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
We report theoretical studies on the plasmon resonances in linear Au atomic chains by using ab initio time- dependent density functional theory. The dipole responses are investigated each as a function of chain length...We report theoretical studies on the plasmon resonances in linear Au atomic chains by using ab initio time- dependent density functional theory. The dipole responses are investigated each as a function of chain length. They converge into a single resonance in the longitudinal mode but split into two transverse modes. As the chain length increases, the longitudinal plasmon mode is redshifted in energy while the transverse modes shift in the opposite direction （blueshifts）. In addition, the energy gap between the two transverse modes reduces with chain length increasing. We find that there are unique characteristics, different from those of other metallic chains. These characteristics are crucial to atomic-scale engineering of single-molecule sensing, optical spectroscopy, and so on.展开更多
We propose a method for calculating the nonradiative decay rates for polyatomic molecules including anharmonic effects of the potential energy surface(PES)in the Franck-Condon region.The method combines the n-mode rep...We propose a method for calculating the nonradiative decay rates for polyatomic molecules including anharmonic effects of the potential energy surface(PES)in the Franck-Condon region.The method combines the n-mode repre-sentation method to construct the ab initio PES and the nearly exact time-dependent density matrix renormalization group method(TD-DMRG)to simulate quantum dynamics.In addition,in the framework of TD-DMRG,we further develop an algorithm to calculate the final-state-resolved rate coefficient which is very useful to analyze the contribution from each vibrational mode to the transition process.We use this method to study the internal conversion(IC)process of azulene after taking into account the anharmonicity of the ground state PES.The results show that even for this semi-rigid molecule,the intramode anharmonicity enhances the IC rate significantly,and after considering the two-mode coupling effect,the rate increases even further.The reason is that the anharmonicity enables the C-H vibrations to receive electronic energy while C-H vibrations do not contribute on the harmonic PES as the Huang-Rhys factor is close to 0.展开更多
Chiroptical properties including electronic circular dichroism（ECD） and optical rotatory dispersion（ORD） of artemisinin and artemether have been fully studied using quantum-chemical calculation based on time-depen...Chiroptical properties including electronic circular dichroism（ECD） and optical rotatory dispersion（ORD） of artemisinin and artemether have been fully studied using quantum-chemical calculation based on time-dependent density functional theory.Both theoretical ECD and ORD of these two compounds were in good match with the experimental data.ECD spectrum of artemether could be totally attributed to the peroxide group,and that of artemisinin was an overlay of contribution from δ-lactone and peroxide moieties,which leading to a positive maximum at 260 nm.Our results showed that peroxide group could produce a broad ECD band in the far-UV region originated from electron transitions of HOMO →LUMO,HOMO-1 →LUMO and HOMO-2 →LUMO in the case of artemether.This work provided a theoretical interpretation of the ECD behavior of peroxide bond.展开更多
Time-dependent density functional theory(TDDFT)method is used to investigate the details of the excited state intramolecular proton transfer(ESIPT)process and the mechanism for temperature effect on the Enol^(*)/Keto^...Time-dependent density functional theory(TDDFT)method is used to investigate the details of the excited state intramolecular proton transfer(ESIPT)process and the mechanism for temperature effect on the Enol^(*)/Keto^(*)emission ratio for the Me_(2)N-substited flavonoid(MNF)compound.The geometric structures of the S_(0) and S_(1) states are denoted as the Enol,Enol^(*),and Keto*.In addition,the absorption and fluorescence peaks are also calculated.It is noted that the calculated large Stokes shift is in good agreement with the experimental result.Furthermore,our results confirm that the ESIPT process happens upon photoexcitation,which is distinctly monitored by the formation and disappearance of the characteristic peaks of infrared(IR)spectra involved in the proton transfer and in the potential energy curves.Besides,the calculations of highest occupied molecular orbital(HOMO)and lowest unoccupied molecular orbital(LUMO)reveal that the electronegativity change of proton acceptor due to the intramolecular charge redistribution in the S_(1) state induces the ESIPT.Moreover,the thermodynamic calculation for the MNF shows that the Enol^(*)/Keto^(*)emission ratio decreasing with temperature increasing arises from the barrier lowering of ESIPT.展开更多
By using first-principles simulations based on time-dependent density functional theory, the chemical reaction of an HCl molecule encapsulated in C60 induced by femtosecond laser pulses is observed. The H atom starts ...By using first-principles simulations based on time-dependent density functional theory, the chemical reaction of an HCl molecule encapsulated in C60 induced by femtosecond laser pulses is observed. The H atom starts to leave the Cl atom and is reflected by the C60 wall. The coherent nuclear dynamic behaviors of bond breakage and recombination of the HCl molecule occurring in both polarized parallel and perpendicular to the H-Cl bond axis are investigated. The radial oscillation is also found in the two polarization directions of the laser pulse. The relaxation time of the H-Cl bond lengths in transverse polarization is slow in comparison with that in longitudinal polarization. Those results are important for studying the dynamics of the chemical bond at an atomic level.展开更多
Electronic properties, such as HOMO and LUMO energies, band gaps, ionization potential （IP） and electron affinity （EA） of 2,7- and 3,6-1inked carbazole trimers, two conjugated oligomcrs with different linkages of ...Electronic properties, such as HOMO and LUMO energies, band gaps, ionization potential （IP） and electron affinity （EA） of 2,7- and 3,6-1inked carbazole trimers, two conjugated oligomcrs with different linkages of carbazole, were studicd by the density functional theory with Becke-Lee-Young-Parr composite exchange correlation functional （B3LYP）. The absorption spectra of these compounds were also investigated by time-dependent density functional theory （TD-DFT） with 6-3 IG＊ basis set. The calculated results indicated that the HOMO and LUMO of the 2,7- and 3,6-1inked carbazole trimers are both slightly destabilized on going from methyl substitution to sec-butyl substitution. Both IP and EA exhibit their good hole-transporting but poor electronaccepting ability. The presence of alkyl groups on the nitrogen atoms does not affect the intra-chain electronic delocalization along the molecular frame. Thus no significant effect on the band gap and absorption spectra of compounds has been found.展开更多
The time-dependent density functional-based tight-bind （TD-DFTB） method is implemented on the multi-core and the graphical processing unit （GPU） system for excited state calcu-lations of large system with hundreds...The time-dependent density functional-based tight-bind （TD-DFTB） method is implemented on the multi-core and the graphical processing unit （GPU） system for excited state calcu-lations of large system with hundreds or thousands of atoms. Sparse matrix and OpenMP multithreaded are used for building the Hamiltonian matrix. The diagonal of the eigenvalue problem in the ground state is implemented on the GPUs with double precision. The GPU- based acceleration fully preserves all the properties, and a considerable total speedup of 8.73 can be achieved. A Krylov-space-based algorithm with the OpenMP parallel and CPU acceleration is used for finding the lowest eigenvalue and eigenvector of the large TDDFT matrix, which greatly reduces the iterations taken and the time spent on the excited states eigenvalue problem. The Krylov solver with the GPU acceleration of matrix-vector product can converge quickly to obtain the final result and a notable speed-up of 206 times can be observed for system size of 812 atoms. The calculations on serials of small and large systems show that the fast TD-DFTB code can obtain reasonable result with a much cheaper computational requirement compared with the first-principle results of CIS and full TDDFT calculation.展开更多
With the frame of the time-dependent local density approximation, an efficient description of the optical response of clusters has been used to study the photo-absorption cross section of Na2 and Na4 clusters. It is s...With the frame of the time-dependent local density approximation, an efficient description of the optical response of clusters has been used to study the photo-absorption cross section of Na2 and Na4 clusters. It is shown that our calculated results are in good agreement with the experiment. In addition, our calculated spectrum for the Na4 cluster is in better agreement with experiment than the GW absorption spectrum.展开更多
By using first-principles simulations based on time-dependent density functional theory,the chemical reaction of an HCl molecule encapsulated in C60induced by femtosecond laser pulses is observed.The H atom starts to ...By using first-principles simulations based on time-dependent density functional theory,the chemical reaction of an HCl molecule encapsulated in C60induced by femtosecond laser pulses is observed.The H atom starts to leave the Cl atom and is reflected by the C60wall.The coherent nuclear dynamic behaviors of bond breakage and recombination of the HCl molecule occurring in both polarized parallel and perpendicular to the H–Cl bond axis are investigated.The radial oscillation is also found in the two polarization directions of the laser pulse.The relaxation time of the H–Cl bond lengths in transverse polarization is slow in comparison with that in longitudinal polarization.Those results are important for studying the dynamics of the chemical bond at an atomic level.展开更多
The behavior of interacting electrons in a perfect crystal under macroscopic external electric and magnetic fields is studied. Effective Maxwell equations for the macroscopic electric and magnetic fields are derived s...The behavior of interacting electrons in a perfect crystal under macroscopic external electric and magnetic fields is studied. Effective Maxwell equations for the macroscopic electric and magnetic fields are derived starting from time-dependent density functional theory. Effective permittivity and permeability coefficients are obtained.展开更多
Time-dependent density-functional theory(TDDFT)has been successfully applied to predict excited-state properties of isolated and periodic systems.However,it cannot address a system coupled to an environment or whose n...Time-dependent density-functional theory(TDDFT)has been successfully applied to predict excited-state properties of isolated and periodic systems.However,it cannot address a system coupled to an environment or whose number of electrons is not conserved.To tackle these problems,TDDFT needs to be extended to accommodate open systems.This paper provides a comprehensive account of the recent developments of TDDFT for open systems(TDDFT-OS),including both theoretical and practical aspects.The practicality and accuracy of a latest TDDFT-OS method is demonstrated with two numerical examples:the time-dependent electron transport through a series of quasi-one-dimensional atomic chains,and the real-time electronic dynamics on a two-dimensional graphene surface.The advancement of TDDFT-OS may lead to promising applications in various fields of chemistry,including energy conversion and heterogeneous catalysis.展开更多
Catastrophic failure in engineering structures of island reefs would occur when the tertiary creep initiates in coral reef limestone with a transition from short-to long-term load.Due to the complexity of biological s...Catastrophic failure in engineering structures of island reefs would occur when the tertiary creep initiates in coral reef limestone with a transition from short-to long-term load.Due to the complexity of biological structures,the underlying micro-behaviors involving time-dependent deformation are poorly understood.For this,an abnormal phenomenon was observed where the axial and lateral creep deformations were mutually independent by a series of triaxial tests under constant stress and strain rate conditions.The significantly large lateral creep deformation implies that the creep process cannot be described in continuum mechanics regime.Herein,it is hypothesized that sliding mechanism of crystal cleavages dominates the lateral creep deformation in coral reef limestone.Then,approaches of polarizing microscope(PM)and scanning electronic microscope(SEM)are utilized to validate the hypothesis.It shows that the sliding behavior of crystal cleavages combats with conventional creep micro-mechanisms at certain condition.The former is sensitive to time and strain rate,and is merely activated in the creep regime.展开更多
With respect to oceanic fluid dynamics,certain models have appeared,e.g.,an extended time-dependent(3+1)-dimensional shallow water wave equation in an ocean or a river,which we investigate in this paper.Using symbolic...With respect to oceanic fluid dynamics,certain models have appeared,e.g.,an extended time-dependent(3+1)-dimensional shallow water wave equation in an ocean or a river,which we investigate in this paper.Using symbolic computation,we find out,on one hand,a set of bilinear auto-Backlund transformations,which could connect certain solutions of that equation with other solutions of that equation itself,and on the other hand,a set of similarity reductions,which could go from that equation to a known ordinary differential equation.The results in this paper depend on all the oceanic variable coefficients in that equation.展开更多
The rapid miniaturization of elect, ronic devices motivates research interests in quantum transport.Recently time-dependent quantum transport has become an important research topic. Here we re- view recent progresses ...The rapid miniaturization of elect, ronic devices motivates research interests in quantum transport.Recently time-dependent quantum transport has become an important research topic. Here we re- view recent progresses in the development of time-dependent density-functional theory for quantum transport including the theoretical foundation and numerical algorithms. In particular, the reducedsingle electron density matrix based hierarchical equation of motion, which can be derived from Liouville---von Neumann equation, is reviewed in details. The numerical implementation is discussed and simulation results of realistic devices will be given.展开更多
The field of diffusion micro structural magnetic resonance(MR)aims to probe timedependent diffusion,i.e.,an ensemble-averaged mean-squared displacement that is not linear in time.This time-dependence contains rich inf...The field of diffusion micro structural magnetic resonance(MR)aims to probe timedependent diffusion,i.e.,an ensemble-averaged mean-squared displacement that is not linear in time.This time-dependence contains rich information about the surrounding microenvironment.MR methods to measure time-dependent diffusion quantitatively,however,require either non-standard pulse sequences,such as oscillating gradients,or make non-physical assumptions,such as infinitely narrow gradient pulses.Here,we argue that standard spin echo and stimulated echo MR sequences can be used to probe directly.In particular,we propose a framework in which the log-signal ratio obtained from a pair of measurements with different inter-pulse spacingΔis proportional to the MSD between these twoΔvalues along the gradient direction x:-.The framework is quantitative for short,finite-duration gradient pulses and under the Gaussian phase approximation(GPA).To validate the framework,we consider onedimensional diffusion between impermeable,parallel planes,as well as periodicallyspaced,permeable planes.Excellent agreement is obtained between the estimation and the ground truth in the regime where the GPA is expected to hold.Importantly,the GPA can be made to hold for any underlying microstructure,making the proposed framework widely applicable.展开更多
An efficient and accurate method for computing the equilibriurn reduced density matrix is presented for treating open quantum systems characterized by the systern-bath model. The method employs the rnultilayer nmltico...An efficient and accurate method for computing the equilibriurn reduced density matrix is presented for treating open quantum systems characterized by the systern-bath model. The method employs the rnultilayer nmlticonfiguration tirne-dependent Hartree theory for imag- inary time propagation and an importance sampling procedure for calculating the quantum mechanical trace. The method is applied to the spin-boson Harniltonian, which leads to ac- curate results in agreement with those produced by the rnulti-electronic-state path integral molecular dynamics method.展开更多
This article first outlines the fundamental definitions of Mycoplasma pneumoniae and the basic principles of antibiotics. It then analyzes and discusses the progress in antibiotic application and time-eff ect studies ...This article first outlines the fundamental definitions of Mycoplasma pneumoniae and the basic principles of antibiotics. It then analyzes and discusses the progress in antibiotic application and time-eff ect studies for neonatal pneumonia treatment, specifically comparing conventional antibiotic therapy with stepwise treatment regimens, and contrasting monotherapy with penicillin, monotherapy with cephalosporins, and combination therapy. Finally, it offers a prospective outlook on antibiotic application and time-effect research in neonatal pneumonia treatment, aiming to provide valuable reference for further scholarly investigations.展开更多
Heat transfers at the interface of adjacent saturated soil primarily through the soil particles and the water in the voids.The presence of water induces the contraction of heat flow lines at the interface,leading to t...Heat transfers at the interface of adjacent saturated soil primarily through the soil particles and the water in the voids.The presence of water induces the contraction of heat flow lines at the interface,leading to the emergence of the thermal contact resistance effect.In this paper,four thermal contact models were developed to predict the thermal contact resistance at the interface of multilayered saturated soils.Based on the theory of thermal-hydro-mechanical coupling,semi-analytical solutions of thermal consolidation subjected to time-dependent heating and loading were obtained by employing Laplace transform and its inverse transformation.Thermal consolidation characteristics of multilayered saturated soils under four different thermal contact models were discussed,and the effects of thermal resistance coefficient,partition thermal contact coefficient,and temperature amplitude on the thermal consolidation process were investigated.The outcomes indicate that the general thermal contact model results in the most pronounced thermal gradient at the interface,which can be degenerated to the other three thermal contact models.The perfect thermal contact model overestimates the deformation of the saturated soil during the thermal consolidation.Moreover,the effect of temperature on consolidation properties decreases gradually with increasing interfacial contact thermal resistance.展开更多
The Zagros Basin in southwestern Iran is a significant source of coal,with numerous coal mines operating in the region.Ensuring the stability of coal mines is crucial for safe and efficient mining operations.This stud...The Zagros Basin in southwestern Iran is a significant source of coal,with numerous coal mines operating in the region.Ensuring the stability of coal mines is crucial for safe and efficient mining operations.This study investigates the time-varying response of rocks and roof resistance in coal mines in the Zagros Mountains using a novel approach that combines numerical simulation,relaxation testing,and rock displacement studies.The results show that rocks exhibit significant time-dependent behavior,with changes in rock mechanical properties over time.A comprehensive viscoelastic-plastic model is devel-oped to accurately describe the time-varying strain-softening response of rocks and simulate laboratory tests.The model integrates the Burgers and strain-softening models,simulating stress relaxation curves and rock displacement over time.The study reveals that the rock mass displays significant nonlinear behavior,with changes in rock mechanical properties over time.The findings of this study highlight the importance of considering the time-varying response of rocks and roof resistance in coal mine stability analysis.The results provide valuable insights into the time-dependent behavior of rock mass in coal mines in Iran,which can inform mining practices and mitigate potential hazards.Results in this study can contribute to developing strategies for improving roof stability and reducing the likelihood of roof collapses.展开更多
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.
基金Project supported by the National Natural Science Foundation of China (Grant Nos.11074176 and 10976019)the Research Fund for the Doctoral Program of Higher Education of China (Grant No.20100181110080)
文摘We report theoretical studies on the plasmon resonances in linear Au atomic chains by using ab initio time- dependent density functional theory. The dipole responses are investigated each as a function of chain length. They converge into a single resonance in the longitudinal mode but split into two transverse modes. As the chain length increases, the longitudinal plasmon mode is redshifted in energy while the transverse modes shift in the opposite direction （blueshifts）. In addition, the energy gap between the two transverse modes reduces with chain length increasing. We find that there are unique characteristics, different from those of other metallic chains. These characteristics are crucial to atomic-scale engineering of single-molecule sensing, optical spectroscopy, and so on.
基金supported by the National Natural Science Foundation of China through the Project "Science Center for Luminescence from Molecular Aggregates(SCELMA)" (No.21788102)the Ministry of Science and Technology of China through the National Key R&D Plan (No.2017YFA0204501)supported by the National Natural Science Foundation of China (No.22003029)
文摘We propose a method for calculating the nonradiative decay rates for polyatomic molecules including anharmonic effects of the potential energy surface(PES)in the Franck-Condon region.The method combines the n-mode repre-sentation method to construct the ab initio PES and the nearly exact time-dependent density matrix renormalization group method(TD-DMRG)to simulate quantum dynamics.In addition,in the framework of TD-DMRG,we further develop an algorithm to calculate the final-state-resolved rate coefficient which is very useful to analyze the contribution from each vibrational mode to the transition process.We use this method to study the internal conversion(IC)process of azulene after taking into account the anharmonicity of the ground state PES.The results show that even for this semi-rigid molecule,the intramode anharmonicity enhances the IC rate significantly,and after considering the two-mode coupling effect,the rate increases even further.The reason is that the anharmonicity enables the C-H vibrations to receive electronic energy while C-H vibrations do not contribute on the harmonic PES as the Huang-Rhys factor is close to 0.
基金supported by the Fundamental Research Funds for the Central Institutes of China(No.2012ZD03)
文摘Chiroptical properties including electronic circular dichroism（ECD） and optical rotatory dispersion（ORD） of artemisinin and artemether have been fully studied using quantum-chemical calculation based on time-dependent density functional theory.Both theoretical ECD and ORD of these two compounds were in good match with the experimental data.ECD spectrum of artemether could be totally attributed to the peroxide group,and that of artemisinin was an overlay of contribution from δ-lactone and peroxide moieties,which leading to a positive maximum at 260 nm.Our results showed that peroxide group could produce a broad ECD band in the far-UV region originated from electron transitions of HOMO →LUMO,HOMO-1 →LUMO and HOMO-2 →LUMO in the case of artemether.This work provided a theoretical interpretation of the ECD behavior of peroxide bond.
基金Project supported by the National Basic Research Program of China(Grant No.2013CB922204)the National Natural Science Foundation of China(Grant Nos.11574115 and 11704146)the Natural Science Foundation of Jilin Province,China(Grant No.20150101063JC)
文摘Time-dependent density functional theory(TDDFT)method is used to investigate the details of the excited state intramolecular proton transfer(ESIPT)process and the mechanism for temperature effect on the Enol^(*)/Keto^(*)emission ratio for the Me_(2)N-substited flavonoid(MNF)compound.The geometric structures of the S_(0) and S_(1) states are denoted as the Enol,Enol^(*),and Keto*.In addition,the absorption and fluorescence peaks are also calculated.It is noted that the calculated large Stokes shift is in good agreement with the experimental result.Furthermore,our results confirm that the ESIPT process happens upon photoexcitation,which is distinctly monitored by the formation and disappearance of the characteristic peaks of infrared(IR)spectra involved in the proton transfer and in the potential energy curves.Besides,the calculations of highest occupied molecular orbital(HOMO)and lowest unoccupied molecular orbital(LUMO)reveal that the electronegativity change of proton acceptor due to the intramolecular charge redistribution in the S_(1) state induces the ESIPT.Moreover,the thermodynamic calculation for the MNF shows that the Enol^(*)/Keto^(*)emission ratio decreasing with temperature increasing arises from the barrier lowering of ESIPT.
基金Project supported by the National Natural Science Foundation of China （Grant Nos. 11074176 and 10976019） and the Doctoral Program of Higher Education of China （Grant No. 20100181110080）.
文摘By using first-principles simulations based on time-dependent density functional theory, the chemical reaction of an HCl molecule encapsulated in C60 induced by femtosecond laser pulses is observed. The H atom starts to leave the Cl atom and is reflected by the C60 wall. The coherent nuclear dynamic behaviors of bond breakage and recombination of the HCl molecule occurring in both polarized parallel and perpendicular to the H-Cl bond axis are investigated. The radial oscillation is also found in the two polarization directions of the laser pulse. The relaxation time of the H-Cl bond lengths in transverse polarization is slow in comparison with that in longitudinal polarization. Those results are important for studying the dynamics of the chemical bond at an atomic level.
基金The project was supported by the Scientific Research Fund of Hunan Provincial Education Department (No. 05A002)the Prominent Mid-youth Science and Technology Foundation of Hunan Province (No. 04JJ1010)
文摘Electronic properties, such as HOMO and LUMO energies, band gaps, ionization potential （IP） and electron affinity （EA） of 2,7- and 3,6-1inked carbazole trimers, two conjugated oligomcrs with different linkages of carbazole, were studicd by the density functional theory with Becke-Lee-Young-Parr composite exchange correlation functional （B3LYP）. The absorption spectra of these compounds were also investigated by time-dependent density functional theory （TD-DFT） with 6-3 IG＊ basis set. The calculated results indicated that the HOMO and LUMO of the 2,7- and 3,6-1inked carbazole trimers are both slightly destabilized on going from methyl substitution to sec-butyl substitution. Both IP and EA exhibit their good hole-transporting but poor electronaccepting ability. The presence of alkyl groups on the nitrogen atoms does not affect the intra-chain electronic delocalization along the molecular frame. Thus no significant effect on the band gap and absorption spectra of compounds has been found.
文摘The time-dependent density functional-based tight-bind （TD-DFTB） method is implemented on the multi-core and the graphical processing unit （GPU） system for excited state calcu-lations of large system with hundreds or thousands of atoms. Sparse matrix and OpenMP multithreaded are used for building the Hamiltonian matrix. The diagonal of the eigenvalue problem in the ground state is implemented on the GPUs with double precision. The GPU- based acceleration fully preserves all the properties, and a considerable total speedup of 8.73 can be achieved. A Krylov-space-based algorithm with the OpenMP parallel and CPU acceleration is used for finding the lowest eigenvalue and eigenvector of the large TDDFT matrix, which greatly reduces the iterations taken and the time spent on the excited states eigenvalue problem. The Krylov solver with the GPU acceleration of matrix-vector product can converge quickly to obtain the final result and a notable speed-up of 206 times can be observed for system size of 812 atoms. The calculations on serials of small and large systems show that the fast TD-DFTB code can obtain reasonable result with a much cheaper computational requirement compared with the first-principle results of CIS and full TDDFT calculation.
基金The project supported by National Natural Science Foundation of China under Grant Nos. 10405025, 10575012, 10435020, and 10535010
文摘With the frame of the time-dependent local density approximation, an efficient description of the optical response of clusters has been used to study the photo-absorption cross section of Na2 and Na4 clusters. It is shown that our calculated results are in good agreement with the experiment. In addition, our calculated spectrum for the Na4 cluster is in better agreement with experiment than the GW absorption spectrum.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11074176 and 10976019)the Doctoral Program of Higher Education of China(Grant No.20100181110080)
文摘By using first-principles simulations based on time-dependent density functional theory,the chemical reaction of an HCl molecule encapsulated in C60induced by femtosecond laser pulses is observed.The H atom starts to leave the Cl atom and is reflected by the C60wall.The coherent nuclear dynamic behaviors of bond breakage and recombination of the HCl molecule occurring in both polarized parallel and perpendicular to the H–Cl bond axis are investigated.The radial oscillation is also found in the two polarization directions of the laser pulse.The relaxation time of the H–Cl bond lengths in transverse polarization is slow in comparison with that in longitudinal polarization.Those results are important for studying the dynamics of the chemical bond at an atomic level.
文摘The behavior of interacting electrons in a perfect crystal under macroscopic external electric and magnetic fields is studied. Effective Maxwell equations for the macroscopic electric and magnetic fields are derived starting from time-dependent density functional theory. Effective permittivity and permeability coefficients are obtained.
基金supported by the National Natural Science Foundation of China(21103157,21233007,and 21322305)the Fundamental Research Funds for Central Universities(2340000034 and 2340000025)the Strategic Priority Research Program(B)of the CAS(XDB01020000)
文摘Time-dependent density-functional theory(TDDFT)has been successfully applied to predict excited-state properties of isolated and periodic systems.However,it cannot address a system coupled to an environment or whose number of electrons is not conserved.To tackle these problems,TDDFT needs to be extended to accommodate open systems.This paper provides a comprehensive account of the recent developments of TDDFT for open systems(TDDFT-OS),including both theoretical and practical aspects.The practicality and accuracy of a latest TDDFT-OS method is demonstrated with two numerical examples:the time-dependent electron transport through a series of quasi-one-dimensional atomic chains,and the real-time electronic dynamics on a two-dimensional graphene surface.The advancement of TDDFT-OS may lead to promising applications in various fields of chemistry,including energy conversion and heterogeneous catalysis.
基金supported by the National Natural Science Foundation of China(Grant Nos.41877267,41877260)the Priority Research Program of the Chinese Academy of Science(Grant No.XDA13010201).
文摘Catastrophic failure in engineering structures of island reefs would occur when the tertiary creep initiates in coral reef limestone with a transition from short-to long-term load.Due to the complexity of biological structures,the underlying micro-behaviors involving time-dependent deformation are poorly understood.For this,an abnormal phenomenon was observed where the axial and lateral creep deformations were mutually independent by a series of triaxial tests under constant stress and strain rate conditions.The significantly large lateral creep deformation implies that the creep process cannot be described in continuum mechanics regime.Herein,it is hypothesized that sliding mechanism of crystal cleavages dominates the lateral creep deformation in coral reef limestone.Then,approaches of polarizing microscope(PM)and scanning electronic microscope(SEM)are utilized to validate the hypothesis.It shows that the sliding behavior of crystal cleavages combats with conventional creep micro-mechanisms at certain condition.The former is sensitive to time and strain rate,and is merely activated in the creep regime.
基金financially supported by the Scientific Research Foundation of North China University of Technology(Grant Nos.11005136024XN147-87 and 110051360024XN151-86).
文摘With respect to oceanic fluid dynamics,certain models have appeared,e.g.,an extended time-dependent(3+1)-dimensional shallow water wave equation in an ocean or a river,which we investigate in this paper.Using symbolic computation,we find out,on one hand,a set of bilinear auto-Backlund transformations,which could connect certain solutions of that equation with other solutions of that equation itself,and on the other hand,a set of similarity reductions,which could go from that equation to a known ordinary differential equation.The results in this paper depend on all the oceanic variable coefficients in that equation.
文摘The rapid miniaturization of elect, ronic devices motivates research interests in quantum transport.Recently time-dependent quantum transport has become an important research topic. Here we re- view recent progresses in the development of time-dependent density-functional theory for quantum transport including the theoretical foundation and numerical algorithms. In particular, the reducedsingle electron density matrix based hierarchical equation of motion, which can be derived from Liouville---von Neumann equation, is reviewed in details. The numerical implementation is discussed and simulation results of realistic devices will be given.
基金supported by the intramural research program(IRP)of the Eunice Kennedy Shriver National Institute of Child Health and Human Development。
文摘The field of diffusion micro structural magnetic resonance(MR)aims to probe timedependent diffusion,i.e.,an ensemble-averaged mean-squared displacement that is not linear in time.This time-dependence contains rich information about the surrounding microenvironment.MR methods to measure time-dependent diffusion quantitatively,however,require either non-standard pulse sequences,such as oscillating gradients,or make non-physical assumptions,such as infinitely narrow gradient pulses.Here,we argue that standard spin echo and stimulated echo MR sequences can be used to probe directly.In particular,we propose a framework in which the log-signal ratio obtained from a pair of measurements with different inter-pulse spacingΔis proportional to the MSD between these twoΔvalues along the gradient direction x:-.The framework is quantitative for short,finite-duration gradient pulses and under the Gaussian phase approximation(GPA).To validate the framework,we consider onedimensional diffusion between impermeable,parallel planes,as well as periodicallyspaced,permeable planes.Excellent agreement is obtained between the estimation and the ground truth in the regime where the GPA is expected to hold.Importantly,the GPA can be made to hold for any underlying microstructure,making the proposed framework widely applicable.
基金supported by the U.S.National Science Foundation CHE-1500285used resources from the National Energy Research Scientific Computing Center,which is supported by the Office of Science of the U.S.Department of Energy under Contract No.DE-AC02-05CH11231+2 种基金supported by the Ministry of Science and Technology of China(No.2017YFA0204901 and No.2016YFC0202803)the National Natural Science Foundation of China(No.21373018 and No.21573007)the Recruitment Program of Global Experts,and Special Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund(the second phase) under grant No.U1501501
文摘An efficient and accurate method for computing the equilibriurn reduced density matrix is presented for treating open quantum systems characterized by the systern-bath model. The method employs the rnultilayer nmlticonfiguration tirne-dependent Hartree theory for imag- inary time propagation and an importance sampling procedure for calculating the quantum mechanical trace. The method is applied to the spin-boson Harniltonian, which leads to ac- curate results in agreement with those produced by the rnulti-electronic-state path integral molecular dynamics method.
文摘This article first outlines the fundamental definitions of Mycoplasma pneumoniae and the basic principles of antibiotics. It then analyzes and discusses the progress in antibiotic application and time-eff ect studies for neonatal pneumonia treatment, specifically comparing conventional antibiotic therapy with stepwise treatment regimens, and contrasting monotherapy with penicillin, monotherapy with cephalosporins, and combination therapy. Finally, it offers a prospective outlook on antibiotic application and time-effect research in neonatal pneumonia treatment, aiming to provide valuable reference for further scholarly investigations.
基金Projects(U24B20113,42477162) supported by the National Natural Science Foundation of ChinaProject(2025C02228) supported by the Primary Research and Development Plan of Zhejiang Province,China。
文摘Heat transfers at the interface of adjacent saturated soil primarily through the soil particles and the water in the voids.The presence of water induces the contraction of heat flow lines at the interface,leading to the emergence of the thermal contact resistance effect.In this paper,four thermal contact models were developed to predict the thermal contact resistance at the interface of multilayered saturated soils.Based on the theory of thermal-hydro-mechanical coupling,semi-analytical solutions of thermal consolidation subjected to time-dependent heating and loading were obtained by employing Laplace transform and its inverse transformation.Thermal consolidation characteristics of multilayered saturated soils under four different thermal contact models were discussed,and the effects of thermal resistance coefficient,partition thermal contact coefficient,and temperature amplitude on the thermal consolidation process were investigated.The outcomes indicate that the general thermal contact model results in the most pronounced thermal gradient at the interface,which can be degenerated to the other three thermal contact models.The perfect thermal contact model overestimates the deformation of the saturated soil during the thermal consolidation.Moreover,the effect of temperature on consolidation properties decreases gradually with increasing interfacial contact thermal resistance.
文摘The Zagros Basin in southwestern Iran is a significant source of coal,with numerous coal mines operating in the region.Ensuring the stability of coal mines is crucial for safe and efficient mining operations.This study investigates the time-varying response of rocks and roof resistance in coal mines in the Zagros Mountains using a novel approach that combines numerical simulation,relaxation testing,and rock displacement studies.The results show that rocks exhibit significant time-dependent behavior,with changes in rock mechanical properties over time.A comprehensive viscoelastic-plastic model is devel-oped to accurately describe the time-varying strain-softening response of rocks and simulate laboratory tests.The model integrates the Burgers and strain-softening models,simulating stress relaxation curves and rock displacement over time.The study reveals that the rock mass displays significant nonlinear behavior,with changes in rock mechanical properties over time.The findings of this study highlight the importance of considering the time-varying response of rocks and roof resistance in coal mine stability analysis.The results provide valuable insights into the time-dependent behavior of rock mass in coal mines in Iran,which can inform mining practices and mitigate potential hazards.Results in this study can contribute to developing strategies for improving roof stability and reducing the likelihood of roof collapses.
