The Dynamical Density Functional Theory(DDFT)algorithm,derived by associating classical Density Functional Theory(DFT)with the fundamental Smoluchowski dynamical equation,describes the evolution of inhomo-geneous flui...The Dynamical Density Functional Theory(DDFT)algorithm,derived by associating classical Density Functional Theory(DFT)with the fundamental Smoluchowski dynamical equation,describes the evolution of inhomo-geneous fluid density distributions over time.It plays a significant role in studying the evolution of density distributions over time in inhomogeneous systems.The Sunway Bluelight II supercomputer,as a new generation of China’s developed supercomputer,possesses powerful computational capabilities.Porting and optimizing industrial software on this platform holds significant importance.For the optimization of the DDFT algorithm,based on the Sunway Bluelight II supercomputer and the unique hardware architecture of the SW39000 processor,this work proposes three acceleration strategies to enhance computational efficiency and performance,including direct parallel optimization,local-memory constrained optimization for CPEs,and multi-core groups collaboration and communication optimization.This method combines the characteristics of the program’s algorithm with the unique hardware architecture of the Sunway Bluelight II supercomputer,optimizing the storage and transmission structures to achieve a closer integration of software and hardware.For the first time,this paper presents Sunway-Dynamical Density Functional Theory(SW-DDFT).Experimental results show that SW-DDFT achieves a speedup of 6.67 times within a single-core group compared to the original DDFT implementation,with six core groups(a total of 384 CPEs),the maximum speedup can reach 28.64 times,and parallel efficiency can reach 71%,demonstrating excellent acceleration performance.展开更多
We have examined the theoretical implications of combining two main and three auxiliary ligands to form several Ir(Ⅲ)complexes featuring a transition metal as their core atom to identify some appropriate organic ligh...We have examined the theoretical implications of combining two main and three auxiliary ligands to form several Ir(Ⅲ)complexes featuring a transition metal as their core atom to identify some appropriate organic lightemitting diode(OLED)materials.By utilizing electronic structure,frontier molecular orbitals,minimum single-line absorption,triplet excited states,and emission spectral data derived from the density functional theory,the usefulness of these Ir(Ⅲ)complexes,including(piq)_(2)Ir(acac),(piq)_(2)Ir(tmd),(piq)_(2)Ir(tpip),(fpiq)_(2)Ir(acac),(fpiq)_(2)Ir(tmd),and(fpiq)_(2)Ir(tpip),in OLEDs was examined,where piq=1-phenylisoquinoline,fpiq=1-(4-fluorophenyl)isoquinoline,acac=(3Z)-4-hydroxypent-3-en-2-one,tmd=(4Z)-5-hydroxy-2,2,6,6-tetramethylhept-4-en-3-one,and tpip=tetraphenylimido-diphosphonate.These complexes all have low-efficiency roll-off properties,especially(fpiq)_(2)Ir(tpip).Some researchers have successfully synthesized complexes extremely similar to(piq)_(2)Ir(acac)through the Suzuki-Miyaura coupling reaction.展开更多
By adopting stochastic density functional theory(SDFT)and mixed stochastic-deterministic density functional theory(MDFT)methods,we perform first-principles calculations to predict the shock Hugoniot curves of boron(pr...By adopting stochastic density functional theory(SDFT)and mixed stochastic-deterministic density functional theory(MDFT)methods,we perform first-principles calculations to predict the shock Hugoniot curves of boron(pressure P=7.9×10^(3)-1.6×10^(6) GPa and temperature T=25-2800 eV),silicon(P=2.6×10^(3)-7.9×10^(5) GPa and T=21.5-1393 eV),and aluminum(P=5.2×10^(3)-9.0×10^(5) GPa and T=25-1393 eV)over wide ranges of pressure and temperature.In particular,we systematically investigate the impact of different cutoff radii in norm-conserving pseudopotentials on the calculated properties at elevated temperatures,such as pressure,ionization energy,and equation of state.By comparing the SDFT and MDFT results with those of other first-principles methods,such as extended first-principles molecular dynamics and path integral Monte Carlo methods,we find that the SDFT and MDFT methods show satisfactory precision,which advances our understanding of first-principles methods when applied to studies of matter at extremely high pressures and temperatures.展开更多
Based on density functional theory(DFT)and basic structure models,the chemical reactions on the surface of vanadium-titanium based selective catalytic reduction(SCR)denitrification catalysts were summarized.Reasonable...Based on density functional theory(DFT)and basic structure models,the chemical reactions on the surface of vanadium-titanium based selective catalytic reduction(SCR)denitrification catalysts were summarized.Reasonable structural models(non-periodic and periodic structural models)are the basis of density functional calculations.A periodic structure model was more appropriate to represent the catalyst surface,and its theoretical calculation results were more comparable with the experimental results than a nonperiodic model.It is generally believed that the SCR mechanism where NH3 and NO react to produce N2 and H2 O follows an Eley-Rideal type mechanism.NH2 NO was found to be an important intermediate in the SCR reaction,with multiple production routes.Simultaneously,the effects of H2 O,SO2 and metal on SCR catalysts were also summarized.展开更多
Metal-organic framework(MOF) has been widely applied in photocatalysis, which is significant for addressing energy crises and environmental issues. Based on density functional theory calculations,the performances of C...Metal-organic framework(MOF) has been widely applied in photocatalysis, which is significant for addressing energy crises and environmental issues. Based on density functional theory calculations,the performances of Cu-BTC, a copper-based MOF, and its derivatives Cu TM-BTC via the substitution of transition metal(TM) elements at the Cu site for photocatalytic overall water splitting(POWS) have been studied. POWS of Cu-BTC suffers from the sluggish hydrogen evolution reaction due to the large overpotential of 2.02 V and limited solar utilization due to a wide HOMO-LUMO gap of 4.11 e V. Via TM substitution, the HOMO-LUMO gap narrows but still satisfies the redox potentials when taken 3d-TM of Cr, Fe, Co or Ni, 4d-TM of Rh or Pd, or 5d-TM of Re or Pt into consideration, benefiting for the light absorption. Furthermore, Cr and Re could serve as active sites for hydrogen evolution with remarkably lowered overpotentials of 0.79 V and 0.28 V, respectively;similarly, oxygen evolution activities could be enhanced by Fe, Co and Rh because of their reduced overpotentials which are less than 0.5 V. Therefore,our findings pave guidance for designing Cu-BTC derivatives in overall water splitting.展开更多
Understanding the thermodynamic behavior of complex fluids in confined environments is critical for various industrial and natural processes including but not limited to polymer flooding enhanced oil recovery(EOR).In ...Understanding the thermodynamic behavior of complex fluids in confined environments is critical for various industrial and natural processes including but not limited to polymer flooding enhanced oil recovery(EOR).In this work,we develop Atif-V2.0,an extended classical density functional theory(cDFT)framework that integrates the interfacial statistical associating fluid theory(iSAFT)to model multicomponent associating fluids composed of water-soluble polymers,alkanes,and water.Building on the original theoretical framework of Atif for modeling nanoconfined inhomogeneous fluids,Atif-V2.0 embeds explicit solvent and captures additional physical interactions-hydrogen bonding,which are critical in associating fluid systems.The other key feature of Atif-V2.0 is its ability to account for polymer topology.We demonstrate its capability by predicting the equilibrium structure and thermodynamic behavior of branched hydrolyzed polyacrylamide solutions near hard walls with various branching topologies,which provides a robust theoretical tool for the rational design of EOR polymers.展开更多
In this study,a framework for predicting the gas-sensitive properties of gas-sensitive materials by combining machine learning and density functional theory(DFT)has been proposed.The framework rapidly predicts the gas...In this study,a framework for predicting the gas-sensitive properties of gas-sensitive materials by combining machine learning and density functional theory(DFT)has been proposed.The framework rapidly predicts the gas response of materials by establishing relationships between multisource physical parameters and gas-sensitive properties.In order to prove its effectiveness,the perovskite Cs_(3)Cu_(2)I_(5) has been selected as the representative material.The physical parameters before and after the adsorption of various gases have been calculated using DFT,and then a machine learning model has been trained based on these parameters.Previous studies have shown that a single physical parameter alone is not enough to accurately predict the gas sensitivity of materials.Therefore,a variety of physical parameters have been selected for machine learning,and the final machine learning model achieved 92%accuracy in predicting gas sensitivity.It is important to note that although there have been no previous reports on the response of Cs_(3)Cu_(2)I_(5) to hydrogen sulfide,the resulting model predicts the gas response of H2S;it is subsequently confirmed experimentally.This method not only enhances the understanding of the gas sensing mechanism,but also has a universal nature,making it suitable for the development of various new gas-sensitive materials.展开更多
A sparsely introduced basal intrinsic 2-type stacking fault(I_(2)-SF)with a dense segregation of clusters(cluster-arranged layer;CAL)inα-Mg exerts a sufficient strengthening effect with a reduced content of additive ...A sparsely introduced basal intrinsic 2-type stacking fault(I_(2)-SF)with a dense segregation of clusters(cluster-arranged layer;CAL)inα-Mg exerts a sufficient strengthening effect with a reduced content of additive elements.Moreover,the dynamic nucleation and growth of CALs during deformation largely improves the creep resistance.This paper analyzes the cosegregation behaviors of yttrium(Y)and zinc(Zn)atoms at an I_(2)-SF in bulk and at basal edge dislocations using density functional theory calculations.We also study the modification of the generalized stacking-fault energy(GSFE)curves associated with the cosegregation.The segregation energies of Y and Zn atoms in the I_(2)-SF are relatively small during the initial segregation of a cluster,but increases stepwise as the cluster grows.After introducing Y and Zn atoms in the I_(2)-SF in an energetically stable order,we obtain an L1_(2)-type cluster resembling that reported in the literature.Small structural changes driven by vacancy diffusion produce an exact L1_(2)-type cluster.Meanwhile,the core of the Shockley partial dislocation generates sufficient segregation energy for cluster nucleation.Migration of the Shockley partial dislocation and expansion of the I_(2)-SF part are observed at a specific cluster size.The migration is triggered by a large modification of the GSFE curve and destabilization of the hexagonal close-packed stacking(hcp)by the segregated atoms.At this point,the cluster has reached sufficient size and continues to follow the growth in the I_(2)-SF part.According to our findings,the CAL at elevated temperature is formed through repeated synchronized behavior of cluster nucleation at the Shockley partial dislocation,dislocation migration triggered by the destabilized hcp stacking,and following of cluster growth in the I_(2)-SF part of the dislocation.展开更多
Localized corrosion of 304 stainless steel being the significant parts of Starship rocket seriously threatens the long-term service of such aerospace equipment.Scanning electron microscopy,in situ instruments combinin...Localized corrosion of 304 stainless steel being the significant parts of Starship rocket seriously threatens the long-term service of such aerospace equipment.Scanning electron microscopy,in situ instruments combining electrochemical workstation and Raman spectroscopy,and Density Dunctional Theory(DFT)calculations were employed.The surface morphologies,alloying elements,molecular fingerprint Raman evidence and theoretical mechanism for the localized corrosion of 304 stainless steel during the electrochemical polarization in the mixture solutions containing 0.5 mol/L H_(2)SO_(4) and 2,2'-bipyridine(bipy)with concentrations of 0.001,0.010,0.100 mol/L were discussed.In comparison,the presence of bipy up to 0.100 mol/L in such mixture solutions displayed the neglectable effect on the Fe(Ⅱ)/Fe(Ⅲ)reaction in the polarization process.Raman vibrational frequency around 1492 cm^(-1)was the evidence of pink color appearance due to the formation of[Fe^(Ⅱ)(bipy)_(3)]^(2+).Raman and DFT indicated the yellow color emergence due to the presence ofμ-O-[Fe^(Ⅲ)(bipy)_(2)(H_(2)O)]_(2)^(4+)due to the oxidation reaction of[Fe^(Ⅱ)(bipy)_(3)]^(2+)with H_(2)O_(2) oxidant,and the dimerization of[Fe^(Ⅲ)(bipy)_(3)]^(3+),Furthermore,a quantitative model between[Fe^(Ⅱ)(bipy)_(3)]^(2+)concentration and Raman intensity at 1492 cm^(-1) has been built up.Two linear functions were revealed when[Fe^(Ⅱ)(bipy)_(3)]^(2+)concentrations were at 0-0.002 mol/L and 0.002-0.004 mol/L and a concentration error of less than 5%was evidenced in comparison with that investigated by the inductively coupled plasma.The proposed passivation mechanism and quantitative concentration model of 304 stainless steel have certain significance for its corrosion protection andcorrosionevaluation.展开更多
This study explores the molecular design of sulfur-containing polymers with high refractive indices(RI)and optimized Abbe numbers for advanced optical applications.The high molar refraction and low dispersion of sulfu...This study explores the molecular design of sulfur-containing polymers with high refractive indices(RI)and optimized Abbe numbers for advanced optical applications.The high molar refraction and low dispersion of sulfur make it an ideal component for enhancing the optical properties of polymers.Density functional theory(DFT)calculations were employed to predict the RI and Abbe numbers for a range of sulfurbased polymers.To improve the accuracy of the theoretical predictions,a correction function was developed by comparing the calculated values with experimental data.The key polymer families investigated included sulfur-containing polycarbonates,heterocyclic optical resins,and cycloolefins,all modified to balance RI enhancement with dispersion control.The results demonstrate that increasing the sulfur content and introducing specific heterocycles and bridged rings can effectively increase the RI while maintaining desirable Abbe numbers.Polymers incorporating 1,4-dithiane and sulfur-bridged rings exhibit excellent optical clarity and minimal visible light absorption,making them suitable for lens and coating applications.The study also calculated the UV-visible spectra for the most promising polymers,confirming their high transparency.This work establishes a predictive framework for developing high-performance optical polymers and offers a systematic approach for balancing the refractive index and dispersion,thereby providing valuable insights for the design of next-generation optical materials.展开更多
Ab initio modeling of dynamic structure factors(DSF)and related density response properties in the warm dense matter(WDM)regime is a challenging computational task.The DSF,convolved with a probing X-ray beam and instr...Ab initio modeling of dynamic structure factors(DSF)and related density response properties in the warm dense matter(WDM)regime is a challenging computational task.The DSF,convolved with a probing X-ray beam and instrument function,is measured in X-ray Thom-son scattering(XRTS)experiments,which allow the study of electronic structure properties at the microscopic level.Among the various ab initio methods,linear-response time-dependent density-functional theory(LR-TDDFT)is a key framework for simulating the DSF.The standard approach in LR-TDDFT for computing the DSF relies on the orbital representation.A significant drawback of this method is the unfavorable scaling of the number of required empty bands as the wavenumber increases,making LR-TDDFT impractical for modeling XRTS measurements over large energy scales,such as in backward scattering geometry.In this work,we consider and test an alternative approach to LR-TDDFT that employs the Liouville–Lanczos(LL)method for simulating the DSF of WDM.This approach does not require empty states and allows the DSF at large momentum transfer values and over a broad frequency range to be accessed.We compare the results obtained from the LL method with those from the solution of Dyson’s equation using the standard LR-TDDFT within the projector augmented-wave formalism for isochorically heated aluminum and warm dense hydrogen.Additionally,we utilize exact path integral Monte Carlo results for the imaginary-time density-density correlation function(ITCF)of warm dense hydrogen to rigorously benchmark the LL approach.We discuss the application of the LL method for calculating DSFs and ITCFs at different wavenumbers,the effects of pseudopotentials,and the role of Lorentzian smearing.The successful validation of the LL method under WDM conditions makes it a valuable addition to the ab initio simulation landscape,supporting experimental efforts and advancing WDM theory.展开更多
In 2014, 50 years following the introduction of density functional theory (DFT), a rigorous understanding of it was published [AIP Advances, 4, 127,104 (2014)]. This understanding includes two features that complete t...In 2014, 50 years following the introduction of density functional theory (DFT), a rigorous understanding of it was published [AIP Advances, 4, 127,104 (2014)]. This understanding includes two features that complete the theory in practice, inasmuch as they are necessary for its correct application in electronic structure calculations;this understanding elucidates what appears to have been the crucial misunderstanding for 50 years, namely, the confusion between a stationary solution, attainable with most basis sets, following self-consistent iterations, with the ground state solution. The latter is obtained by a calculation that employs the well-defined optimal basis set for the system. The aim of this work is to review the above understanding and to extend it to the relativistic generalization of density functional theory by Rajagopal and Callaway [Phys. Rev. B7, 1912 (1973)]. This extension straightforwardly follows similar steps taken in the non-relativistic case, with the four-component current density, in the former, replacing the electronic charge density, in the latter. This new understanding, which completes relativistic DFT in practice, is expected to be needed for the study of heavy atoms and of materials (from molecules to solids) containing them—as is the case for some high temperature superconductors.展开更多
We report on a temperature-dependent resonance Raman spectral characterization of the polyene chain of canthax- anthin. It is observed that all vibrational intensities of the polyene chain are inversely proportional t...We report on a temperature-dependent resonance Raman spectral characterization of the polyene chain of canthax- anthin. It is observed that all vibrational intensities of the polyene chain are inversely proportional to temperature, which is analyzed by the resonance Raman effect and the coherent weakly damped electron/lattice vibrations. The increase in intensity of the CC overtone/combination relative to the fundamental with temperature decreasing is detected and discussed in terms of electron/phonon coupling and the activation energy Uop. Moreover, the polyene chain studies using the density functional theory B3LYP/6-31 G＊ level reveal a prominent peak at 1525 cm-1 consisting of two closely spaced modes that are both dominated by C=C stretching coordinates of the polyene chain.展开更多
As a substitute for lithium ion batteries, Na chemistry for ion battery systems is promising materials for energy storage applications for the next generation. Herein, the structures, IR and UV-visible spectra of 2-am...As a substitute for lithium ion batteries, Na chemistry for ion battery systems is promising materials for energy storage applications for the next generation. Herein, the structures, IR and UV-visible spectra of 2-aminoterephthalic acid (H2ATA), disodium 2-aminoterephthalate (Na2ATA), trisodium 2-aminotere-phthalate (Na3ATA) and tetrasodium 2-aminoterephthalate (Na4ATA) have been studied using density functional theory (DFT/B3LYP/6-311++G(d,p)). The theoretical geometric parameters and FTIR results showed very good agreement with the experimental results. Different conformers of Na2ATA, Na3ATA and Na4ATA showed that the binding energy per sodium in Na2ATA, Na3ATA and Na4ATA is -694.94, -543.44 and -407.46 kJ/mol, respectively. The Na3ATA and Na4ATA salts are higher in energy (151.46 and 287.48 kJ/mol, respectively) than Na2ATA, indicating the higher stability of the Na2ATA complex. The calculated binding energy, enthalpy and Gibbs free energy of Na2ATA, Na3ATA and Na4ATA revealed that the compounds are thermodynamically stable. Natural bond orbital (NBO) analysis of Na2ATA, Na3ATA and Na4ATA indicated that the major interaction occurs between the lone pair electrons of the oxygen atom and anti-bonding orbitals of carbon atoms of the two carboxylate ions. UV-visible spectrum of the free H2ATA and its sodium salts Na2ATA, Na3ATA and Na4ATA were performed using the time-dependent density functional theory (TD-DFT) method at the level of B3LYP/6-311++G(d,p). The frontier molecular orbital energetic parameters and global reactivity descriptors revealed that the Na4ATA and Na3ATA complexes exhibited a higher band gap (ΔEgap) and electronegativity (χeV) than Na2ATA.展开更多
The structural, electronic, and optical properties of Cu2Zn1−xBaxSn1−ySiyS4 compounds have been calculated using GGA-PBE function within the framework of Density Functional Theory (DFT). In the present work, lattice p...The structural, electronic, and optical properties of Cu2Zn1−xBaxSn1−ySiyS4 compounds have been calculated using GGA-PBE function within the framework of Density Functional Theory (DFT). In the present work, lattice parameters remained the same, that is tetragonal crystal structure for 0% and 100% doping concentration. The electronic band gap of Cu2Zn1−xBaxSn1−ySiyS4 compounds has been gradually increased for continuous increment of doping concentration where the highest electronic band gap is 1.117 eV for Cu2BaSiS4 structure. Moreover, the band gap changes from direct to indirect band gap with the increase of doping concentration in the parent compound. The absorption coefficient has been found to be high (> 104 cm−1) in UV-region for all the doping concentration which makes the studied compound as a potential candidate of absorber layer in the UV detector. The theoretical study of the effect of double doping in the CZTS compound is very interesting for improving the quality of it and it would be a reference for the theoretical and experimental researchers.展开更多
Adsorption of water on sulfide surfaces and natural floatability of sulfide minerals were studied using density functional theory （DFT） method. All computational models were built in a vacuum environment to eliminat...Adsorption of water on sulfide surfaces and natural floatability of sulfide minerals were studied using density functional theory （DFT） method. All computational models were built in a vacuum environment to eliminate the effects of oxygen and other factors. H2O molecule prefers to stay with pyrite and sphalerite surfaces rather than water, whereas for galena, chalcocite, stibnite, and molybdenite, H2O molecule prefers to stay with water rather than the mineral surfaces. On the other hand, pyrite surface favors N2 more than water, while sphalerite surface cannot adsorb N2. These results show that galena, stibnite, chalcocite, and molybdenite are hydrophobic, while sphalerite is hydrophilic. Although pyrite has certain hydrophilicity, it tends to be aerophilic because the reaction of pyrite with H2O is weaker than pyrite with N2. Thus, pyrite, galena, chalcocite, stibnite and molybdenite all have natural floatability.展开更多
The electronic property of pyrite supercell containing As,Se,Te,Co or Ni hetero atoms were calculated using density functional theory（DFT）,and the reactivities of pyrite with oxygen and xanthate were discussed by fr...The electronic property of pyrite supercell containing As,Se,Te,Co or Ni hetero atoms were calculated using density functional theory（DFT）,and the reactivities of pyrite with oxygen and xanthate were discussed by frontier orbital methods.The cell volume expands due to the presence of impurity.Co and Ni mainly affect the bands near Fermi levels,while As mainly affects the shallow and deep valence bands,and Se and Te mainly affect the deep valence bands.Electronic density analysis suggests that there exists a strong covalent interaction between hetero atom and its surrounding atoms.By frontier orbital calculation,it is suggested that As,Co and Ni have greater influence on the HOMO and LUMO of pyrite than Se and Te.In addition,pyrite containing As,Co or Ni is easier to oxidize by oxygen than pyrite containing Se or Te,and pyrite containing Co or Ni has greater interaction with collector.These are in agreement with the observed pyrite practice.展开更多
Based on the parent tetrazole 2N-oxide, six series of novel carbon-linked ditetrazole 2N- oxides with different energetic substituent groups （-NH2, -Na, -NO2, NF2, -NHNO2） and energetic bridge groups （-CH2-, -CH2-C...Based on the parent tetrazole 2N-oxide, six series of novel carbon-linked ditetrazole 2N- oxides with different energetic substituent groups （-NH2, -Na, -NO2, NF2, -NHNO2） and energetic bridge groups （-CH2-, -CH2-CH2-, -NH-, -N=N-, -NH-NH-） were designed. The overall performance and the effects of different energetic substituent groups and energetic bridge groups on the performance were investigated by density functional theory and electrostatic potential methods. The results showed that most of designed compounds have oxygen balance around zero, high heats of formation, high density, high energy, and acceptable sensitivity, indicating that tetrazole N-oxide is a useful parent energetic compound employed for obtaining high energy compounds, even only combined with some very common energetic substituent groups and bridge groups. Comprehensively considering the effects on energy and sensitivity, the -NO2, -NF2, -NH- and-NH-NH- are appropriate substituent groups for combining tetrozale N-oxide to design new energetic compounds, while -NH2, -Na, -CH2-CH2-, and -N=N- are inappropriate.展开更多
Designing and fabricating high-performance photovoltaic devices have remained a major challenge in organic solar cell technologies. In this work, the photovoltaic performances of BTBPD-PC61BM system were theoretically...Designing and fabricating high-performance photovoltaic devices have remained a major challenge in organic solar cell technologies. In this work, the photovoltaic performances of BTBPD-PC61BM system were theoretically investigated by means of density functional theory calculations coupled with the Marcus charge transfer model in order to seek novel photovoltaic systems. Moreover, the hole-transfer properties of BTBPD thin-film were also studied by an amorphous cell with 100 BTBPD molecules. Results revealed that the BTBPD- PC61BM system possessed a middle-sized open-circuit voltage of 0.70 V, large short-circuit current density of 16.874 mA/cm2, large fill factor of 0.846, and high power conversion effi- ciency of 10%. With the Marcus model, the charge-dissociation rate constant was predicted to be as fast as 3.079×10^13 s^-1 in the BTBPD-PC61BM interface, which was as 3-5 orders of magnitude large as the decay （radiative and non-radiative） rate constant （108-10^10 s^-1）, indicating very high charge-dissociation efficiency （-100%） in the BTBPD-PC61BM system. Furthermore, by the molecular dynamics simulation, the hole mobility for BTBPD thin-film was predicted to be as high as 3.970× 10^-3 cm^2V^-1s^-1, which can be attributed to its tight packing in solid state.展开更多
We study the geometries, stabilities, electronic and magnetic properties of （MgO）n （n=2-10） clusters doped with a single Mn atom using the density functional theory with the gener- alized gradient approximation. T...We study the geometries, stabilities, electronic and magnetic properties of （MgO）n （n=2-10） clusters doped with a single Mn atom using the density functional theory with the gener- alized gradient approximation. The optimized geometries show that the impurity Mn atom prefers to replace the Mg atom which has low coordination number in all the lowest-energy MnMgn-1On （n=2-10） structures. The stability analysis clearly represents that the average binding energies of the doped clusters are larger than those of the corresponding pure （MgO）n clusters. Maximum peaks of the second order energy differences are observed for MnMg~_1On clusters at n=6, 9, implying that these clusters exhibit higher stability than their neighboring clusters. In addition, all the Mn-doped Mg clusters exhibit high total magnetic moments with the exception of MnMgO2 which has 3.00μB. Their magnetic behavior is attributed to the impurity Mn atom, the charge transfer modes, and the size of MnMgn- 1On clusters.展开更多
基金supported by National Key Research and Development Program of China under Grant 2024YFE0210800National Natural Science Foundation of China under Grant 62495062Beijing Natural Science Foundation under Grant L242017.
文摘The Dynamical Density Functional Theory(DDFT)algorithm,derived by associating classical Density Functional Theory(DFT)with the fundamental Smoluchowski dynamical equation,describes the evolution of inhomo-geneous fluid density distributions over time.It plays a significant role in studying the evolution of density distributions over time in inhomogeneous systems.The Sunway Bluelight II supercomputer,as a new generation of China’s developed supercomputer,possesses powerful computational capabilities.Porting and optimizing industrial software on this platform holds significant importance.For the optimization of the DDFT algorithm,based on the Sunway Bluelight II supercomputer and the unique hardware architecture of the SW39000 processor,this work proposes three acceleration strategies to enhance computational efficiency and performance,including direct parallel optimization,local-memory constrained optimization for CPEs,and multi-core groups collaboration and communication optimization.This method combines the characteristics of the program’s algorithm with the unique hardware architecture of the Sunway Bluelight II supercomputer,optimizing the storage and transmission structures to achieve a closer integration of software and hardware.For the first time,this paper presents Sunway-Dynamical Density Functional Theory(SW-DDFT).Experimental results show that SW-DDFT achieves a speedup of 6.67 times within a single-core group compared to the original DDFT implementation,with six core groups(a total of 384 CPEs),the maximum speedup can reach 28.64 times,and parallel efficiency can reach 71%,demonstrating excellent acceleration performance.
文摘We have examined the theoretical implications of combining two main and three auxiliary ligands to form several Ir(Ⅲ)complexes featuring a transition metal as their core atom to identify some appropriate organic lightemitting diode(OLED)materials.By utilizing electronic structure,frontier molecular orbitals,minimum single-line absorption,triplet excited states,and emission spectral data derived from the density functional theory,the usefulness of these Ir(Ⅲ)complexes,including(piq)_(2)Ir(acac),(piq)_(2)Ir(tmd),(piq)_(2)Ir(tpip),(fpiq)_(2)Ir(acac),(fpiq)_(2)Ir(tmd),and(fpiq)_(2)Ir(tpip),in OLEDs was examined,where piq=1-phenylisoquinoline,fpiq=1-(4-fluorophenyl)isoquinoline,acac=(3Z)-4-hydroxypent-3-en-2-one,tmd=(4Z)-5-hydroxy-2,2,6,6-tetramethylhept-4-en-3-one,and tpip=tetraphenylimido-diphosphonate.These complexes all have low-efficiency roll-off properties,especially(fpiq)_(2)Ir(tpip).Some researchers have successfully synthesized complexes extremely similar to(piq)_(2)Ir(acac)through the Suzuki-Miyaura coupling reaction.
基金supported by the National Key R&D Program of China under Grant No.2025YFB3003603the National Natural Science Foundation of China under Grant Nos.12135002 and 12105209.
文摘By adopting stochastic density functional theory(SDFT)and mixed stochastic-deterministic density functional theory(MDFT)methods,we perform first-principles calculations to predict the shock Hugoniot curves of boron(pressure P=7.9×10^(3)-1.6×10^(6) GPa and temperature T=25-2800 eV),silicon(P=2.6×10^(3)-7.9×10^(5) GPa and T=21.5-1393 eV),and aluminum(P=5.2×10^(3)-9.0×10^(5) GPa and T=25-1393 eV)over wide ranges of pressure and temperature.In particular,we systematically investigate the impact of different cutoff radii in norm-conserving pseudopotentials on the calculated properties at elevated temperatures,such as pressure,ionization energy,and equation of state.By comparing the SDFT and MDFT results with those of other first-principles methods,such as extended first-principles molecular dynamics and path integral Monte Carlo methods,we find that the SDFT and MDFT methods show satisfactory precision,which advances our understanding of first-principles methods when applied to studies of matter at extremely high pressures and temperatures.
基金supported by the National Key Research&Development(R&D)Program of China(No.2017YFC0210500)the National Natural Science Foundation of China(No.51938014)
文摘Based on density functional theory(DFT)and basic structure models,the chemical reactions on the surface of vanadium-titanium based selective catalytic reduction(SCR)denitrification catalysts were summarized.Reasonable structural models(non-periodic and periodic structural models)are the basis of density functional calculations.A periodic structure model was more appropriate to represent the catalyst surface,and its theoretical calculation results were more comparable with the experimental results than a nonperiodic model.It is generally believed that the SCR mechanism where NH3 and NO react to produce N2 and H2 O follows an Eley-Rideal type mechanism.NH2 NO was found to be an important intermediate in the SCR reaction,with multiple production routes.Simultaneously,the effects of H2 O,SO2 and metal on SCR catalysts were also summarized.
基金the financial support from National Natural Science Foundation of China (No. 21503097)Postgraduate Research & Practice Innovation Program of Jiangsu Province (No. KYCX23_3905)。
文摘Metal-organic framework(MOF) has been widely applied in photocatalysis, which is significant for addressing energy crises and environmental issues. Based on density functional theory calculations,the performances of Cu-BTC, a copper-based MOF, and its derivatives Cu TM-BTC via the substitution of transition metal(TM) elements at the Cu site for photocatalytic overall water splitting(POWS) have been studied. POWS of Cu-BTC suffers from the sluggish hydrogen evolution reaction due to the large overpotential of 2.02 V and limited solar utilization due to a wide HOMO-LUMO gap of 4.11 e V. Via TM substitution, the HOMO-LUMO gap narrows but still satisfies the redox potentials when taken 3d-TM of Cr, Fe, Co or Ni, 4d-TM of Rh or Pd, or 5d-TM of Re or Pt into consideration, benefiting for the light absorption. Furthermore, Cr and Re could serve as active sites for hydrogen evolution with remarkably lowered overpotentials of 0.79 V and 0.28 V, respectively;similarly, oxygen evolution activities could be enhanced by Fe, Co and Rh because of their reduced overpotentials which are less than 0.5 V. Therefore,our findings pave guidance for designing Cu-BTC derivatives in overall water splitting.
基金financially supported by the Key Technologies R&D Program of China National Offshore Oil Corporation(No.KJGG2021-0504)。
文摘Understanding the thermodynamic behavior of complex fluids in confined environments is critical for various industrial and natural processes including but not limited to polymer flooding enhanced oil recovery(EOR).In this work,we develop Atif-V2.0,an extended classical density functional theory(cDFT)framework that integrates the interfacial statistical associating fluid theory(iSAFT)to model multicomponent associating fluids composed of water-soluble polymers,alkanes,and water.Building on the original theoretical framework of Atif for modeling nanoconfined inhomogeneous fluids,Atif-V2.0 embeds explicit solvent and captures additional physical interactions-hydrogen bonding,which are critical in associating fluid systems.The other key feature of Atif-V2.0 is its ability to account for polymer topology.We demonstrate its capability by predicting the equilibrium structure and thermodynamic behavior of branched hydrolyzed polyacrylamide solutions near hard walls with various branching topologies,which provides a robust theoretical tool for the rational design of EOR polymers.
基金supported by Natural Science Foundation of Jiangsu Province(No.BK20210494)National Natural Science Foundation of China(No.52303356).
文摘In this study,a framework for predicting the gas-sensitive properties of gas-sensitive materials by combining machine learning and density functional theory(DFT)has been proposed.The framework rapidly predicts the gas response of materials by establishing relationships between multisource physical parameters and gas-sensitive properties.In order to prove its effectiveness,the perovskite Cs_(3)Cu_(2)I_(5) has been selected as the representative material.The physical parameters before and after the adsorption of various gases have been calculated using DFT,and then a machine learning model has been trained based on these parameters.Previous studies have shown that a single physical parameter alone is not enough to accurately predict the gas sensitivity of materials.Therefore,a variety of physical parameters have been selected for machine learning,and the final machine learning model achieved 92%accuracy in predicting gas sensitivity.It is important to note that although there have been no previous reports on the response of Cs_(3)Cu_(2)I_(5) to hydrogen sulfide,the resulting model predicts the gas response of H2S;it is subsequently confirmed experimentally.This method not only enhances the understanding of the gas sensing mechanism,but also has a universal nature,making it suitable for the development of various new gas-sensitive materials.
基金supported by the Japan Science and Technology Agency(JST),CREST(grant number JapanJPR2094)。
文摘A sparsely introduced basal intrinsic 2-type stacking fault(I_(2)-SF)with a dense segregation of clusters(cluster-arranged layer;CAL)inα-Mg exerts a sufficient strengthening effect with a reduced content of additive elements.Moreover,the dynamic nucleation and growth of CALs during deformation largely improves the creep resistance.This paper analyzes the cosegregation behaviors of yttrium(Y)and zinc(Zn)atoms at an I_(2)-SF in bulk and at basal edge dislocations using density functional theory calculations.We also study the modification of the generalized stacking-fault energy(GSFE)curves associated with the cosegregation.The segregation energies of Y and Zn atoms in the I_(2)-SF are relatively small during the initial segregation of a cluster,but increases stepwise as the cluster grows.After introducing Y and Zn atoms in the I_(2)-SF in an energetically stable order,we obtain an L1_(2)-type cluster resembling that reported in the literature.Small structural changes driven by vacancy diffusion produce an exact L1_(2)-type cluster.Meanwhile,the core of the Shockley partial dislocation generates sufficient segregation energy for cluster nucleation.Migration of the Shockley partial dislocation and expansion of the I_(2)-SF part are observed at a specific cluster size.The migration is triggered by a large modification of the GSFE curve and destabilization of the hexagonal close-packed stacking(hcp)by the segregated atoms.At this point,the cluster has reached sufficient size and continues to follow the growth in the I_(2)-SF part.According to our findings,the CAL at elevated temperature is formed through repeated synchronized behavior of cluster nucleation at the Shockley partial dislocation,dislocation migration triggered by the destabilized hcp stacking,and following of cluster growth in the I_(2)-SF part of the dislocation.
基金supported by the National Natural Science Foundation of China(No.51701239)the University-Industry Collaborative Education Program of MOEinChina(No.BINTECH-KJZX-20220831-35)the Basic-Scientific-Research-Business-Fee Supporting Project of Henan Province,China(Nos.2023KY35,2023KY40).
文摘Localized corrosion of 304 stainless steel being the significant parts of Starship rocket seriously threatens the long-term service of such aerospace equipment.Scanning electron microscopy,in situ instruments combining electrochemical workstation and Raman spectroscopy,and Density Dunctional Theory(DFT)calculations were employed.The surface morphologies,alloying elements,molecular fingerprint Raman evidence and theoretical mechanism for the localized corrosion of 304 stainless steel during the electrochemical polarization in the mixture solutions containing 0.5 mol/L H_(2)SO_(4) and 2,2'-bipyridine(bipy)with concentrations of 0.001,0.010,0.100 mol/L were discussed.In comparison,the presence of bipy up to 0.100 mol/L in such mixture solutions displayed the neglectable effect on the Fe(Ⅱ)/Fe(Ⅲ)reaction in the polarization process.Raman vibrational frequency around 1492 cm^(-1)was the evidence of pink color appearance due to the formation of[Fe^(Ⅱ)(bipy)_(3)]^(2+).Raman and DFT indicated the yellow color emergence due to the presence ofμ-O-[Fe^(Ⅲ)(bipy)_(2)(H_(2)O)]_(2)^(4+)due to the oxidation reaction of[Fe^(Ⅱ)(bipy)_(3)]^(2+)with H_(2)O_(2) oxidant,and the dimerization of[Fe^(Ⅲ)(bipy)_(3)]^(3+),Furthermore,a quantitative model between[Fe^(Ⅱ)(bipy)_(3)]^(2+)concentration and Raman intensity at 1492 cm^(-1) has been built up.Two linear functions were revealed when[Fe^(Ⅱ)(bipy)_(3)]^(2+)concentrations were at 0-0.002 mol/L and 0.002-0.004 mol/L and a concentration error of less than 5%was evidenced in comparison with that investigated by the inductively coupled plasma.The proposed passivation mechanism and quantitative concentration model of 304 stainless steel have certain significance for its corrosion protection andcorrosionevaluation.
基金supported by the Project of Shenzhen Science and Technology(Nos.JCYJ20210324095210028 and JSGGZD20220822095201003)the Shenzhen University 2035Program for Excellent Research(No.000003011002)the National Natural Science Foundation of China(No.U21A2087)。
文摘This study explores the molecular design of sulfur-containing polymers with high refractive indices(RI)and optimized Abbe numbers for advanced optical applications.The high molar refraction and low dispersion of sulfur make it an ideal component for enhancing the optical properties of polymers.Density functional theory(DFT)calculations were employed to predict the RI and Abbe numbers for a range of sulfurbased polymers.To improve the accuracy of the theoretical predictions,a correction function was developed by comparing the calculated values with experimental data.The key polymer families investigated included sulfur-containing polycarbonates,heterocyclic optical resins,and cycloolefins,all modified to balance RI enhancement with dispersion control.The results demonstrate that increasing the sulfur content and introducing specific heterocycles and bridged rings can effectively increase the RI while maintaining desirable Abbe numbers.Polymers incorporating 1,4-dithiane and sulfur-bridged rings exhibit excellent optical clarity and minimal visible light absorption,making them suitable for lens and coating applications.The study also calculated the UV-visible spectra for the most promising polymers,confirming their high transparency.This work establishes a predictive framework for developing high-performance optical polymers and offers a systematic approach for balancing the refractive index and dispersion,thereby providing valuable insights for the design of next-generation optical materials.
基金supported by the Center for Advanced Systems Understanding(CASUS),financed by Germany’s Federal Ministry of Education and Research(BMBF)and the Saxon State Government out of the State Budget approved by the Saxon State Parliamentfunding from the European Research Council(ERC)under the European Union’s Horizon 2022 research and innovation programme(Grant Agreement No.101076233,“PREXTREME”)funding from the European Union’s Just Transition Fund(JTF)within the project Röntgenlaser-Optimierung der Laserfusion(ROLF),Contract No.5086999001,co-financed by the Saxon State Government out of the State Budget approved by the Saxon State Parliament.
文摘Ab initio modeling of dynamic structure factors(DSF)and related density response properties in the warm dense matter(WDM)regime is a challenging computational task.The DSF,convolved with a probing X-ray beam and instrument function,is measured in X-ray Thom-son scattering(XRTS)experiments,which allow the study of electronic structure properties at the microscopic level.Among the various ab initio methods,linear-response time-dependent density-functional theory(LR-TDDFT)is a key framework for simulating the DSF.The standard approach in LR-TDDFT for computing the DSF relies on the orbital representation.A significant drawback of this method is the unfavorable scaling of the number of required empty bands as the wavenumber increases,making LR-TDDFT impractical for modeling XRTS measurements over large energy scales,such as in backward scattering geometry.In this work,we consider and test an alternative approach to LR-TDDFT that employs the Liouville–Lanczos(LL)method for simulating the DSF of WDM.This approach does not require empty states and allows the DSF at large momentum transfer values and over a broad frequency range to be accessed.We compare the results obtained from the LL method with those from the solution of Dyson’s equation using the standard LR-TDDFT within the projector augmented-wave formalism for isochorically heated aluminum and warm dense hydrogen.Additionally,we utilize exact path integral Monte Carlo results for the imaginary-time density-density correlation function(ITCF)of warm dense hydrogen to rigorously benchmark the LL approach.We discuss the application of the LL method for calculating DSFs and ITCFs at different wavenumbers,the effects of pseudopotentials,and the role of Lorentzian smearing.The successful validation of the LL method under WDM conditions makes it a valuable addition to the ab initio simulation landscape,supporting experimental efforts and advancing WDM theory.
文摘In 2014, 50 years following the introduction of density functional theory (DFT), a rigorous understanding of it was published [AIP Advances, 4, 127,104 (2014)]. This understanding includes two features that complete the theory in practice, inasmuch as they are necessary for its correct application in electronic structure calculations;this understanding elucidates what appears to have been the crucial misunderstanding for 50 years, namely, the confusion between a stationary solution, attainable with most basis sets, following self-consistent iterations, with the ground state solution. The latter is obtained by a calculation that employs the well-defined optimal basis set for the system. The aim of this work is to review the above understanding and to extend it to the relativistic generalization of density functional theory by Rajagopal and Callaway [Phys. Rev. B7, 1912 (1973)]. This extension straightforwardly follows similar steps taken in the non-relativistic case, with the four-component current density, in the former, replacing the electronic charge density, in the latter. This new understanding, which completes relativistic DFT in practice, is expected to be needed for the study of heavy atoms and of materials (from molecules to solids) containing them—as is the case for some high temperature superconductors.
基金supported by the National Natural Science Foundation of China(Grant Nos.10974067 and 11104107)the Program of Jilin Province Science and Technology Department,China(Grant Nos.20090534 and 20101508)the China Postdoctoral Science Foundation,China(Grant No.20110491320)
文摘We report on a temperature-dependent resonance Raman spectral characterization of the polyene chain of canthax- anthin. It is observed that all vibrational intensities of the polyene chain are inversely proportional to temperature, which is analyzed by the resonance Raman effect and the coherent weakly damped electron/lattice vibrations. The increase in intensity of the CC overtone/combination relative to the fundamental with temperature decreasing is detected and discussed in terms of electron/phonon coupling and the activation energy Uop. Moreover, the polyene chain studies using the density functional theory B3LYP/6-31 G＊ level reveal a prominent peak at 1525 cm-1 consisting of two closely spaced modes that are both dominated by C=C stretching coordinates of the polyene chain.
文摘As a substitute for lithium ion batteries, Na chemistry for ion battery systems is promising materials for energy storage applications for the next generation. Herein, the structures, IR and UV-visible spectra of 2-aminoterephthalic acid (H2ATA), disodium 2-aminoterephthalate (Na2ATA), trisodium 2-aminotere-phthalate (Na3ATA) and tetrasodium 2-aminoterephthalate (Na4ATA) have been studied using density functional theory (DFT/B3LYP/6-311++G(d,p)). The theoretical geometric parameters and FTIR results showed very good agreement with the experimental results. Different conformers of Na2ATA, Na3ATA and Na4ATA showed that the binding energy per sodium in Na2ATA, Na3ATA and Na4ATA is -694.94, -543.44 and -407.46 kJ/mol, respectively. The Na3ATA and Na4ATA salts are higher in energy (151.46 and 287.48 kJ/mol, respectively) than Na2ATA, indicating the higher stability of the Na2ATA complex. The calculated binding energy, enthalpy and Gibbs free energy of Na2ATA, Na3ATA and Na4ATA revealed that the compounds are thermodynamically stable. Natural bond orbital (NBO) analysis of Na2ATA, Na3ATA and Na4ATA indicated that the major interaction occurs between the lone pair electrons of the oxygen atom and anti-bonding orbitals of carbon atoms of the two carboxylate ions. UV-visible spectrum of the free H2ATA and its sodium salts Na2ATA, Na3ATA and Na4ATA were performed using the time-dependent density functional theory (TD-DFT) method at the level of B3LYP/6-311++G(d,p). The frontier molecular orbital energetic parameters and global reactivity descriptors revealed that the Na4ATA and Na3ATA complexes exhibited a higher band gap (ΔEgap) and electronegativity (χeV) than Na2ATA.
文摘The structural, electronic, and optical properties of Cu2Zn1−xBaxSn1−ySiyS4 compounds have been calculated using GGA-PBE function within the framework of Density Functional Theory (DFT). In the present work, lattice parameters remained the same, that is tetragonal crystal structure for 0% and 100% doping concentration. The electronic band gap of Cu2Zn1−xBaxSn1−ySiyS4 compounds has been gradually increased for continuous increment of doping concentration where the highest electronic band gap is 1.117 eV for Cu2BaSiS4 structure. Moreover, the band gap changes from direct to indirect band gap with the increase of doping concentration in the parent compound. The absorption coefficient has been found to be high (> 104 cm−1) in UV-region for all the doping concentration which makes the studied compound as a potential candidate of absorber layer in the UV detector. The theoretical study of the effect of double doping in the CZTS compound is very interesting for improving the quality of it and it would be a reference for the theoretical and experimental researchers.
基金Project(51164001)supported by the National Natural Science Foundation of ChinaProject(NCET-11-0925)supported by New Century Excellent Talents in University,China
文摘Adsorption of water on sulfide surfaces and natural floatability of sulfide minerals were studied using density functional theory （DFT） method. All computational models were built in a vacuum environment to eliminate the effects of oxygen and other factors. H2O molecule prefers to stay with pyrite and sphalerite surfaces rather than water, whereas for galena, chalcocite, stibnite, and molybdenite, H2O molecule prefers to stay with water rather than the mineral surfaces. On the other hand, pyrite surface favors N2 more than water, while sphalerite surface cannot adsorb N2. These results show that galena, stibnite, chalcocite, and molybdenite are hydrophobic, while sphalerite is hydrophilic. Although pyrite has certain hydrophilicity, it tends to be aerophilic because the reaction of pyrite with H2O is weaker than pyrite with N2. Thus, pyrite, galena, chalcocite, stibnite and molybdenite all have natural floatability.
基金Project (50864001) supported by the National Natural Science Foundation of China
文摘The electronic property of pyrite supercell containing As,Se,Te,Co or Ni hetero atoms were calculated using density functional theory（DFT）,and the reactivities of pyrite with oxygen and xanthate were discussed by frontier orbital methods.The cell volume expands due to the presence of impurity.Co and Ni mainly affect the bands near Fermi levels,while As mainly affects the shallow and deep valence bands,and Se and Te mainly affect the deep valence bands.Electronic density analysis suggests that there exists a strong covalent interaction between hetero atom and its surrounding atoms.By frontier orbital calculation,it is suggested that As,Co and Ni have greater influence on the HOMO and LUMO of pyrite than Se and Te.In addition,pyrite containing As,Co or Ni is easier to oxidize by oxygen than pyrite containing Se or Te,and pyrite containing Co or Ni has greater interaction with collector.These are in agreement with the observed pyrite practice.
基金This work was supported by the Natural Science Foundation of Nanjing Institute of Technology （YKJ201507, CKJA201603） and the Youth Natural Sci- ence Foundation of Jiangsu Province （BK20160774）, and Outstanding Scientific and Technological Innovation Team in Colleges and Universities of Jiangsu Province.
文摘Based on the parent tetrazole 2N-oxide, six series of novel carbon-linked ditetrazole 2N- oxides with different energetic substituent groups （-NH2, -Na, -NO2, NF2, -NHNO2） and energetic bridge groups （-CH2-, -CH2-CH2-, -NH-, -N=N-, -NH-NH-） were designed. The overall performance and the effects of different energetic substituent groups and energetic bridge groups on the performance were investigated by density functional theory and electrostatic potential methods. The results showed that most of designed compounds have oxygen balance around zero, high heats of formation, high density, high energy, and acceptable sensitivity, indicating that tetrazole N-oxide is a useful parent energetic compound employed for obtaining high energy compounds, even only combined with some very common energetic substituent groups and bridge groups. Comprehensively considering the effects on energy and sensitivity, the -NO2, -NF2, -NH- and-NH-NH- are appropriate substituent groups for combining tetrozale N-oxide to design new energetic compounds, while -NH2, -Na, -CH2-CH2-, and -N=N- are inappropriate.
基金This work was supported by the National Natural Science Foundation of China （No.21373132, No.21502109, No.21603133）, the Education Department of Shmunxi Provincial Government Research Projects （No.16JK1142, No.16JK1134）, and the Scientific Research Foundation of Shaanxi University of Technology for Recruited Talents （No.SLGKYQD2-13, No.SLGKYQD2-10, No.SLGQD14-10）.
文摘Designing and fabricating high-performance photovoltaic devices have remained a major challenge in organic solar cell technologies. In this work, the photovoltaic performances of BTBPD-PC61BM system were theoretically investigated by means of density functional theory calculations coupled with the Marcus charge transfer model in order to seek novel photovoltaic systems. Moreover, the hole-transfer properties of BTBPD thin-film were also studied by an amorphous cell with 100 BTBPD molecules. Results revealed that the BTBPD- PC61BM system possessed a middle-sized open-circuit voltage of 0.70 V, large short-circuit current density of 16.874 mA/cm2, large fill factor of 0.846, and high power conversion effi- ciency of 10%. With the Marcus model, the charge-dissociation rate constant was predicted to be as fast as 3.079×10^13 s^-1 in the BTBPD-PC61BM interface, which was as 3-5 orders of magnitude large as the decay （radiative and non-radiative） rate constant （108-10^10 s^-1）, indicating very high charge-dissociation efficiency （-100%） in the BTBPD-PC61BM system. Furthermore, by the molecular dynamics simulation, the hole mobility for BTBPD thin-film was predicted to be as high as 3.970× 10^-3 cm^2V^-1s^-1, which can be attributed to its tight packing in solid state.
文摘We study the geometries, stabilities, electronic and magnetic properties of （MgO）n （n=2-10） clusters doped with a single Mn atom using the density functional theory with the gener- alized gradient approximation. The optimized geometries show that the impurity Mn atom prefers to replace the Mg atom which has low coordination number in all the lowest-energy MnMgn-1On （n=2-10） structures. The stability analysis clearly represents that the average binding energies of the doped clusters are larger than those of the corresponding pure （MgO）n clusters. Maximum peaks of the second order energy differences are observed for MnMg~_1On clusters at n=6, 9, implying that these clusters exhibit higher stability than their neighboring clusters. In addition, all the Mn-doped Mg clusters exhibit high total magnetic moments with the exception of MnMgO2 which has 3.00μB. Their magnetic behavior is attributed to the impurity Mn atom, the charge transfer modes, and the size of MnMgn- 1On clusters.
