Dissociation Probability Research Articles

Structure of the Charge-Transfer State in PM6/Y6 and PM6/Y6:YT Composites Studied by Electron Spin Echo Technique

Nowadays, Y-shaped non-fullerene acceptors become increasingly important in organic photovoltaics (OPV). Their use in binary and ternary bulk heterojunction composites continuously pushes up the efficiency of OPV devices. However, the mechanism of OPV performance enhancement by the third component of a ternary composite is rarely understood. In the present work, pulse EPR technique was used to reveal the similarities and the differences of photoinduced charge separation process in binary PM6/Y6 and ternary PM6/Y6:Y-T composites, where PM6 is polymer donor, Y6 and Y-T are different non-fullerene acceptors. Out-of-phase electron spin echo signal was detected for both composites, which is the signature of the charge-transfer state (CT state) formed at the donor/acceptor interface upon exciton splitting. Nearly identical distribution of the distances between the electron and the hole constituting the CT state was obtained for these composites from the analysis of this signal. In both cases the average electron-hole distance was 3.5 nm. It implies that OPV efficiency increase with Y-T addition is not caused by the increased probability of CT state dissociation followed by free charge generation for PM6/Y6:Y-T composite.

Chlorinated Narrow Bandgap Polymer Suppresses Non-Radiative Recombination Energy Loss Enabling Perylene Diimides-Based Organic Solar Cells Exceeding 10% Efficiency.

The scarcity of narrow bandgap donor polymers matched with perylene diimides (PDI)-based nonfullerene acceptors (NFAs) hinders improvement of the power conversion efficiency (PCE) value of organic solar cells (OSCs). Here, it is reported that a narrow bandgap donor polymer PDX, the chlorinated derivative of the famous polymer donor PTB7-Th, blended with PDI-based NFA boosts the PCE value exceeding 10%. The electroluminescent quantum efficiency of PDX-based OSCs is two orders of magnitude higher than that of PTB7-Th-based OSCs;therefore, the nonradiative energy loss is 0.103eV lower. This is the highest PCE value for OSCs with the lowest energy loss using the blend of PTB7-Th derivatives and PDI-based NFAs as the active layer. Besides, PDX-based devices showed larger phase separation, faster charge mobilities, higher exciton dissociation probability, suppressed charge recombination, elevated charge transfer state, and decreased energetic disorder compared with the PTB7-Th-based OSCs. All these factors contribute to the simultaneously improved short circuit current density, open circuit voltage, and fill factor, thus significantly improving PCE. These results prove that chlorinated conjugated side thienyl groups can efficiently suppress the non-radiative energy loss and highlight the importance of fine-modifying or developing novel narrow bandgap polymers to further elevate the PCE value of PDI-based OSCs.

Dynamics of Dissociative Chemisorption of NH3 on Fe(111) on a Twelve-Dimensional Potential Energy Surface

We constructed a new, accurate twelve-dimensional potential energy surface (PES) for ammonia dissociative chemisorption (DC) on a rigid Fe(111) surface using the fundamental invariant-neural network fitting to a large number of density functional theory data points. The DC dynamics simulations were carried out by the quasi-classical trajectory (QCT) approach. At very low collision energies, the molecules experienced a large number of rebounds due to the deep pre-transition-state adsorption well and finally decomposed around the global transition state. At high collision energies, the bridge site with a loose transition state was the most favorable site for dissociation. The mode-specific dynamics revealed that excitations in symmetric stretch and umbrella modes were most efficient in promoting the dissociation and were more efficacious than the same amount of translational energy. The computed large dissociation probability for NH3/Fe(111) supported the fact that iron is an effective catalyst for ammonia dissociation, which is of practical importance in producing clean hydrogen.

Semiclassical Dynamics on Machine-Learned Coupled Multireference Potential Energy Surfaces: Application to the Photodissociation of the Simplest Criegee Intermediate.

Determination of high-dimensional potential energy surfaces (PESs) and nonadiabatic couplings have always been quite challenging. To this end, machine learning (ML) models, trained with a finite set of ab initio data, allow accurate prediction of such properties. To express the PESs in terms of atomic contributions is the cornerstone of any ML based technique because it can be easily scaled to large systems. In this work, we have constructed high fidelity PESs and nonadiabatic coupling terms at the CASSCF level of ab initio data using a machine learning technique, namely, kernel-ridge regression. Additional MRCI-level calculations were carried out to assess the quality of the PESs. We use these machine-learned PESs and nonadiabatic couplings to simulate excited-state molecular dynamics based on Tully's fewest-switches surface hopping method (FSSH). FSSH is a semiclassical method in which nuclei move on the PESs due to the electrons according to the laws of classical mechanics. Nonadiabatic effects are taken into account in terms of transitions between PESs. We apply this scheme to study the O-O photodissociation of the simplest Criegee intermediate (CH2OO). The FSSH trajectories were initiated on the lowest optically bright singlet excited state (S2) and propagated along the three most important internal coordinates, namely, O-O and C-O bond distances and the COO bond angle. Some of the trajectories end up on energetically lower PESs as a result of radiationless transfer through conical intersections. All of the trajectories lead to the dissociation of the O-O bond due to the dissociative nature of the excited PESs through one of the two dissociative channels. The simulation reveals that there is about 88.4% probability of dissociation through the lower channel leading to the H2CO (X1A1) and O (1D) products, whereas there is only 11.6% probability of dissociation through the upper channel leading to H2CO (a3A″) and O (3P) products.

Micro-mechanism study on the effect of O2 poisoned ZrCo surface on hydrogen absorption performance

Hydrogen storage alloys are usually susceptible to poisoning by O2, CO, CO2, etc., which decreases the hydrogen storage property sharply. In this paper, the adsorption characteristics of oxygen on the ZrCo(110) surface were investigated, and the effect of oxygen occupying an active site on the surface on the hydrogen adsorption behavior was discussed. The results show that the dissociation barrier of H2 is increased by more than 26% after O occupies the active sites on the ZrCo(110) surface, and the probability of H2 adsorption and dissociation decreases significantly. The adsorption energy of H atoms on the O–ZrCo(110) surface decreased by 18–56%, and the adsorption stability of H decreased. In addition, H atom diffusion on the surface and into bulk are prevented with higher reaction energetic barriers by O occupying active sites. Eventually, the ability of the ZrCo surface to adsorb hydrogen is seriously reduced.

Moderate Constraint Facilitates Association and Force-Dependent Dissociation of HA-CD44 Complex.

Binding of cell surface glycoprotein CD44 to hyaluronic acid (HA) is a key event for mediating cell adhesion, motility, metastasis, inflammatory responses and tumor development, but the regulation mechanism and its molecular basis under diverse mechanical constraints remain unclear. We herein investigated interaction of CD44 HABD (HA binding site domain) to HA through free and steered molecular dynamics (MD) simulations as well as atomic force microscope (AFM) measurement using different constraints on HA. The middle, two ends or both of the constrained HA chains were fixed for MD simulations, while one and two biotin-avidin linkage or physical absorption were used to immobilize HA on substrates for AFM experiments, to model HA chains with low, moderate and high HA flexibilities, respectively. We found that binding of CD44 to moderate fixed HA was possessed of a better thermo-stability, a lower mechanical strength and a higher dissociation probability, while higher adhesive frequency, smaller rupture force and shorter lifetime were assigned to CD44 on the two biotin-immobilized HA rather than one biotin-immobilized or physically absorbed HA on substrates, suggesting a moderate HA flexibility requirement in favor of association and force-induced dissociation of CD44-HA complex. Tensile-induced convex conformation of HA chain was responsible for reduction of complex mechano-stability and did inversely a shrunken CD44 HABD under stretching; transition from catch bond to slip bond governed CD44-HA interaction. This study uncovered the regulation mechanism and its molecular basis for CD44-HA affinity under diverse mechano-microenvironments and provided a new insight into CD44-HA interaction-mediated cell inflammatory responses and tumor development.

UV photodissociation dynamics of the acetone oxide Criegee intermediate: experiment and theory.

The photodissociation dynamics of the dimethyl-substituted acetone oxide Criegee intermediate [(CH3)2COO] is characterized following electronic excitation to the bright 1ππ* state, which leads to O (1D) + acetone [(CH3)2CO, S0] products. The UV action spectrum of (CH3)2COO recorded with O (1D) detection under jet-cooled conditions is broad, unstructured, and essentially unchanged from the corresponding electronic absorption spectrum obtained using a UV-induced depletion method. This indicates that UV excitation of (CH3)2COO leads predominantly to the O (1D) product channel. A higher energy O (3P) + (CH3)2CO (T1) product channel is not observed, although it is energetically accessible. In addition, complementary MS-CASPT2 trajectory surface-hopping (TSH) simulations indicate minimal population leading to the O (3P) channel and non-unity overall probability for dissociation (within 100 fs). Velocity map imaging of the O (1D) products is utilized to reveal the total kinetic energy release (TKER) distribution upon photodissociation of (CH3)2COO at various UV excitation energies. Simulation of the TKER distributions is performed using a hybrid model that combines an impulsive model with a statistical component, the latter reflecting the longer-lived (>100 fs) trajectories identified in the TSH calculations. The impulsive model accounts for vibrational activation of (CH3)2CO arising from geometrical changes between the Criegee intermediate and the carbonyl product, indicating the importance of CO stretch, CCO bend, and CC stretch along with activation of hindered rotation and rock of the methyl groups in the (CH3)2CO product. Detailed comparison is also made with the TKER distribution arising from photodissociation dynamics of CH2OO upon UV excitation.

Nonadiabatic wave packet dynamics and predissociation resonances in sodium hydride.

Vibrational wave packet dynamics provides an opportunity to explore the energy landscape and the population transfer between nonadiabatically coupled excited electronic states. Here the coupled nonadiabatic dynamics of the C1Σ+ and D1Σ+ states of sodium hydride (NaH) in the gas phase in the adiabatic picture is studied, using a sequence of ultra-fast laser pulses in the femtosecond region. Emergence of different population dynamics and dissociation probabilities is shown by carefully choosing the pulse wavelength, duration and time-shift between the pulses, exciting the molecule from the ground X1Σ+ state via the immediate A1Σ+ state. Quantum dynamics simulations were performed in the adiabatic picture, avoiding the adiabatic to diabatic transformation. Predissociation resonances, i.e. vibrational states with finite lifetimes, arise due to nonadiabatic couplings between bound and continuum states. Here accurate resonance energies and widths are computed providing further insight into the dissociation dynamics.

Analysis of the first infrared spectrum of quasi-bound H2 line emission in Herbig-Haro 7

Context. Highly excited molecular hydrogen (H2) has been observed in many regions of shocked molecular gas. A recently published K-band spectrum of Herbig-Haro 7 (HH7) contains several vibration-rotation lines of H2 from highly excited energy levels that have not been detected elsewhere, including a line at 2.179 μm identified as arising from the v = 2, J = 29 level, which lies above the dissociation limit of H2. One emission line at 2.104 μm in this spectrum was unidentified. Aims. We aim to complete the analysis of the spectrum of HH7 by including previously missing molecular data that have been recently computed. Methods. We re-analysed the K-band spectrum, emphasising the physics of quasi-bound upper levels that can produce infrared emission lines in the K band. Results. We confirm the identification of the 2 − 1 S(27) line at 2.1785 μm and identify the line at 2.1042 μm as due to the 1−0 S(29) transition of H2, whose upper level energy is also higher than the dissociation limit. This latter identification, its column density, and the energy of its upper level further substantiate the existence of a hot thermal component at 5000 K in the HH7 environment. Conclusions. The presence of the newly identified 1 − 0 S(29) line, whose quasi-bound upper level (v = 1, J = 31) has a significant spontaneous dissociation probability, shows that dissociation of H2 is occurring. The mechanism by which virtually all of the H2 in levels with energies from 20 000 K to 53 000 K is maintained in local thermodynamic equilibrium at a single temperature of ∼5000 K remains to be understood.

Dissociation dynamics of a diatomic molecule in an optical cavity.

We study the dissociation dynamics of a diatomic molecule, modeled as a Morse oscillator, coupled to an optical cavity. A marked suppression of the dissociation probability, both classical and quantum, is observed for cavity frequencies significantly below the fundamental transition frequency of the molecule. We show that the suppression in the probability is due to the nonlinearity of the dipole function. The effect can be rationalized entirely in terms of the structures in the classical phase space of the model system.

Unconventional energetics of small vacancy clusters in BCC high-entropy alloy Nb0.75ZrTiV0.5

The stability of small vacancy clusters including divacancy, trivacancy and tetravacancy has been studied in body-centered cubic high-entropy alloy Nb0.75ZrTiV0.5 in structures of random solid solution and short-range order by first-principles calculations and molecular dynamics simulations. Different from conventional body-centered cubic metals, the tightly bound configurations have a lower structural stability and are not preferred energetically in the studied high-entropy alloy. Instability of vacancy configurations leads to vacancy-atom exchanges that favor less compact configurations. The formation energy of small vacancy clusters is much smaller than its constituent elements of Nb and V due to the large structural adjustment induced by severe local lattice distortion. The difference in local lattice distortion and elemental arrangement in the vacancy neighborhood leads to significant site-to-site variation in vacancy cluster energy and configuration. The formation energy has a strong correlation with the local energy state of the vacancy configuration and the extent of structural relaxation. Compared to random solid solution, the structure of short-range order has a higher stability for the most compact cluster configurations and tends to have higher vacancy cluster formation energy. According to classical molecular dynamics simulations of cluster diffusion at high temperature, the studied high-entropy alloy has a higher probability of cluster dissociation compared to Nb and V. The unconventional energetics of small vacancy clusters is expected to have a profound impact on their generation, diffusion, dissociation, coalescence, as well as the defect microstructure evolution during irradiation.

Thermal Activation of PEDOT:PSS/PM6:Y7 Based Films Leads to Unprecedent High Short‐Circuit Current Density in Nonfullerene Organic Photovoltaics

AbstractFinding an effective approach to suppress trap formation is a potential route for enhancing the performance of nonfullerene organic photovoltaic (NF‐OPVs) devices. Here, an extraordinary short‐circuit current density (JSC) value of 32.65 mA cm‐2 is achieved, higher than the state‐of‐the art NF‐OPVs reported, reaching a high power conversion efficiency (PCE) of 17.92%. This remarkable enhancement is exhibited through the fine‐tuning of PEDOT:PSS/PM6:Y7 films and interface morphologies via applying the prethermal treatment approach (Pre‐TT) to the devices, which exhibit JSC and PCE enhancement of 21% and 8%, respectively, compared to the pristine devices. Accordingly, the dependence of the JSC upon the Pre‐TT approach through a range of morphological, optical, electrical, and advanced transient measurements is investigated. The Pre‐TT‐based films are found to possess optimal smooth blend morphology with better dispersity owing to reduced domain size. Moreover, the measurements show that the optimized treated devices present higher exciton dissociation probabilities and generation rate of the free charge carriers, showing an ideal balanced electron/hole mobility that reveals the JSC and PCE enhancement. Hence, Pre‐TT approach provides a facile passivation strategy that reduces the trap state density of the blend film, improves interface charge transfer, allows balanced electron/hole mobility, and thus promotes device performance.

Non-equilibrium dissociation rate coefficient of O2+O2 collision at high temperatures

We focus on the collision dissociation process of O2+O2→O+O+O2 at high temperatures (8000 K–30000 K). The research method is the new general non-equilibrium dynamics model proposed by Singh et al. The model parameters are determined by calculating the dissociation probability under the specific vibrational energy and the energy distribution functions in the quasi-steady state (QSS). It is found that the dissociation rate is more easily at high vibrational energy levels. Moreover, the energy distribution function deviates from the Boltzmann distribution in the QSS state. We obtain the dissociation rate coefficients at high temperatures by integrating the dissociation probability and the internal energy distribution functions (the Boltzmann distribution, the QSS state distribution, and the non-Boltzmann distribution). Our results demonstrate that the rate coefficients depend on the vibrational temperature and more strongly at a lower translational temperature.

A simple doping strategy to improve PEDOT:PSS charge extraction capability in polymer solar cells

Black Phosphorus (BP) has shown great potential in optoelectronic devices due to its remarkable semiconductor properties. Herein, liquid-exfoliated BP nanosheets is doped into poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) to form a hybrid hole transport layers (HTLs). The incorporation of BP nanosheets in PEDOT:PSS dramatically changes the nanostructure and electrical conductivity of film. The BP doped PEDOT:PSS HTLs possess excellent charge selectivity and transport capability, which are proved in non-fullerene and fullerene blend system based polymer solar cells (PSCs). Furthermore, the nanostructure of PM6:Y6 light absorber changes a lot after introduction of BP nanosheets. Thus, weak charge recombination loss, high exciton generation rate and dissociation probability, and low transport resistance are observed in BP nanosheets doped PEDOT:PSS HTLs based cells, which result in improved power conversion efficiency (PCE). As a result, significant improvement of PCE (>18%) is observed in both non-fullerene and fullerene blend systems based cells. This result demonstrates a simple and effective strategy to form efficient HTLs in high-efficiency PSCs.

The nature of excitons in PPDT2FBT:PCBM solar cells: Role played by PCBM

In organic semiconductor-based bulk heterojunction solar cells, the presence of an acceptor increases the formation of charge-transfer (CT) excitons, thereby leading to higher exciton dissociation probabilities. In this work we used steady-state electroabsorption (EA) measurements to probe the change in the nature of excitons as the blend composition of the solar cell active layer material was varied. We investigated blends of poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c]-[1,2,5]thiadiazole)] (PPDT2FBT) and (6,6)-phenyl C71 butyric acid methyl ester (PCBM). Analysis of the EA spectra showed that in the presence of a fullerene-based acceptor, like PCBM, CT characteristics of the excitons were modified, though no new CT signature was observed in the blend. Enhancement in the CT characteristics in the blend was reflected in photoluminescence (PL) measurements of the blends, where PL quenching of ∼63% was observed for 1% PCBM. The quenching reaches saturation at about 20% PCBM. However, efficiency of the device increased with a PCBM percentage beyond 20%. Maximum efficiency was obtained for the blend with 50% PCBM, among the blend compositions studied in this work, indicating the optimum concentration of PCBM for best power conversion efficiency to be around that value. When we compared the experimental results with simulations, the variation of the device efficiency with PCBM percentage was shown to arise from multiple factors, such as an increase in the polarizability and dipole moment of excitons, and the efficiency of the carrier collection from the bulk of the active layer.

Effect of molecular orientation on predissociation of NaI molecules

Based on the time-depend quantum wave packet method, a scheme is proposed to investigate the effect of the molecular orientation on the predissociation of NaI molecules. The molecular orientation in the ground state is steered by THz half-cycle pulse. Then the oriented molecule is excited by femtosecond pump pulse. Molecular orientation has a significant effect on the angular distribution of wave packets. The excited wave packet is distributed in a more narrow region with the increase of molecular orientation degree. The angular distribution of dissociated products is essentially consistent with the angular distribution of excited wave packet. The dissociation probability is proportional to the excitation probability of pump pulse, which is related to the molecular orientations. Compared with the result of predissociation without molecular orientation, the maximal dissociation probability can increase by 6.5% in our work. The electric field intensity of the pump pulse also has a significant influence on dissociation probability.

Anisotropic tomography of heavy quark dissociation by using the general propagator structure in a finite magnetic field

In this work we have explored the imaginary part of the Heavy Quark (HQ) potential and subsequently the dissociation of heavy quarkonia at finite temperature and magnetic field. With respect to earlier investigations on this topic, present work contain three new ingredients. First one is considering all Landau level summation, for which present work can be applicable in entire magnetic field domain - from weak to strong. Second one is the general structure of the gauge boson propagator in a hot magnetized medium, which is used here in heavy quark potential problem first time. Third one is a rich anisotropic structure of the complex heavy quark potential, which explicitly depends on the longitudinal and transverse distance. By comparing with earlier references, we have attempted to display our new contributions by plotting heavy quark potential tomography and dissociation probability at finite temperature and magnetic field.

Multilayer Multiconfiguration Time-Dependent Hartree Study on the Mode-/Bond-Specific Quantum Dynamics of Water Dissociation on Cu(111).

In this work, full-dimensional (9D) quantum dynamics calculations on mode-/bond-specific surface scattering of a water molecule on a copper (111) rigid surface are performed through the multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method. To easily perform the ML-MCTDH calculations on such a triatomic molecule-surface system, we first choose specific Jacobi coordinates as a set of coordinates of water. Next, to efficiently perform the 9D ML-MCTDH wavepacket propagation, the potential energy surface is transferred to a canonical polyadic decomposition form with the aid of a Monte Carlo-based method. Excitation-specific dissociation probabilities of H2O on Cu(111) are computed, and mode-/bond-specific dynamics are demonstrated by comparison with a probability curve computed for a water molecule in the ground state. The dependence of the dissociation probability of the initial state of H2O is studied, and it is found that the excitation-specific dissociation probabilities can be divided into three groups. We find that the vibrationally excited states enhance the dissociation reactivity of H2O, while the rotationally excited states hardly influence it.

Accurate description of the quantum dynamical surface temperature effects on the dissociative chemisorption of H2 from Cu(111).

Accurately describing surface temperature effects for the dissociative scattering of H2 on a metal surface on a quantum dynamical (QD) level is currently one of the open challenges for theoretical surface scientists. We present the first QD simulations of hydrogen dissociating on a Cu(111) surface, which accurately describe all relevant surface temperature effects, using the static corrugation model. The reaction probabilities we obtain show very good agreement with those found using quasi-classical dynamics (QCD), both for individual surface slabs and for an averaged, thus Monte Carlo sampled, set of thermally distorted surface configurations. Rovibrationally elastic scattering probabilities show a much clearer difference between the QCD and QD results, which appears to be traceable back toward thermally distorted surface configurations with very low dissociation probabilities and underlines the importance of investigating more observables than just dissociation. By reducing the number of distorted surface atoms included in the dynamical model, we also show that only including one surface atom, or even three surface atoms, is generally not enough to accurately describe the effects of the surface temperature on dissociation and elastic scattering. These results are a major step forward in accurately describing hydrogen scattering from a thermally excited Cu(111) surface and open up a pathway to better describe reaction and scattering from other relevant crystal facets, such as stepped surfaces, at moderately elevated surface temperatures where quantum effects are expected to play a more important role in the dissociation of H2 on Cu.

Effects of vibrational and rotational excitations on dissociative chemisorption dynamics of N2 on Fe(111)

The dissociative chemisorption of N2 is the rate-limiting step for ammonia synthesis in industry. Here, we investigated the role of initially vibrational excitation and rotational excitation of N2 for its reactivity on the Fe(111) surface, based on a recently developed six-dimensional potential energy surface. Six-dimensional quantum dynamics study was carried out to investigate the effect of vibrational excitation for incidence energy below 1.6 eV, due to significant quantum effects for this reaction. The effects of vibrational and rotational excitations at high incidence energies were revealed by quasiclassical trajectory calculations. We found that raising the translational energy can enhance the dissociation probability to some extent, however, the vibrational excitation or rotational excitation can promote dissociation more efficiently than the same amount of translational energy. This study provides valuable insight into the mode-specific dynamics of this heavy diatom-surface reaction.