/Na) but also excellent cycle performance with a capacity retention of ∼80.38% after 200 cycles at 52 mA g−1 with high coulombic efficiencies above 99%. Although there are some issues such as low Na contents in the as-prepared state, these findings suggest potential strategies to stabilize the anionic-redox reaction and structure in layered-oxide cathodes for high-energy and low-cost Na-ion batteries.

As a 3D topological insulator, bismuth selenide (Bi

A Kohn-Sham (KS) inversion determines a KS potential and orbitals corresponding to a given electron density, a procedure that has applications in developing and evaluating functionals used in density functional theory. Despite the utility of KS inversions, application of these methods among the research community is disproportionately small. We implement the KS inversion methods of Zhao-Morrison-Parr and Wu-Yang in a framework that simplifies analysis and conversion of the resulting potential in real-space. Fully documented Python scripts integrate with PySCF, a popular electronic structure prediction software, and Fortran alternatives are provided for computational hot spots., 13 pages, 4 figures, 11 blocks of code

As a 3D topological insulator, bismuth selenide (Bi2Se3) has potential applications for electrically and optically controllable magnetic and optoelectronic devices. Understanding the coupling with its topological phase requires studying the interactions of carriers with the lattice on time scales down to the subpicosecond regime. Here, we investigate the ultrafast carrier-induced lattice contractions and interlayer modulations in Bi2Se3 thin films by time-resolved diffraction using an X-ray free-electron laser. The lattice contraction depends on the carrier concentration and is followed by an interlayer expansion accompanied by oscillations. Using density functional theory and the Lifshitz model, the initial contraction can be explained by van der Waals force modulation of the confined free carrier layers. Our theoretical calculations suggest that the band inversion, related to a topological phase transition, is modulated by the expansion of the interlayer distance. These results provide insights into the topological phase control by light-induced structural change on ultrafast time scales.

Most torsional barriers are predicted to high accuracy (about 1kJ/mol) by standard semilocal functionals, but a small subset has been found to have much larger errors. We create a database of almost 300 carbon-carbon torsional barriers, including 12 poorly behaved barriers, all stemming from Y=C-X group, where X is O or S, and Y is a halide. Functionals with enhanced exchange mixing (about 50%) work well for all barriers. We find that poor actors have delocalization errors caused by hyperconjugation. These problematic calculations are density sensitive (i.e., DFT predictions change noticeably with the density), and using HF densities (HF-DFT) fixes these issues. For example, conventional B3LYP performs as accurately as exchange-enhanced functionals if the HF density is used. For long-chain conjugated molecules, HF-DFT can be much better than exchange-enhanced functionals. We suggest that HF-PBE0 has the best overall performance., Comment: 13 pages, 7 main figures, 6 supporting figures

HF-DFT, the practice of evaluating approximate density functionals on Hartree-Fock densities, has long been used in testing density functional approximations. Density-corrected DFT (DC-DFT) is a general theoretical framework for identifying failures of density functional approximations by separating errors in a functional from errors in its self-consistent (SC) density. Most modern DFT calculations yield highly accurate densities, but important characteristic classes of calculation have large density-driven errors, including reaction barrier heights, electron affinities, radicals and anions in solution, dissociation of heterodimers, and even some torsional barriers. Here, the HF density (if not spin-contaminated) usually yields more accurate and consistent energies than those of the SC density. We use the term DC(HF)-DFT to indicate DC-DFT using HF densities only in such cases. A recent comprehensive study (J. Chem. Theory Comput. 2021, 17, 1368-1379) of HF-DFT led to many unfavorable conclusions. A reanalysis using DC-DFT shows that DC(HF)-DFT substantially improves DFT results precisely when SC densities are flawed.

We have studied how the light-matter colocalization effect, which is the overlap effect between target and electric field distribution, affects the sensitivity of nanogap-based surface plasmon resonance (SPR) sensors. The SPR characteristics of the nanogap structure were calculated using a rigorous coupled-wave analysis program with DNA immobilization and hybridization cases. The colocalized shift (COS) and its relative value, relative optical signature (ROS), were defined to explain the capability change according to the gap size (g) along with the momentum matching condition of the nanogap. The maximum sensitivity, defined as the COS value compared to the changed refractive index, was 514.8 deg / (μm * RIU), which appeared at a relatively large interval (g = 17nm). When increasing the nanogap size, the ROS and reflectance also increased. However, the trend reversed, and the decrease in ROS reached a negative range at a 9 nm gap or more. This ROS is due to damping in the multiple localized surface plasmon polariton mode, and the strong field confinement inside the nanogap induces a negative shift. The zero-shift, the most avoidable when designing an SPR sensor, and near-field distribution with plasmon mode, is observed across different gap size and period pairs. The effect of colocalization inside the nanogap, as identified through various metrics, promises a highly sensitive detection potential for biological applications.

Kohn-Sham (KS) inversion, that is, the finding of the exact KS potential for a given density, is difficult in localized basis sets. We study the precision and reliability of several inversion schemes, finding estimates of density-driven errors at a useful level of accuracy. In typical cases of substantial density-driven errors, Hartree-Fock density functional theory (HF-DFT) is almost as accurate as DFT evaluated on CCSD(T) densities. A simple approximation in practical HF-DFT also makes errors much smaller than the density-driven errors being calculated. Two paradigm examples, stretched NaCl and the HO·Cl- radical, illustrate just how accurate HF-DFT is.

Empirical fitting of parameters in approximate density functionals is common. Such fits conflate errors in the self-consistent density with errors in the energy functional, but density-corrected DFT (DC-DFT) separates these two. We illustrate with catastrophic failures of a toy functional applied to $H_2^+$ at varying bond lengths, where the standard fitting procedure misses the exact functional; Grimme's D3 fit to noncovalent interactions, which can be contaminated by large density errors such as in the WATER27 and B30 datasets; and double-hybrids trained on self-consistent densities, which can perform poorly on systems with density-driven errors. In these cases, more accurate results are found at no additional cost, by using Hartree-Fock (HF) densities instead of self-consistent densities. For binding energies of small water clusters, errors are greatly reduced. Range-separated hybrids with 100\% HF at large distances suffer much less from this effect.

We have investigated conformational structures of meso- meso linked porphyrin arrays (Z n) by single molecule fluorescence spectroscopy. Modulation depths ( M values) were measured by excitation polarization fluorescence spectroscopy. The M value decreases from 0.85 to 0.46 as the number of porphyrin units increases from 3 to 128, indicating that longer arrays exhibit coiled structures. Such conformational changes depending on the length have been confirmed by coarse-grained simulation. The histograms of M values and traces of centroid position of emitting sites by localization microscopy showed that the structures of longer arrays changed to more stretched after solvent vapor annealing with tetrahydrofuran.

All-electron fixed-node diffusion Monte Carlo provides benchmark spin gaps for four Fe(II) octahedral complexes. Standard quantum chemical methods (semilocal DFT and CCSD(T)) fail badly for the energy difference between their high- and low-spin states. Density-corrected DFT is both significantly more accurate and reliable and yields a consistent prediction for the Fe-Porphyrin complex.

Three Schiff base ligands such as 2‑[(2‑Hydroxy‑3‑methoxy‑benzylidene)‑amino]‑2‑hydroxymethyl‑propane‑1,3‑diol (HL1), 2‑[(2‑Hydroxy‑benzylidene)‑amino]‑2‑hydroxymethyl‑propane‑1,3‑diol (HL2), 2‑[(3,5‑Dichloro‑2‑hydroxy‑benzylidene)‑amino]‑2‑hydroxymethyl‑propane‑1,3‑diol (HL3) have been synthesized by condensation of aldehydes (such as 3,5‑Dichloro‑2‑hydroxy benzaldehyde, 2‑Hydroxy‑benzaldehyde, and 2‑Hydroxy‑3‑methoxy‑benzaldehyde) with Tris‑(hydroxymethyl)amino methane and characterized by IR, UV–vis and 1H NMR spectroscopy. Then all these three ligands have been used to prepare Pb(II) complexes by reaction with lead(II) acetate tri-hydrate in methanol. In view of analytical and spectral (IR, UV–vis and Mass) studies, it has been concluded that, except HL2, other two ligands form 1:1 metal complexes (1 and 3) with lead. Between two complexes, complex 3 is highly fluorescent and this property has been used to identify the pollutant nitroaromatics. Finally, the quenching mechanism has been established by means of spectroscopic investigation.

A nanoscale gap aperture has been used as a fundamental tool for diverse applications. In this paper, we investigate the effect of nanogap aperture parameters on optical sensors, primarily based on surface plasmon resonance. A simple 2-D model was used for DNA immobilization and hybridization, in which nanogap enables light-matter colocalization to amplify detection signatures, thereby enhancing performance characteristics. Interestingly, the optimum gap geometry that produces maximum light-matter overlap and the largest resonance shift was not associated with the smallest gap size. Highest sensitivity was observed to correlate with negative resonance shift due to increased damping as well as the excitation of higher order surface plasmon polariton modes. Zero-shift nanogap was also discussed. The results suggest that careful design of nanogap apertures should be carried out to make the most of what they can achieve.

We review the role of self-consistency in density functional theory. We apply a recent analysis to both Kohn-Sham and orbital-free DFT, as well as to Partition-DFT, which generalizes all aspects of standard DFT. In each case, the analysis distinguishes between errors in approximate functionals versus errors in the self-consistent density. This yields insights into the origins of many errors in DFT calculations, especially those often attributed to self-interaction or delocalization error. In many classes of problems, errors can be substantially reduced by using `better' densities. We review the history of these approaches, many of their applications, and give simple pedagogical examples., Comment: submitted for publication to the Annual Review of Physical Chemistry

Cesium-based perovskite nanocrystals (NCs) have outstanding photophysical properties improving the performances of lighting devices. Fundamental studies on excitonic properties and hot-carrier dynamics in perovskite NCs further suggest that these materials show higher efficiencies compared to the bulk form of perovskites. However, the relaxation rates and pathways of hot-carriers are still being elucidated. By using ultrafast transient spectroscopy and calculating electronic band structures, we investigated the dependence of halide in Cs-based perovskite (CsPbX3 with X=Br, I, or their mixtures) NCs on the hot-carrier relaxation processes. All samples exhibit ultrafast ( CsPbBr1.5I1.5 (380 fs)>CsPbI3 NC (580 fs). These result accounts for a reduced light emission efficiency of CsPbI3 NC compared to CsPbBr3 NC.

Density-corrected density functional theory (DC-DFT) is enjoying substantial success in improving semilocal DFT calculations in a wide variety of chemical problems. This paper provides the formal theoretical framework and assumptions for the analysis of any functional minimization with an approximate functional. We generalize DC-DFT to allow comparison of any two functionals, not just comparison with the exact functional. We introduce a linear interpolation between any two approximations, and use the results to analyze global hybrid density functionals. We define the basins of density-space in which this analysis should apply, and give quantitative criteria for when DC-DFT should apply. We also discuss the effects of strong correlation on density-driven error, utilizing the restricted HF Hubbard dimer as an illustrative example., 14 pages, 9 figures

For conjugated macrocycles, conformational disorder plays a key role in determining whether the unique form of excitons that are fully delocalized over the cyclic framework (cyclic excitons) is formed by photoexcitation. We have investigated the ring size dependence of conformations and photophysical properties of macrocyclic thiophenes of varying ring sizes (C-5NTNV) by using single-molecule fluorescence spectroscopy. We measured modulation depth, M, values and fluorescence intensities. As the ring size increases, the correlation plots of the two parameters show bimodal distributions, revealing that larger macrocycles exhibit extremely congested linear structures. The size dependence of structural changes in macrocyclic thiophenes have been clearly confirmed by molecular dynamics simulation. The number of torsional defects from simulated structures, in conjunction with survival times from fluorescence intensity trajectories and photon coincidence measurements, demonstrated the existence of multiple acycl...

Heat induced by electromagnetic absorption affects optical properties and experimental conditions. For this reason, thermal effects in optics remain important. In this work, we investigate thermal properties of a wire-grid polarizer (WGP). A WGP is a well-known optical polarizing device and easy to combine with planar structures such as microfluidic channel and other optical components. We analyzed thermal characteristics of a WGP by considering the effects of various geometric parameters: wire-grid period, height, and fill factor. For far-field calculation of optical characteristics, rigorous-coupled wave analysis (RCWA) has been used with 40 spatial harmonics. Together, we solved wave-coupled heat transfer equation by 2D finite element method (FEM) for computing electromagnetic-thermal characteristics. 2D FEM calculation was verified with RCWA and 3D FEM. From the analysis, it was shown that a fill factor was the most dominant geometrical parameter for near-field thermal extinction. In addition, TM polarized light has higher local temperature Tmax = 354.5 K than that of TE polarized light Tmax = 331.7 K with an incident power at 0.1 mW/μm2. Polarization switching was found to induce thermal extinction of 4.78 dB with a temperature difference uT = 54.3 K in an identical WGP structure. Furthermore, the ratio of steady-state time was almost uniform within 15%, because the heat transfer mechanism is almost identical for TE and TM polarization. Time scale was on the order of μs. We expect this result to be useful for the integration of WGPs in polarization-sensitive thermal switching applications.

We explore heat transfer and thermal characteristics of a wire-grid polarizer (WGP) on a microscale by investigating the effect of various geometrical parameters such as wire-grid period, height, and a fill factor. The thermal properties arise from heat transfer by light absorption and conduction in wire-grids. Fill factor was found to be the most dominant geometrical parameter. For TM polarized light, a higher fill factor with thicker wire-grids increased the temperature. The local temperature was found to rise up to Tmax = 354.5 K. TE polarization tended to produce lower temperature. Thermal extinction due to polarimetric extinction by a WGP was also evaluated and highest extinction was observed to be 4.78 dB, which represents a temperature difference ΔT = 54.3 °C. We expect the results to be useful for WGPs in polarization-sensitive thermal switching applications.

We argue that any general mathematical measure of density error, no matter how reasonable, is too arbitrary to be of universal use. However, the energy functional itself provides a universal relevant measure of density errors. For the self-consistent density of any Kohn-Sham calculation with an approximate functional, the theory of density-corrected density functional theory (DC-DFT) provides an accurate, practical estimate of this ideal measure. We show how to estimate the significance of the density-driven error even when exact densities are unavailable. In cases with large density errors, the amount of exchange-mixing is often adjusted, but we show that this is unnecessary. Many chemically relevant examples are given.

We analyze the characteristics of plasmonics-based enhancement of a wire-grid polarizer (WGP) by rigorous coupledwave analysis (RCWA). We consider blazed WGP (bWGP) for improvement of polarimetric performance based on plasmonic momentum-matching in the metal/dielectric interface. The analysis used a model of triangular wire-grids approximated with five graded layers of identical thickness. We have compared the performance to that of a conventional WGP (cWGP) with a corresponding lamellar grating shape profile. As a performance measure, we calculated transmittance (TR) and extinction ratio (ER). It was found that TR in both cases tends to decrease monotonically with a longer period (Λ). The maximum TR of bWGPs is lower than cWGPs. On the other hand, maximum ER of bWGPs is much higher than that of cWGPs, particularly at a longer period, with an extinction peak peaked at Λ = 800 nm. For cWGPs, an extinction peak is observed at Λ = 200 nm with comparable enhancement (~42 dB). We have also computed relative TR (RTR) and relative ER (RER) for assessment of performance relative to cWGP. RTR decreases slowly in a manner similar to TR, however, RER increases exponentially with a longer wire-grid period. The results suggest that strong localization of near-fields observed with bWGPs can be used to improve polarimetric performance of a WGP.

We present enhanced characteristics of surface plasmon resonance biosensing with nanogap-based light-matter colocalization. Optical signature was shown to increase by nearly 15 times than conventional detection with highest sensitivity at a relatively large gap.

We investigate the polarimetric performance of surface plasmon-enhanced blazed wire-grid polarizer (WGP) compared with conventional WGP. Highest extinction ratio was found to be 15,740 at 800 nm period which allows easier fabrication of WGPs.

Excited-state dynamic planarization processes play a crucial role in determining exciton size in cyclic systems, as reported for π-conjugated linear oligomers. Herein, we report time-resolved fluorescence spectra and molecular dynamics simulations of π-conjugated cyclic oligothiophenes in which the number of subunits was chosen to show the size-dependent dynamic planarization in the vicinity of a ring-to-linear behavioral turning point. Analyses on the evolution of the total fluorescence intensity and the ratio between 0-1 to 0-0 vibronic bands suggest that excitons formed in a cyclic oligothiophene composed of six subunits fully delocalize over the cyclic carbon backbone, whereas those formed in larger systems fail to achieve complete delocalization. With the aid of molecular dynamics simulations, it is shown that distorted structures unfavorable for efficient exciton delocalization are more easily populated as the size of the cyclic system increases.