An accurate and simultaneous ab initio prediction for both light nuclei and nuclear matter has been a longstanding challenge in nuclear physics, due to the significant uncertainties associated with the three-nucleon f...An accurate and simultaneous ab initio prediction for both light nuclei and nuclear matter has been a longstanding challenge in nuclear physics, due to the significant uncertainties associated with the three-nucleon forces.In this Letter, we develop the relativistic quantum Monte Carlo methods for the nuclear ab initio problem, and calculate the ground-state energies of A ≤ 4 nuclei using the two-nucleon Bonn force with an unprecedented high accuracy. The present relativistic results significantly outperform the nonrelativistic results with only twonucleon forces. We demonstrate that both light nuclei and nuclear matter can be well described simultaneously in the relativistic ab initio calculations, even in the absence of three-nucleon forces, and a correlation between the properties of light A ≤ 4 nuclei and the nuclear saturation is revealed. This provides a quantitative understanding of the connection between the light nuclei and nuclear matter saturation properties.展开更多
Understanding the adsorption behavior of heavy metals and metalloids on clay minerals is essential for remediating heavy metal-contaminated soils.The adsorption of heavy metals and metalloids on illite(001)and sodium ...Understanding the adsorption behavior of heavy metals and metalloids on clay minerals is essential for remediating heavy metal-contaminated soils.The adsorption of heavy metals and metalloids on illite(001)and sodium montmorillonite(Na-MMT)(001)surfaces was investigated using first-principles calculations in this study,especially As atom and H_(3)AsO_(3) molecule.The adsorption energies of the As atom were−1.94 eV on the illite(001)and−0.56 eV on the Na-MMT(001),whereas,the adsorption energies of the H_(3)AsO_(3) molecule were−1.40 eV on illite(001)and−1.01 eV on Na-MMT(001).The above results indicate that the adsorption was more energetically favorable on illite(001).Additionally,compared to Na-MMT(001),there were more significant interactions between the atoms/molecules on the illite(001).After As atom and H_(3)AsO_(3) molecule adsorption,the electrons were transferred from mineral surface atoms to the adsorbates on both illite(001)and Na-MMT(001)surfaces.Moreover,the adsorption of As atom on illite(001)and Na-MMT(001)surfaces were more energy favorable compared to Hg,Cd,and Cr atoms.Overall,this work provides new insights into the adsorption behavior of As atoms and As molecules on illite and Na-MMT.The results indicate that illite rich soils are more prone to contamination by arsenic compared to soils primarily composed of Na-MMT minerals.展开更多
The electrical conductivity of minerals under extreme conditions is governed by their variations in composition and structure.Constitution water,which is present in various polymorphic phases of olivine,can significan...The electrical conductivity of minerals under extreme conditions is governed by their variations in composition and structure.Constitution water,which is present in various polymorphic phases of olivine,can significantly enhance electrical conductivity under mantle pressure-temperature conditions,therefore playing a key role in proton transport.Despite this,the conductive mechanisms in hydrous olivine,particularly in hydrous ringwoodite,and the dynamic behavior of hydrogen at elevated temperatures,remain poorly understood.In this study,we investigated the proton conduction mechanisms in hydrous ringwoodite through first-principles calculations.Several hydrous models were considered,and ab initio molecular dynamics(AIMD)simulations were employed to simulate hydrous configurations at high temperatures.Calculations based on density functional perturbation theory(DFPT)and vibrational density of states(VDOS)analyses were conducted to probe the stability of hydrous structures,and investigate the dynamic behavior of internal hydrogen.Our results indicate that hydrogen trapped in Mg^(2+)and Fe^(3+)defects exhibits significantly higher mobility than hydrogen trapped in Si^(4+)defects.At elevated temperatures,we observed the ionization of hydrogen from cationic defects,leading to high and highly anisotropic proton conductivity along the[100]crystallographic direction.This thermal ionization-induced anisotropic conductivity is consistent with experimental observations of olivine single crystals.Finally,the conductivity of the 0.79 wt%hydrous ringwoodite structure was found to range from 10^(-0.3)to 10^(0.4)S/m,the 1.19 wt%structure ranged from 10^(0.4)to 10^(0.9)S/m in the transition region,and the 1.62 wt%structure exhibited conductivity ranging from 10^(0.7)to 10^(1.2)S/m.These results are in excellent agreement with prior experimental data,providing further insight into the proton conduction mechanisms of hydrous olivine under extreme mantle conditions.展开更多
We calculate the electrical and thermal conductivity of hydrogen for a wide range of densities and temperatures by using molecular dynamics simulations informed by density functional theory.On the basis of the corresp...We calculate the electrical and thermal conductivity of hydrogen for a wide range of densities and temperatures by using molecular dynamics simulations informed by density functional theory.On the basis of the corresponding extended ab initio data set,we construct interpolation formulas covering the range from low-density,high-temperature to high-density,low-temperature plasmas.Our conductivity model repro-duces the well-known limits of the Spitzer and Ziman theory.We compare with available experimental data andfind very good agreement.The new conductivity model can be applied,for example,in dynamo simulations for magneticfield generation in gas giant planets,brown dwarfs,and stellar envelopes.展开更多
As the size of transistors shrinks and power density increases,thermal simulation has become an indispensable part of the device design procedure.However,existing works for advanced technology transistors use simplifi...As the size of transistors shrinks and power density increases,thermal simulation has become an indispensable part of the device design procedure.However,existing works for advanced technology transistors use simplified empirical models to calculate effective thermal conductivity in the simulations.In this work,we present a dataset of size-dependent effective thermal conductivity with electron and phonon properties extracted from ab initio computations.Absolute in-plane and cross-plane thermal conductivity data of eight semiconducting materials(Si,Ge,GaN,AlN,4H-SiC,GaAs,InAs,BAs)and four metallic materials(Al,W,TiN,Ti)with the characteristic length ranging from 5 nm to 50 nm have been provided.Besides the absolute value,normalized effective thermal conductivity is also given,in case it needs to be used with updated bulk thermal conductivity in the future.展开更多
Over the last decade,nuclear theory has made dramatic progress in few-body and ab initio many-body calculations.These great advances stem from chiral efective feld theory(xEFT),which provides an efcient expansion and ...Over the last decade,nuclear theory has made dramatic progress in few-body and ab initio many-body calculations.These great advances stem from chiral efective feld theory(xEFT),which provides an efcient expansion and consistent treatment of nuclear forces as inputs of modern many-body calculations,among which the in-medium similarity renormalization group(IMSRG)and its variants play a vital role.On the other hand,signifcant eforts have been made to provide a unifed description of the structure,decay,and reactions of the nuclei as open quantum systems.While a fully comprehensive and microscopic model has yet to be realized,substantial progress over recent decades has enhanced our understanding of open quantum systems around the dripline,which are often characterized by exotic structures and decay modes.To study these interesting phenomena,Gamow coupled-channel(GCC)method,in which the open quantum nature of few-body valence nucleons coupled to a deformed core,has been developed.This review focuses on the developments of the advanced IMSRG and GCC and their applications to nuclear structure and reactions.展开更多
Potential energy surfaces(PESs), vibrational frequencies, and infrared spectra are calculated for NF_(3)^(+) using ab initio calculations, based on UCCSD(T)/cc-p VTZ combined with vibrational configuration interaction...Potential energy surfaces(PESs), vibrational frequencies, and infrared spectra are calculated for NF_(3)^(+) using ab initio calculations, based on UCCSD(T)/cc-p VTZ combined with vibrational configuration interaction(VCI). Based on an iterative algorithm, the surfaces(SURF) program adds automatic points to the lattice representation of the potential function, the one-dimensional and two-dimensional PESs are calculated after reaching a convergence threshold, finally the smooth image of the potential energy surface is fitted. The PESs accurately account for the interaction between the different modes, with the mode q_(6) symmetrical stretching vibrations having the greatest effect on the potential energy change of the whole system throughout the potential energy surface shift. The anharmonic frequencies are obtained when the VCI matrix is diagonalized. Fundamental frequencies, overtones, and combination bands of NF_(3)^(+) are calculated, which generate the degenerate phenomenon between their frequencies. Finally, the calculated anharmonic frequency is used to plot the infrared spectra.Modal antisymmetric stretching ν_(5) and symmetric stretching ν_(6) exhibit a phenomenon of large-intensity borrowing. This study can provide data to support the characterization in the laboratory.展开更多
The C–H bond activation in alkane dehydrogenation reactions is a key step in determining the reaction rate.To understand the impact of entropy,we performed ab initio static and molecular dynamics free energy simulati...The C–H bond activation in alkane dehydrogenation reactions is a key step in determining the reaction rate.To understand the impact of entropy,we performed ab initio static and molecular dynamics free energy simulations of ethane dehydrogenation over Co@BEA zeolite at different temperatures.AIMD simulations showed that a sharp decrease in free energy barrier as temperature increased.Our analysis of the temperature dependence of activation free energies uncovered an unusual entropic effect accompanying the reaction.The unique spatial structures around the Co active site at different temperatures influenced both the extent of charge transfer in the transition state and the arrangement of 3d orbital energy levels.We provided explanations consistent with the principles of thermodynamics and statistical physics.The insights gained at the atomic level have offered a fresh interpretation of the intricate long-range interplay between local chemical reactions and extensive chemical environments.展开更多
The experimental research programs of 1950s, to understand the adsorption of CO on W surfaces, changed to ab initio studies in 2000s. The goals were to seek improved practical applications. Most of the studies were ba...The experimental research programs of 1950s, to understand the adsorption of CO on W surfaces, changed to ab initio studies in 2000s. The goals were to seek improved practical applications. Most of the studies were based on density functional theory. Many studies also used programs, such as VASP (Vienna Abinitio simulation package) and CPMD. The computational procedures used plane wave approximations. This needed studies with selection of K points and cutoff energy selection to assure convergence in energy calculations. Observations and analysis of papers published from 2006 to 2022 indicate that the cutoff energies were selected arbitrarily without any needed convergence studies. By selecting a published 2006 paper, this paper has clearly showed that an arbitrary selection of cutoff energy, such as 460 eV, is not in the range of, cutoff energies that assure convergence of energy calculations, with ab initio methods and have indicated correction procedures. .展开更多
Fourteen conformers of 3-amino-1-propanol as the minima on the potential energy surface are examined at the MP2/6-311＋＋G＊＊ level. Their relative energies calculated at B3LYP, MP3 and MP4 levels of theory indicated...Fourteen conformers of 3-amino-1-propanol as the minima on the potential energy surface are examined at the MP2/6-311＋＋G＊＊ level. Their relative energies calculated at B3LYP, MP3 and MP4 levels of theory indicated that two most stable conformers display the intramolecular OH - N hydrogen bonds. The vertical ionization energies of these conformers calculated with ab initio electron propagator theory in the P3/aug-cc-pVTZ approximation are in agreement with experimental data from photoelectron spectroscopy. Natural bond orbital analyses were used to explain the differences of IEs of the highest occupied molecular ortibal of conformers. Combined with statistical mechanics principles, conformational distributions at various temperatures are obtained and the temperature dependence of photoelectron spectra is interpreted.展开更多
We report an ab initio〉/I〉 study of spectral properties of Ce^3＋ doped at Na＋ site of the NaF crys-tal, with the charge imbalance compensated by two oxygen substitutions for fluoride （OF＇） in the first coordina...We report an ab initio〉/I〉 study of spectral properties of Ce^3＋ doped at Na＋ site of the NaF crys-tal, with the charge imbalance compensated by two oxygen substitutions for fluoride （OF＇） in the first coordination shell or two sodium vacancies （VNa＇） in the second coordination sphere. Density functional theory calculations within the supercell model are first performed to op-timize the local structures of the charge-compensated Ce^3＋, based on which Ce-centered embedded clusters are constructed and wave function-based CASSCF/CASPT2/RASSI-SO calculations are carried out to obtain the energies of 4f1 and 5d1 levels. By comparing the calculated 4f→5d transition energies with experimental excitation spectra at low temper-atures, the lowest 4f→5d transition band peaked at 390 nm is assigned to the Ce^3＋ with charge compensation by two coordinating OF＇ substitutions, rather than to the Ce^3＋ with compensation by two VNa0 vacancies, as proposed earlier. The electronic reason for the large redshift （by -8000 cm-1） of the lowest 4f→5d transition as induced by the two nearby OF＇ substitutions is analyzed in terms of the changes in the centroid shift and crystal-field splitting.展开更多
The electronic structure of five conformers of 2-chloroethanol was studied by ab initio calculations at B3LYP and MP2 levels of theory with aug-cc-pVTZ basis set. The existing hydrogen bond and hyperconjugation effect...The electronic structure of five conformers of 2-chloroethanol was studied by ab initio calculations at B3LYP and MP2 levels of theory with aug-cc-pVTZ basis set. The existing hydrogen bond and hyperconjugation effects on the stability of 2-chloroethanol conformers were discussed on the base of natural bond orbital analyses. The result exhibits that hyperconjugation is the main factor to determine the stability of conformers. Such effects on the electron wavefunctions of the highest-occupied molecular orbital （HOMO） of different conformers are demonstrated with electron momentum spectroscopy, exhibiting the obviously different symmetries of the HOMO wavefunctions in momentum space.展开更多
118 kinds of Pt-Zr phases were established and investigated by considering various structures. Then the related physical properties, such as structural stability, lattice constants, formation enthalpies, elastic const...118 kinds of Pt-Zr phases were established and investigated by considering various structures. Then the related physical properties, such as structural stability, lattice constants, formation enthalpies, elastic constants and bulk moduli, are obtained by ab initio calculations. Based on the calculated results of formation enthalpies, the ground-state convex hull is derived for the Pt-Zr system. The calculated physical data would provide a basis for further thermodynamic calculations and atomistic simulations. For these Pt-Zr compounds, it is found there are a positive linear correlation between the formation enthalpies and atomic volumes, and a negative linear correlation between the bulk modules and atomic volumes.展开更多
The energy bands,electronic structures of CuN3 and AgN3 crystallines were investigated by periodic ab initio method.The charge density projection shows that there are overlaps of isodensities between the terminal nitr...The energy bands,electronic structures of CuN3 and AgN3 crystallines were investigated by periodic ab initio method.The charge density projection shows that there are overlaps of isodensities between the terminal nitrogen and metallic ion,indicating that the metals and the azides are combined by covalent bonds.The crystal lattice energies are-781.05 and-840.83 kJ/mol for CuN3 and AgN3 respectively.These results approach the data obtained by Gray′s approximate method.The frontier crystal orbital mainly consists of the atomic orbital of azide′s terminal nitrogen.The energy gap for AgN3 is smaller than that of CuN3,and the highest occupied crystal orbitals of AgN-3 consist of both the atomic orbitals of the terminal nitrogen in azide and the silver ion,which facilitates the electron to leap from terminal nitrogen in azide to metallic ion directly.Hence silver azide is slightly more sensitive than copper azide.The elastic coefficients C11,C22 and C33 of CuN3 are predicted to be 96.52,96.86 and 154.06 GPa,C11 and C22 of AgN3 are 303.29 and 138.80 GPa.展开更多
基金supported in part by the National Natural Science Foundation of China (Grant Nos. 12141501, 123B2080, 12435006, 12475117, and 11935003)the National Key Laboratory of Neutron Science and Technology (Grant No. NST202401016)+2 种基金the National Key R&D Program of China (Grant No. 2024YFE0109803)the High-performance Computing Platform of Peking Universitythe funding support from the State Key Laboratory of Nuclear Physics and Technology, Peking University (Grant No. NPT2023ZX03)。
文摘An accurate and simultaneous ab initio prediction for both light nuclei and nuclear matter has been a longstanding challenge in nuclear physics, due to the significant uncertainties associated with the three-nucleon forces.In this Letter, we develop the relativistic quantum Monte Carlo methods for the nuclear ab initio problem, and calculate the ground-state energies of A ≤ 4 nuclei using the two-nucleon Bonn force with an unprecedented high accuracy. The present relativistic results significantly outperform the nonrelativistic results with only twonucleon forces. We demonstrate that both light nuclei and nuclear matter can be well described simultaneously in the relativistic ab initio calculations, even in the absence of three-nucleon forces, and a correlation between the properties of light A ≤ 4 nuclei and the nuclear saturation is revealed. This provides a quantitative understanding of the connection between the light nuclei and nuclear matter saturation properties.
基金Project(22376221)supported by the National Natural Science Foundation of ChinaProject(2024JJ2074)supported by the Natural Science Foundation of Hunan Province,ChinaProject(2023QNRC001)supported by the Young Elite Scientists Sponsorship Program by CAST。
文摘Understanding the adsorption behavior of heavy metals and metalloids on clay minerals is essential for remediating heavy metal-contaminated soils.The adsorption of heavy metals and metalloids on illite(001)and sodium montmorillonite(Na-MMT)(001)surfaces was investigated using first-principles calculations in this study,especially As atom and H_(3)AsO_(3) molecule.The adsorption energies of the As atom were−1.94 eV on the illite(001)and−0.56 eV on the Na-MMT(001),whereas,the adsorption energies of the H_(3)AsO_(3) molecule were−1.40 eV on illite(001)and−1.01 eV on Na-MMT(001).The above results indicate that the adsorption was more energetically favorable on illite(001).Additionally,compared to Na-MMT(001),there were more significant interactions between the atoms/molecules on the illite(001).After As atom and H_(3)AsO_(3) molecule adsorption,the electrons were transferred from mineral surface atoms to the adsorbates on both illite(001)and Na-MMT(001)surfaces.Moreover,the adsorption of As atom on illite(001)and Na-MMT(001)surfaces were more energy favorable compared to Hg,Cd,and Cr atoms.Overall,this work provides new insights into the adsorption behavior of As atoms and As molecules on illite and Na-MMT.The results indicate that illite rich soils are more prone to contamination by arsenic compared to soils primarily composed of Na-MMT minerals.
基金supported by the National Natural Science Foundation of China(41930112,91755215)the Sichuan Students'Innovation and entrepreneurship training program(s202310616086).
文摘The electrical conductivity of minerals under extreme conditions is governed by their variations in composition and structure.Constitution water,which is present in various polymorphic phases of olivine,can significantly enhance electrical conductivity under mantle pressure-temperature conditions,therefore playing a key role in proton transport.Despite this,the conductive mechanisms in hydrous olivine,particularly in hydrous ringwoodite,and the dynamic behavior of hydrogen at elevated temperatures,remain poorly understood.In this study,we investigated the proton conduction mechanisms in hydrous ringwoodite through first-principles calculations.Several hydrous models were considered,and ab initio molecular dynamics(AIMD)simulations were employed to simulate hydrous configurations at high temperatures.Calculations based on density functional perturbation theory(DFPT)and vibrational density of states(VDOS)analyses were conducted to probe the stability of hydrous structures,and investigate the dynamic behavior of internal hydrogen.Our results indicate that hydrogen trapped in Mg^(2+)and Fe^(3+)defects exhibits significantly higher mobility than hydrogen trapped in Si^(4+)defects.At elevated temperatures,we observed the ionization of hydrogen from cationic defects,leading to high and highly anisotropic proton conductivity along the[100]crystallographic direction.This thermal ionization-induced anisotropic conductivity is consistent with experimental observations of olivine single crystals.Finally,the conductivity of the 0.79 wt%hydrous ringwoodite structure was found to range from 10^(-0.3)to 10^(0.4)S/m,the 1.19 wt%structure ranged from 10^(0.4)to 10^(0.9)S/m in the transition region,and the 1.62 wt%structure exhibited conductivity ranging from 10^(0.7)to 10^(1.2)S/m.These results are in excellent agreement with prior experimental data,providing further insight into the proton conduction mechanisms of hydrous olivine under extreme mantle conditions.
基金supported by the Priority Program SPP 1992 of the German Science Foundation(DFG)The Diversity of Exoplanets under project number 362460292.
文摘We calculate the electrical and thermal conductivity of hydrogen for a wide range of densities and temperatures by using molecular dynamics simulations informed by density functional theory.On the basis of the corresponding extended ab initio data set,we construct interpolation formulas covering the range from low-density,high-temperature to high-density,low-temperature plasmas.Our conductivity model repro-duces the well-known limits of the Spitzer and Ziman theory.We compare with available experimental data andfind very good agreement.The new conductivity model can be applied,for example,in dynamo simulations for magneticfield generation in gas giant planets,brown dwarfs,and stellar envelopes.
基金Project supported by the National Key R&D Project from Ministry of Science and Technology of China(Grant No.2022YFA1203100)the National Natural Science Foundation of China(Grant No.52122606)the funding from Shanghai Polytechnic University.
文摘As the size of transistors shrinks and power density increases,thermal simulation has become an indispensable part of the device design procedure.However,existing works for advanced technology transistors use simplified empirical models to calculate effective thermal conductivity in the simulations.In this work,we present a dataset of size-dependent effective thermal conductivity with electron and phonon properties extracted from ab initio computations.Absolute in-plane and cross-plane thermal conductivity data of eight semiconducting materials(Si,Ge,GaN,AlN,4H-SiC,GaAs,InAs,BAs)and four metallic materials(Al,W,TiN,Ti)with the characteristic length ranging from 5 nm to 50 nm have been provided.Besides the absolute value,normalized effective thermal conductivity is also given,in case it needs to be used with updated bulk thermal conductivity in the future.
基金National Key R&D Program of China under Grant Nos.2023YFA1606400 and 2022YFA1602303National Natural Science Foundation of China under Grants Nos.12335007,12035001,11921006,12347106,12147101,and 12205340+1 种基金Gansu Natural Science Foundation under Grant No.22JR5RA123U.S.Department of Energy(DOE),Office of Science,under SciDAC-5(NUCLEI collaboration)。
文摘Over the last decade,nuclear theory has made dramatic progress in few-body and ab initio many-body calculations.These great advances stem from chiral efective feld theory(xEFT),which provides an efcient expansion and consistent treatment of nuclear forces as inputs of modern many-body calculations,among which the in-medium similarity renormalization group(IMSRG)and its variants play a vital role.On the other hand,signifcant eforts have been made to provide a unifed description of the structure,decay,and reactions of the nuclei as open quantum systems.While a fully comprehensive and microscopic model has yet to be realized,substantial progress over recent decades has enhanced our understanding of open quantum systems around the dripline,which are often characterized by exotic structures and decay modes.To study these interesting phenomena,Gamow coupled-channel(GCC)method,in which the open quantum nature of few-body valence nucleons coupled to a deformed core,has been developed.This review focuses on the developments of the advanced IMSRG and GCC and their applications to nuclear structure and reactions.
基金Project supported by the National Natural Science Foundation of China (Grant Nos.52002318 and 22103061)。
文摘Potential energy surfaces(PESs), vibrational frequencies, and infrared spectra are calculated for NF_(3)^(+) using ab initio calculations, based on UCCSD(T)/cc-p VTZ combined with vibrational configuration interaction(VCI). Based on an iterative algorithm, the surfaces(SURF) program adds automatic points to the lattice representation of the potential function, the one-dimensional and two-dimensional PESs are calculated after reaching a convergence threshold, finally the smooth image of the potential energy surface is fitted. The PESs accurately account for the interaction between the different modes, with the mode q_(6) symmetrical stretching vibrations having the greatest effect on the potential energy change of the whole system throughout the potential energy surface shift. The anharmonic frequencies are obtained when the VCI matrix is diagonalized. Fundamental frequencies, overtones, and combination bands of NF_(3)^(+) are calculated, which generate the degenerate phenomenon between their frequencies. Finally, the calculated anharmonic frequency is used to plot the infrared spectra.Modal antisymmetric stretching ν_(5) and symmetric stretching ν_(6) exhibit a phenomenon of large-intensity borrowing. This study can provide data to support the characterization in the laboratory.
文摘The C–H bond activation in alkane dehydrogenation reactions is a key step in determining the reaction rate.To understand the impact of entropy,we performed ab initio static and molecular dynamics free energy simulations of ethane dehydrogenation over Co@BEA zeolite at different temperatures.AIMD simulations showed that a sharp decrease in free energy barrier as temperature increased.Our analysis of the temperature dependence of activation free energies uncovered an unusual entropic effect accompanying the reaction.The unique spatial structures around the Co active site at different temperatures influenced both the extent of charge transfer in the transition state and the arrangement of 3d orbital energy levels.We provided explanations consistent with the principles of thermodynamics and statistical physics.The insights gained at the atomic level have offered a fresh interpretation of the intricate long-range interplay between local chemical reactions and extensive chemical environments.
文摘The experimental research programs of 1950s, to understand the adsorption of CO on W surfaces, changed to ab initio studies in 2000s. The goals were to seek improved practical applications. Most of the studies were based on density functional theory. Many studies also used programs, such as VASP (Vienna Abinitio simulation package) and CPMD. The computational procedures used plane wave approximations. This needed studies with selection of K points and cutoff energy selection to assure convergence in energy calculations. Observations and analysis of papers published from 2006 to 2022 indicate that the cutoff energies were selected arbitrarily without any needed convergence studies. By selecting a published 2006 paper, this paper has clearly showed that an arbitrary selection of cutoff energy, such as 460 eV, is not in the range of, cutoff energies that assure convergence of energy calculations, with ab initio methods and have indicated correction procedures. .
基金This work was supported by the Province Natural Science Foundation of Henan （No.082300410030）, the Foundation of Henan Educational Committee （No.2011A140015）, and the Doctoral Research Pund of Henan Normal University （No.525449）.
文摘Fourteen conformers of 3-amino-1-propanol as the minima on the potential energy surface are examined at the MP2/6-311＋＋G＊＊ level. Their relative energies calculated at B3LYP, MP3 and MP4 levels of theory indicated that two most stable conformers display the intramolecular OH - N hydrogen bonds. The vertical ionization energies of these conformers calculated with ab initio electron propagator theory in the P3/aug-cc-pVTZ approximation are in agreement with experimental data from photoelectron spectroscopy. Natural bond orbital analyses were used to explain the differences of IEs of the highest occupied molecular ortibal of conformers. Combined with statistical mechanics principles, conformational distributions at various temperatures are obtained and the temperature dependence of photoelectron spectra is interpreted.
文摘We report an ab initio〉/I〉 study of spectral properties of Ce^3＋ doped at Na＋ site of the NaF crys-tal, with the charge imbalance compensated by two oxygen substitutions for fluoride （OF＇） in the first coordination shell or two sodium vacancies （VNa＇） in the second coordination sphere. Density functional theory calculations within the supercell model are first performed to op-timize the local structures of the charge-compensated Ce^3＋, based on which Ce-centered embedded clusters are constructed and wave function-based CASSCF/CASPT2/RASSI-SO calculations are carried out to obtain the energies of 4f1 and 5d1 levels. By comparing the calculated 4f→5d transition energies with experimental excitation spectra at low temper-atures, the lowest 4f→5d transition band peaked at 390 nm is assigned to the Ce^3＋ with charge compensation by two coordinating OF＇ substitutions, rather than to the Ce^3＋ with compensation by two VNa0 vacancies, as proposed earlier. The electronic reason for the large redshift （by -8000 cm-1） of the lowest 4f→5d transition as induced by the two nearby OF＇ substitutions is analyzed in terms of the changes in the centroid shift and crystal-field splitting.
文摘The electronic structure of five conformers of 2-chloroethanol was studied by ab initio calculations at B3LYP and MP2 levels of theory with aug-cc-pVTZ basis set. The existing hydrogen bond and hyperconjugation effects on the stability of 2-chloroethanol conformers were discussed on the base of natural bond orbital analyses. The result exhibits that hyperconjugation is the main factor to determine the stability of conformers. Such effects on the electron wavefunctions of the highest-occupied molecular orbital （HOMO） of different conformers are demonstrated with electron momentum spectroscopy, exhibiting the obviously different symmetries of the HOMO wavefunctions in momentum space.
基金Projects (50971072,51131003) support by the National Natural Science Foundation of ChinaProjects (2011CB606301,2012CB825700) supported by the Ministry of Science and Technology of ChinaProject supported by the Administration of Tsinghua University
文摘118 kinds of Pt-Zr phases were established and investigated by considering various structures. Then the related physical properties, such as structural stability, lattice constants, formation enthalpies, elastic constants and bulk moduli, are obtained by ab initio calculations. Based on the calculated results of formation enthalpies, the ground-state convex hull is derived for the Pt-Zr system. The calculated physical data would provide a basis for further thermodynamic calculations and atomistic simulations. For these Pt-Zr compounds, it is found there are a positive linear correlation between the formation enthalpies and atomic volumes, and a negative linear correlation between the bulk modules and atomic volumes.
文摘The energy bands,electronic structures of CuN3 and AgN3 crystallines were investigated by periodic ab initio method.The charge density projection shows that there are overlaps of isodensities between the terminal nitrogen and metallic ion,indicating that the metals and the azides are combined by covalent bonds.The crystal lattice energies are-781.05 and-840.83 kJ/mol for CuN3 and AgN3 respectively.These results approach the data obtained by Gray′s approximate method.The frontier crystal orbital mainly consists of the atomic orbital of azide′s terminal nitrogen.The energy gap for AgN3 is smaller than that of CuN3,and the highest occupied crystal orbitals of AgN-3 consist of both the atomic orbitals of the terminal nitrogen in azide and the silver ion,which facilitates the electron to leap from terminal nitrogen in azide to metallic ion directly.Hence silver azide is slightly more sensitive than copper azide.The elastic coefficients C11,C22 and C33 of CuN3 are predicted to be 96.52,96.86 and 154.06 GPa,C11 and C22 of AgN3 are 303.29 and 138.80 GPa.
