A narrowband radio interferometer has been developed and used to locate the entire sources of VHF radiations from a negative cloud-to-ground (CG) lightning discharge which contains 19 strokes. This system uses five an...A narrowband radio interferometer has been developed and used to locate the entire sources of VHF radiations from a negative cloud-to-ground (CG) lightning discharge which contains 19 strokes. This system uses five antennas to form an array consisting of short- and long-baselines along two or- thogonal directions. The system error which comes from frequency conversion is reduced by phase detection through direct high frequency amplifying. An interactive graphic analysis procedure is used to remove the fringe ambiguities which exist inherently in interferometry and to determine the direction of lightning radiation sources in two dimensions (azimuth and elevation) as a function of time at a time resolution of microsecond orders. With the developed system, the whole progression process in time and space of a lightning flash can be reconstructed. In this paper, combining the synchronous data of electric filed change and VHF radiation, the whole processes of an example negative CG flash have been studied in detail. It is found that the preliminary breakdown event of the CG flash started from negative charge region and exhibited firstly a downward pregression and then an upward propagation. There were very intense and continuous radiations during stepped leaders which became much stronger when the first return stroke began. In contrast, there were less and only discrete radiations during dart leaders. Stepped leader and dart leader may transform to each other depending on the state of the ionization of the path. The progression speed of initial stepped leaders was about 105 ms?1, while that was about 4.1×106 and 6.0×106 ms?1 for dart leaders and dart-stepped leaders, respectively. M events produced hook-shaped field changes accompanied by active burst of radiations at their begin- nings. Followed these active radiation processes, M events appeared to contact finally into conducting main discharge channels. The mean progression speed of M events was about 7×107 ms?1, greater than that of the dart leaders and dart-ste展开更多
The insertion reaction mechanism of CBr2 with CH3CH2O has been studied by using the B3LYP/6-311G(d) and CCSD(T)/6-311G(d) at single point. The geometries of reactions,transition state and products were completely opti...The insertion reaction mechanism of CBr2 with CH3CH2O has been studied by using the B3LYP/6-311G(d) and CCSD(T)/6-311G(d) at single point. The geometries of reactions,transition state and products were completely optimized. All the transition state is verified by the vibrational analysis and the internal re-action coordinate (IRC) calculations. The results show that reaction (1) is the dominant reaction path,which proceeds via two steps: i) two reactants form an intermediate (IM1),which is an exothermal re-action of 8.62 kJ·mol?1 without energy barrier; ii) P1 is obtained via the TS1 and the H-shift,in which the energy barrier is 44.53 kJ·mol?1. The statistical thermodynamics and Eyring transition state theory with Wigner correction are used to study the thermodynamic and kinetic characters of this reaction in temperature range from 100 to 2200 K. The results show that the appropriate reaction temperature ranges from 200 to 1900 K at 1.0 atm,in which the reaction has a bigger spontaneity capability,equi-librium constant (K) and higher rate constant (k).展开更多
Food systems have the potential to promote human health and enhance environmental sustainability;yet most African countries have decadal starvation and malnourishment due to unstable food systems lacking basic nutriti...Food systems have the potential to promote human health and enhance environmental sustainability;yet most African countries have decadal starvation and malnourishment due to unstable food systems lacking basic nutritional profiles. To understand the key questions of the African food production and food security crisis, it is important to evaluate the past and the present balance of food production and consumption quantitatively and comprehensively and identify resource constraints. This continental study analyzed water-land-food (WLF) nexus in recent decades (1997-2017) and accessed whether these resources cope with different population growth projections, dietary changes and agricultural water management. The findings revealed that in 2017, total production in Africa for the four major crops was 83.3, 34.1, 21.0 and 26.7 million tons for, respectively, maize, rice, sorghum and wheat. Together with the imported food, 38 countries experienced an increase in kcal by food supply, while 7 countries encountered a decrease. However, only 6 countries were above the 1500 kcal∙capita<sup>−1</sup>∙day<sup>−1</sup>—the global average food consumption from the four major crops. The study also found that in the context of food production and out of the total African population, 268 million (21.6%) have enough land and water, 310 million (25.0%) is without enough land and water, further 279 million (22.5%) have enough water but not enough land, and 381 million (30.8%) encounter enough land but not enough water. This is the first WLF nexus study for the African continent and emphasizes the need for efficient and rapid changes in the food systems of the African population, both in production and consumption, in order to provide sustainable and secure food systems, and ultimately approach the first three Sustainable Development Goals.展开更多
The insertion reaction mechanism of CBr_2 with CH_3CH_O has been studied by using the B3LYP/6-31G(d) method. The geometries of reactions, transition state and products were completely optimized. All the energy of the ...The insertion reaction mechanism of CBr_2 with CH_3CH_O has been studied by using the B3LYP/6-31G(d) method. The geometries of reactions, transition state and products were completely optimized. All the energy of the species was obtained at the CCSD(T)/6-31G(d) level. All the transition state is verified by the vibrational analysis and the internal reaction coordinate (IRC) calculations. The results show that the propionaldehyde (~HP1) is the main product of CH_2 insertion with CH_3CH_O. The calculated results indicated that all the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CBr_2 not only can insert the C_α-H [reaction I(1)]) but also can react with C_β-H [reaction II(1)]. The statistical thermodynamics and Eyring transition state theory with Wigner correc- tion are used to study the thermodynamic and kinetic characters of I(1) and II(1) in temperature range from 100 to 2200 K. The results show that the appropriate reaction temperature rang is 250 to 1750 K and 250 to 1600 K at 1.0 atm for I(1) and II(1) respectively. The rate constant and equilibrium constant are distinct in the range from 250 to 1000 K so that I(1) more easily occurs, while the reactions are not selected in the temperature range of 1000-1600展开更多
The intersystem crossing channels of gaseous 4H-pyran-4-thione were investigated using the CASSCF//TD-B3LYP methods and group theory. Using the effective one-electron spin-orbit Harniltonian, the strengths of spin-orb...The intersystem crossing channels of gaseous 4H-pyran-4-thione were investigated using the CASSCF//TD-B3LYP methods and group theory. Using the effective one-electron spin-orbit Harniltonian, the strengths of spin-orbit coupling were estimated, which plays an essential role in the spin transitions between different spin states. Calculated results show that phosphorescence and non-radiative decay via intersystem crossing to the So state are concurrent processes occurring at the T1 state. A rapid depletion of the S1 state via intersystem crossing to the T1 state can be mediated by the T2 state, if spin relaxation is fast within the triplet levels. Our calculated results are in close agreement with experimental observations.展开更多
The insertion and abstraction reaction mechanisms of singlet and triplet CCl2 with CH3MH (M=O, S) have been studied by using the DFT, NBO and AIM methods. The geometries of reactions, the transition state and products...The insertion and abstraction reaction mechanisms of singlet and triplet CCl2 with CH3MH (M=O, S) have been studied by using the DFT, NBO and AIM methods. The geometries of reactions, the transition state and products were completely optimized by B3LYP/6–311G(d, p). All the energy of the species was obtained at the CCSD(T)/6–311G(d, p) level. The calculated results indicated that the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CCl2 can not only trigger the insertion reaction with C-H and M-H in four pathways, by which the products P1 [CH3OCHCl2, reaction I(1)], P3[Cl2HCCH2OH, reaction I(2)], P5[CH3SCHCl2, reaction II(1)] and P7[Cl2HCCH2SH, reaction II(2)] are produced respectively, but also abstract M-H, resulting P4 [CH2O+CH2Cl2, reaction I(3)] and P8[CH2S+CH2Cl2, reaction II(3)]. In addition, the important geometries in domain pathways have been studied by AIM and NBO theories.展开更多
The two-state mechanism of the reaction of Nb(NH2)3 with N2O on the singlet and triplet potential energy surfaces has been investigated at the B3LYP level.Crossing points between the potential energy surfaces have bee...The two-state mechanism of the reaction of Nb(NH2)3 with N2O on the singlet and triplet potential energy surfaces has been investigated at the B3LYP level.Crossing points between the potential energy surfaces have been located using different methods.Analysis of the strain model shows that the singlet state of the four-coordinate(N2O)Nb(NH2)3 complex with N2O bonded via terminal N atom coordination(12) is more stable in the initial stage of reaction,since the bending of the N2O fragment [Edef(N2O) = 86.1 kcal mol-1] results in an energy splitting of the doubly degenerate LUMO;the low-energy LUMO can now strongly couple with the occupied Nb-localized d orbitals,forming a back-bond and transferring charge(q = 0.82 e) from Nb(NH2)3 to the N2O ligand.Going from 32 to 12,the reacting system changes spin multiplicity near the MECP(minimal energy crossing point) region,which takes place with a spin crossing barrier of 9.6-10.0 kcal mol-1.Analysis of spin-orbit coupling(SOC) indicates that MECP will produce a significant SOC matrix element.The value of SOC is 111.52 cm-1,due to the electron shift between two perpendicular φ orbitals with the same rotation direction,and the magnitude of the spin-multi-plicity mixing increases in the small energy gap between high-and low-spin states,greatly enhancing the probability of intersystem crossing.The probabilities of single(P1 ISC) and double(P2 ISC) passes estimated at MECP(SOC = 111.52 cm-1) are approximately 1.17×10-2 and 2.32×10-2,respectively.展开更多
The insertion reaction mechanisms of siglet and striglet CCl2 with CH3CHO have been studied by using the DFT, NBO, CCSD(T) and AIM method. The geometries of reactions, transition state and products were completely opt...The insertion reaction mechanisms of siglet and striglet CCl2 with CH3CHO have been studied by using the DFT, NBO, CCSD(T) and AIM method. The geometries of reactions, transition state and products were completely optimized by B3LYP/6-31G(d). All the energy of the species was obtained at the CCSD(T)/6-31G(d,p) level. The calculated results indicated that all the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CCl2 can not only insert the Cα—H (reaction I) but also can react with Cβ—H (reaction Ⅱ). There are three main existing pathways and the products are P1 (CH3COHCCl2), P2 (CH2COHCHCl2) and P4[CHCl2CHCHOH] respectively. Reaction Ⅱ happens more easily according to the energy changes and the barrier in rate-controlling step. In addi-tion, the important geometries in domain pathways have been studied by AIM theory. And also, the en-ergy changes of H in the inserted C—H bond have been investigated.展开更多
Myotonic dystrophy type 1 (DM1),or Steiner’s disease,is an autosomal dominant disorder caused by the expansion of unstable trinucleotide repeats (CTG) in the 3’ untranslated region of the myotonic dystrophy protein ...Myotonic dystrophy type 1 (DM1),or Steiner’s disease,is an autosomal dominant disorder caused by the expansion of unstable trinucleotide repeats (CTG) in the 3’ untranslated region of the myotonic dystrophy protein kinase gene (DMPK) (Brook et al.,1992;Mahadevan et al.,1992).The number of CTG repeats observed in normal individuals is in a range of 5-34,while the individuals with 35-49 CTG repeats are usually asymptomatic but at risk of展开更多
The structures of 2,7＇-（ethylene）-bis-8-hydroxyquinoline and its derivatives were optimized at the ground states using ab initio HF and B3LYP methods. At the same time, the molecular structures of the first singlet...The structures of 2,7＇-（ethylene）-bis-8-hydroxyquinoline and its derivatives were optimized at the ground states using ab initio HF and B3LYP methods. At the same time, the molecular structures of the first singlet excited state for 2,7＇-（ethylene）-bis-8-hydroxyqulnoline and its derivatives were optimized by CIS/6-31G（d）. The absorption and emission spectra based on the above structures were obtained by the time-dependent density functional theory （TD-DFT） by the B3LYP method with the 6-31G（d） basis set. The calculated results of luminescence originate from the electronic transition from the hydroxphenol ring of 8-hydroxyquinoline A to the pyridine ring of 8-hydroxyquinoline B. Their luminescence wave bands can be tuned by different substituents on the ligand of 8-hydroxyquinoline.展开更多
We used density functional calculations to investigate the electronic origins of the magnetic properties of the high-spin ferric enzyme-substrate complex protocatechuate 3,4-dioxygenase(3,4-PCD).The calculated g-tenso...We used density functional calculations to investigate the electronic origins of the magnetic properties of the high-spin ferric enzyme-substrate complex protocatechuate 3,4-dioxygenase(3,4-PCD).The calculated g-tensors show that ligand-to-metal charge transfer transitions are from the protocatechuate(PCA) and Tyr408 orbitals to the Fe d orbitals,which lead to x-and y-polarized transitions.These polarized transitions require a spin-orbit coupling(SOC) matrix element in the z-direction,Lz(z=z'),resulting in a g z value of 2.0158,significantly deviating from 2.0023.A large zero-field splitting parameter value of+1.147cm-1 is due to △S =-1 spin-orbit mixing with the quartet states for the sextet ground state,accounting for around 73% of the SOC contribution.The SOC matrix elements indicate that the high-spin d 5 system Fe(Ⅲ),3,4-PCD-PCA is a weak spin-crossover compound with an SOC of 31.56 cm-1.展开更多
Red long lasting phosphorescence（LLP） was firstly observed in LaA103：Eu3＋ phosphor synthesized by solid state method at 1773 K. It reveals that the Eu3＋ ions occupy the asymmetric La3＋ sites, resulting in the or...Red long lasting phosphorescence（LLP） was firstly observed in LaA103：Eu3＋ phosphor synthesized by solid state method at 1773 K. It reveals that the Eu3＋ ions occupy the asymmetric La3＋ sites, resulting in the orange-red emission of Eu3＋. The LLP of the optimum LaA103：0.6%Eu3＋ sample can come to about 2000 s according to a definition of 0.32 mcd/m2. The LLP decay curve can not be fitted even by a function of three exponential terms, due to the complicated retrapping process of carriers. The result of a classical multi-peak fitting method on thermo- luminescence reveals that the excellent LLP performance of LaA103：Eu3＋ material originates from the rich distribu- tion of shallow traps（E=0.7875 eV）.展开更多
An isospin-dependent quantum molecular dynamical model （IQMD） is developed, with the isospin degree of freedom in the momentum-dependent interaction（MDI） included in IQMD, to obtain an isospin- and momentum-depend...An isospin-dependent quantum molecular dynamical model （IQMD） is developed, with the isospin degree of freedom in the momentum-dependent interaction（MDI） included in IQMD, to obtain an isospin- and momentum-dependent interaction （IMDI） in IQMD. We investigate the effect of IMDI on the isospin fractionation ratio and its dynamical mechanism in the intermediate energy heavy ion collisions. It is found that the IMDI induces the significant reductions in the isospin fractionation ratio for all of beam energies, impact parameters, neutron-proton ratios and mass number of colliding systems. However, the strong dependence of isospin fractionation ratio on the symmetrical potential is preserved, with the isospin degree of freedom included in the MDI, i.e. the isospin fractionation ratio is still a good probe for extracting the information about the equation of state of isospin asymmetrical nuclear matter.展开更多
Based on the concept of the pseudo amino acid composition （PseAAC）, protein structural classes are predicted by using an approach of increment of diversity combined with support vector machine （ID-SVM）, in which t...Based on the concept of the pseudo amino acid composition （PseAAC）, protein structural classes are predicted by using an approach of increment of diversity combined with support vector machine （ID-SVM）, in which the dipeptide amino acid composition of proteins is used as the source of diversity. Jackknife test shows that total prediction accuracy is 96.6% and higher than that given by other approaches. Besides, the specificity （Sp） and the Matthew＇s correlation coefficient （MCC） are also calculated for each protein structural class, the Sp is more than 88%, the MCC is higher than 92%, and the higher MCC and Sp imply that it is credible to use ID-SVM model predicting protein structural class. The results indicate that： 1 the choice of the source of diversity is reasonable, 2 the predictive performance of IDSVM is excellent, and3 the amino acid sequences of proteins contain information of protein structural classes.展开更多
The excited-state intramolecular hydrogen abstraction reactions of butanal have been investigated using the CAS-MP2/6-311＋G^＊//CASSCF/6-31G^＊ methods. Calculated results show that the hydrogen transfer induced fluo...The excited-state intramolecular hydrogen abstraction reactions of butanal have been investigated using the CAS-MP2/6-311＋G^＊//CASSCF/6-31G^＊ methods. Calculated results show that the hydrogen transfer induced fluorescence quenching of the n,π^＊-excited state of covalent butanal with three paths： （1） The first path corresponds to direct S0-react reconstitution, which involves the first S1 decay by partial hydrogen atom transfer. （2） The second stepwise mechanism can be viewed as a full hydrogen atom transfer followed by a partial hydrogen atom back transfer, electron transfer （near S1/S0 or S0-TS） and finally a proton transfer to S0-react. （3） On the triplet surface, the surface crossing to the singlet state would be clearly much efficient at the T1/S0 region due to the large SOC value of 8.3 cm^-1. The S0-react decay route from T1/S0 was studied with an intrinsic reaction coordinate （IRC） calculation at the CASSCF level, resulting in the S0-React minimum.展开更多
The potential energy surface crossings for 1,2-dithiete have been investigated using the complete active space self-consistent field (CASSCF) method and simple group theory. Using the full Pauli-Breit spin-orbit coupl...The potential energy surface crossings for 1,2-dithiete have been investigated using the complete active space self-consistent field (CASSCF) method and simple group theory. Using the full Pauli-Breit spin-orbit coupling (SOC) operator $$ (\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\frown}$}}{H} _{SO} ) $$ which consists of the one-electron $$ (\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\frown}$}}{H} _{SO1} ) $$ and two-electron $$ (\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\frown}$}}{H} _{SO2} ) $$ terms, we estimate the strengths of the SOC (198.37 cm?1 when symmetry is imposed, and 211.35 cm?1 with no symmetry constraints), which plays an essential role in the spin transitions between different spin states. The calculations show that the photolysis of 1,3-dithiol-2-one leads to the formation of trans-dithioglyoxal (trans-MinS0) as a primary product which subsequently gives a secondary product identified as thiolthioketene. Our calculated results are in close agreement with the experimental observations.展开更多
Electron-impact single ionization cross sections for W^q＋（q = 4–5） were calculated using the flexible atomic code（FAC） in the level-to-level distorted-wave method, considering the explicit branching ratio. The c...Electron-impact single ionization cross sections for W^q＋（q = 4–5） were calculated using the flexible atomic code（FAC） in the level-to-level distorted-wave method, considering the explicit branching ratio. The calculated cross sections are compared with the available theoretical and experiment results in detail. In the case of the contribution from the same channles as the available theoretical results, all of the calculated ionization cross sections agree with the experimental measured cross sections. But the present calculated results are larger than the experimental measurement when all channels contributions are included. Some important channels excitation autoionization（EA） contributions, such as the excitation to higher higher nl subshell from 4 f and 5[s,p], were not included into the available theoretical calculation. In general, the distorted-wave（DW） results are overestimated.展开更多
The optimized geometries of the complexes between HnY (n=2, 3; Y=O, S, N) and LiNH2 have been calculated at the B3LYP/6-311++G** and MP2/6-311++G** levels. Three stable complexes were obtained. Frequency analysis show...The optimized geometries of the complexes between HnY (n=2, 3; Y=O, S, N) and LiNH2 have been calculated at the B3LYP/6-311++G** and MP2/6-311++G** levels. Three stable complexes were obtained. Frequency analysis showed that the enlarged 2N―4Li presents the abnormal blue shift in three complexes. The calculated binding energy with basis set super-position error (BSSE) and zero-point vibrational energy (ZPE) corrections of complex I―III is _58.65, _31.66 and _69.59 kJ·mol-1 (MP2), respectively. Natural bond orbital theory (NBO) analysis has been performed, and the results revealed that the H2O…LiNH2 (complex I) and H3N…LiNH2 (complex III) are formed with coexisting σ-s and n-s type lithium bond interactions, complexⅡis formed with π-s type lithium bond interaction between HnY (n=2,3; Y=O, N) and LiNH2, and H2S…LiNH2 (complex II) is formed with n-s type lithium bond interaction between H2S and LiNH2. Natural resonance theory (NRT) and atom in molecule (AIM) theory have also been studied to investigate the bond order and topological properties of the lithium bond structures.展开更多
The spin-forbidden reaction 1HNO(1A')+OH-→3NO-(3Σ-)+H2O has been extensively explored using various CASSCF active spaces with MP2 corrections in several basis sets. Natural bond orbital (NBO) analysis, together ...The spin-forbidden reaction 1HNO(1A')+OH-→3NO-(3Σ-)+H2O has been extensively explored using various CASSCF active spaces with MP2 corrections in several basis sets. Natural bond orbital (NBO) analysis, together with the NBO energetic (deletion) analysis, indicates that the two isomers have nearly equal total energy and could compete with each other in the title reaction. More significantly, the singlet/triplet surface crossing regions have been examined and the spinorbit coupling (SOC) and energetics have been computed. The computational results indicate that the SOC is very large at the crossing point T1/S0 trans (ca.40.9 cm-1). Moreover, the T1/S0 trans has a low energy of 10.67 kcal/mol relative to that of trans-S0. Therefore, the surface crossing to the triplet state seems much more efficient at the T1/S0 trans region along the minimum energy path (MEP), However, The values of single (P1ISC) and double (P2ISC) passes estimated at T1/S0 trans show that the ISC occurs with a little probability.展开更多
Based on both very obvious isospin effect of the neutron-proton number ratio of nucleon emissions （n/p）nud on symmetry potential and （n/p）nucl＇s sensitive dependence on symmetry potential in the nuclear reactions...Based on both very obvious isospin effect of the neutron-proton number ratio of nucleon emissions （n/p）nud on symmetry potential and （n/p）nucl＇s sensitive dependence on symmetry potential in the nuclear reactions induced by halo-neutron projectiles, compared to the same mass stable projectile, probing symmetry potential is investigated within the isospin-dependent quantum molecular dynamics with isospin and momentum-dependent interactions for different symmetry potentials U;ym and U2^sym. It is found that the neutron-halo projectile induces very obvious increase of （n/p）nucl and strengthens the dependence of （n/p） l on the symmetry potential for all the beam energies and impact parameters, compared to the same mass stable projectile under the same incident channel condition. Therefore （n/p）nucl induced by the neutron-halo projectile is a more favourable probe than the normal neutron-rich and neutron-poor projectiles for extracting the symmetry potential.展开更多
基金the Knowledge Innovation Program of the Chinese Academy of Sci-ences (Grant No. KZCX2-YW-206-2)the National Natural Science Foundation of China (Grant No. 40775004)the National Science Fund for Distinguished Young Scholars (Grant No. 40325013)
文摘A narrowband radio interferometer has been developed and used to locate the entire sources of VHF radiations from a negative cloud-to-ground (CG) lightning discharge which contains 19 strokes. This system uses five antennas to form an array consisting of short- and long-baselines along two or- thogonal directions. The system error which comes from frequency conversion is reduced by phase detection through direct high frequency amplifying. An interactive graphic analysis procedure is used to remove the fringe ambiguities which exist inherently in interferometry and to determine the direction of lightning radiation sources in two dimensions (azimuth and elevation) as a function of time at a time resolution of microsecond orders. With the developed system, the whole progression process in time and space of a lightning flash can be reconstructed. In this paper, combining the synchronous data of electric filed change and VHF radiation, the whole processes of an example negative CG flash have been studied in detail. It is found that the preliminary breakdown event of the CG flash started from negative charge region and exhibited firstly a downward pregression and then an upward propagation. There were very intense and continuous radiations during stepped leaders which became much stronger when the first return stroke began. In contrast, there were less and only discrete radiations during dart leaders. Stepped leader and dart leader may transform to each other depending on the state of the ionization of the path. The progression speed of initial stepped leaders was about 105 ms?1, while that was about 4.1×106 and 6.0×106 ms?1 for dart leaders and dart-stepped leaders, respectively. M events produced hook-shaped field changes accompanied by active burst of radiations at their begin- nings. Followed these active radiation processes, M events appeared to contact finally into conducting main discharge channels. The mean progression speed of M events was about 7×107 ms?1, greater than that of the dart leaders and dart-ste
基金the fund of Tianshui Normal University (Grant No. TSA0604)
文摘The insertion reaction mechanism of CBr2 with CH3CH2O has been studied by using the B3LYP/6-311G(d) and CCSD(T)/6-311G(d) at single point. The geometries of reactions,transition state and products were completely optimized. All the transition state is verified by the vibrational analysis and the internal re-action coordinate (IRC) calculations. The results show that reaction (1) is the dominant reaction path,which proceeds via two steps: i) two reactants form an intermediate (IM1),which is an exothermal re-action of 8.62 kJ·mol?1 without energy barrier; ii) P1 is obtained via the TS1 and the H-shift,in which the energy barrier is 44.53 kJ·mol?1. The statistical thermodynamics and Eyring transition state theory with Wigner correction are used to study the thermodynamic and kinetic characters of this reaction in temperature range from 100 to 2200 K. The results show that the appropriate reaction temperature ranges from 200 to 1900 K at 1.0 atm,in which the reaction has a bigger spontaneity capability,equi-librium constant (K) and higher rate constant (k).
文摘Food systems have the potential to promote human health and enhance environmental sustainability;yet most African countries have decadal starvation and malnourishment due to unstable food systems lacking basic nutritional profiles. To understand the key questions of the African food production and food security crisis, it is important to evaluate the past and the present balance of food production and consumption quantitatively and comprehensively and identify resource constraints. This continental study analyzed water-land-food (WLF) nexus in recent decades (1997-2017) and accessed whether these resources cope with different population growth projections, dietary changes and agricultural water management. The findings revealed that in 2017, total production in Africa for the four major crops was 83.3, 34.1, 21.0 and 26.7 million tons for, respectively, maize, rice, sorghum and wheat. Together with the imported food, 38 countries experienced an increase in kcal by food supply, while 7 countries encountered a decrease. However, only 6 countries were above the 1500 kcal∙capita<sup>−1</sup>∙day<sup>−1</sup>—the global average food consumption from the four major crops. The study also found that in the context of food production and out of the total African population, 268 million (21.6%) have enough land and water, 310 million (25.0%) is without enough land and water, further 279 million (22.5%) have enough water but not enough land, and 381 million (30.8%) encounter enough land but not enough water. This is the first WLF nexus study for the African continent and emphasizes the need for efficient and rapid changes in the food systems of the African population, both in production and consumption, in order to provide sustainable and secure food systems, and ultimately approach the first three Sustainable Development Goals.
基金Supported by the Research Fund of Gangsu Province (Grant No. 0708-11)Tianshui Normal University (Grant No. TSA0604)
文摘The insertion reaction mechanism of CBr_2 with CH_3CH_O has been studied by using the B3LYP/6-31G(d) method. The geometries of reactions, transition state and products were completely optimized. All the energy of the species was obtained at the CCSD(T)/6-31G(d) level. All the transition state is verified by the vibrational analysis and the internal reaction coordinate (IRC) calculations. The results show that the propionaldehyde (~HP1) is the main product of CH_2 insertion with CH_3CH_O. The calculated results indicated that all the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CBr_2 not only can insert the C_α-H [reaction I(1)]) but also can react with C_β-H [reaction II(1)]. The statistical thermodynamics and Eyring transition state theory with Wigner correc- tion are used to study the thermodynamic and kinetic characters of I(1) and II(1) in temperature range from 100 to 2200 K. The results show that the appropriate reaction temperature rang is 250 to 1750 K and 250 to 1600 K at 1.0 atm for I(1) and II(1) respectively. The rate constant and equilibrium constant are distinct in the range from 250 to 1000 K so that I(1) more easily occurs, while the reactions are not selected in the temperature range of 1000-1600
文摘The intersystem crossing channels of gaseous 4H-pyran-4-thione were investigated using the CASSCF//TD-B3LYP methods and group theory. Using the effective one-electron spin-orbit Harniltonian, the strengths of spin-orbit coupling were estimated, which plays an essential role in the spin transitions between different spin states. Calculated results show that phosphorescence and non-radiative decay via intersystem crossing to the So state are concurrent processes occurring at the T1 state. A rapid depletion of the S1 state via intersystem crossing to the T1 state can be mediated by the T2 state, if spin relaxation is fast within the triplet levels. Our calculated results are in close agreement with experimental observations.
基金Supported by the National Natural Science Foundation of China (Grant No. 20335030)Foundation of Education Committee of Gansu Province (Grant No. 0708-11)
文摘The insertion and abstraction reaction mechanisms of singlet and triplet CCl2 with CH3MH (M=O, S) have been studied by using the DFT, NBO and AIM methods. The geometries of reactions, the transition state and products were completely optimized by B3LYP/6–311G(d, p). All the energy of the species was obtained at the CCSD(T)/6–311G(d, p) level. The calculated results indicated that the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CCl2 can not only trigger the insertion reaction with C-H and M-H in four pathways, by which the products P1 [CH3OCHCl2, reaction I(1)], P3[Cl2HCCH2OH, reaction I(2)], P5[CH3SCHCl2, reaction II(1)] and P7[Cl2HCCH2SH, reaction II(2)] are produced respectively, but also abstract M-H, resulting P4 [CH2O+CH2Cl2, reaction I(3)] and P8[CH2S+CH2Cl2, reaction II(3)]. In addition, the important geometries in domain pathways have been studied by AIM and NBO theories.
基金Tianshui Normal University for a grant from the "QingLan" Talent Engineering Fundsthe Key Project of Chinese Ministry of Education(211189) for support of this research
文摘The two-state mechanism of the reaction of Nb(NH2)3 with N2O on the singlet and triplet potential energy surfaces has been investigated at the B3LYP level.Crossing points between the potential energy surfaces have been located using different methods.Analysis of the strain model shows that the singlet state of the four-coordinate(N2O)Nb(NH2)3 complex with N2O bonded via terminal N atom coordination(12) is more stable in the initial stage of reaction,since the bending of the N2O fragment [Edef(N2O) = 86.1 kcal mol-1] results in an energy splitting of the doubly degenerate LUMO;the low-energy LUMO can now strongly couple with the occupied Nb-localized d orbitals,forming a back-bond and transferring charge(q = 0.82 e) from Nb(NH2)3 to the N2O ligand.Going from 32 to 12,the reacting system changes spin multiplicity near the MECP(minimal energy crossing point) region,which takes place with a spin crossing barrier of 9.6-10.0 kcal mol-1.Analysis of spin-orbit coupling(SOC) indicates that MECP will produce a significant SOC matrix element.The value of SOC is 111.52 cm-1,due to the electron shift between two perpendicular φ orbitals with the same rotation direction,and the magnitude of the spin-multi-plicity mixing increases in the small energy gap between high-and low-spin states,greatly enhancing the probability of intersystem crossing.The probabilities of single(P1 ISC) and double(P2 ISC) passes estimated at MECP(SOC = 111.52 cm-1) are approximately 1.17×10-2 and 2.32×10-2,respectively.
基金the Foundation of Education Committee of Gansu Province (Grant No. 0708-11) Foundation of Tianshui Normal University (Grant No. TSA0604)
文摘The insertion reaction mechanisms of siglet and striglet CCl2 with CH3CHO have been studied by using the DFT, NBO, CCSD(T) and AIM method. The geometries of reactions, transition state and products were completely optimized by B3LYP/6-31G(d). All the energy of the species was obtained at the CCSD(T)/6-31G(d,p) level. The calculated results indicated that all the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CCl2 can not only insert the Cα—H (reaction I) but also can react with Cβ—H (reaction Ⅱ). There are three main existing pathways and the products are P1 (CH3COHCCl2), P2 (CH2COHCHCl2) and P4[CHCl2CHCHOH] respectively. Reaction Ⅱ happens more easily according to the energy changes and the barrier in rate-controlling step. In addi-tion, the important geometries in domain pathways have been studied by AIM theory. And also, the en-ergy changes of H in the inserted C—H bond have been investigated.
基金supported by the National Basic Research Program of China(2010CB529601 and 2013CB945404)to B.L.Wuthe Fudan Young Teacher Funding to Y.An,the higher Education Research Project of Gansu Province(2015B-094)to X.LanShanghai Children’s Hospital Funding(2016YMS001)to X.Lan
文摘Myotonic dystrophy type 1 (DM1),or Steiner’s disease,is an autosomal dominant disorder caused by the expansion of unstable trinucleotide repeats (CTG) in the 3’ untranslated region of the myotonic dystrophy protein kinase gene (DMPK) (Brook et al.,1992;Mahadevan et al.,1992).The number of CTG repeats observed in normal individuals is in a range of 5-34,while the individuals with 35-49 CTG repeats are usually asymptomatic but at risk of
基金Supported by the Foundation of Education Committee of Gansu Province (No. 0708-11)foundation of Tianshui Normal University (No. TSA0604)
文摘The structures of 2,7＇-（ethylene）-bis-8-hydroxyquinoline and its derivatives were optimized at the ground states using ab initio HF and B3LYP methods. At the same time, the molecular structures of the first singlet excited state for 2,7＇-（ethylene）-bis-8-hydroxyqulnoline and its derivatives were optimized by CIS/6-31G（d）. The absorption and emission spectra based on the above structures were obtained by the time-dependent density functional theory （TD-DFT） by the B3LYP method with the 6-31G（d） basis set. The calculated results of luminescence originate from the electronic transition from the hydroxphenol ring of 8-hydroxyquinoline A to the pyridine ring of 8-hydroxyquinoline B. Their luminescence wave bands can be tuned by different substituents on the ligand of 8-hydroxyquinoline.
基金supported by the "QingLan" Talent Engineering Fundsthrough Tian Shui Normal Universitythe Key Project of the Chinese Ministry of Education (211189)
文摘We used density functional calculations to investigate the electronic origins of the magnetic properties of the high-spin ferric enzyme-substrate complex protocatechuate 3,4-dioxygenase(3,4-PCD).The calculated g-tensors show that ligand-to-metal charge transfer transitions are from the protocatechuate(PCA) and Tyr408 orbitals to the Fe d orbitals,which lead to x-and y-polarized transitions.These polarized transitions require a spin-orbit coupling(SOC) matrix element in the z-direction,Lz(z=z'),resulting in a g z value of 2.0158,significantly deviating from 2.0023.A large zero-field splitting parameter value of+1.147cm-1 is due to △S =-1 spin-orbit mixing with the quartet states for the sextet ground state,accounting for around 73% of the SOC contribution.The SOC matrix elements indicate that the high-spin d 5 system Fe(Ⅲ),3,4-PCD-PCA is a weak spin-crossover compound with an SOC of 31.56 cm-1.
基金the National Natural Science Foundation of China（No. 11264033） and the Science Research Foundation of Tianshui Normal University, China（No.TSA 1108）.
文摘Red long lasting phosphorescence（LLP） was firstly observed in LaA103：Eu3＋ phosphor synthesized by solid state method at 1773 K. It reveals that the Eu3＋ ions occupy the asymmetric La3＋ sites, resulting in the orange-red emission of Eu3＋. The LLP of the optimum LaA103：0.6%Eu3＋ sample can come to about 2000 s according to a definition of 0.32 mcd/m2. The LLP decay curve can not be fitted even by a function of three exponential terms, due to the complicated retrapping process of carriers. The result of a classical multi-peak fitting method on thermo- luminescence reveals that the excellent LLP performance of LaA103：Eu3＋ material originates from the rich distribu- tion of shallow traps（E=0.7875 eV）.
基金Project supported by the State Key Program of Basic Research of China（Grant No G2000077400）, the Major program of the National Natural Science Foundation of China （Grant Nos 10435080 and 105350101）, the National Natural Science Foundation of China （Grant Nos 10447006, 10575075, 10125521 and 10447113）, the Knowledge Innovation Program of the Chinese Academy of Sciences （Grant No KJCX2-SW-N02）, Jiangsu Planned Projects for Postdoctoral Research Funds and China Postdoctoral Science Foundation.
文摘An isospin-dependent quantum molecular dynamical model （IQMD） is developed, with the isospin degree of freedom in the momentum-dependent interaction（MDI） included in IQMD, to obtain an isospin- and momentum-dependent interaction （IMDI） in IQMD. We investigate the effect of IMDI on the isospin fractionation ratio and its dynamical mechanism in the intermediate energy heavy ion collisions. It is found that the IMDI induces the significant reductions in the isospin fractionation ratio for all of beam energies, impact parameters, neutron-proton ratios and mass number of colliding systems. However, the strong dependence of isospin fractionation ratio on the symmetrical potential is preserved, with the isospin degree of freedom included in the MDI, i.e. the isospin fractionation ratio is still a good probe for extracting the information about the equation of state of isospin asymmetrical nuclear matter.
基金Supported by the National Natural Science Foundation of China (30660044)
文摘Based on the concept of the pseudo amino acid composition （PseAAC）, protein structural classes are predicted by using an approach of increment of diversity combined with support vector machine （ID-SVM）, in which the dipeptide amino acid composition of proteins is used as the source of diversity. Jackknife test shows that total prediction accuracy is 96.6% and higher than that given by other approaches. Besides, the specificity （Sp） and the Matthew＇s correlation coefficient （MCC） are also calculated for each protein structural class, the Sp is more than 88%, the MCC is higher than 92%, and the higher MCC and Sp imply that it is credible to use ID-SVM model predicting protein structural class. The results indicate that： 1 the choice of the source of diversity is reasonable, 2 the predictive performance of IDSVM is excellent, and3 the amino acid sequences of proteins contain information of protein structural classes.
基金supported by ‘Qinglan’ Talent Engineering Funds and Key Subject of Inorganic Chemistry by Tianshui Normal University
文摘The excited-state intramolecular hydrogen abstraction reactions of butanal have been investigated using the CAS-MP2/6-311＋G^＊//CASSCF/6-31G^＊ methods. Calculated results show that the hydrogen transfer induced fluorescence quenching of the n,π^＊-excited state of covalent butanal with three paths： （1） The first path corresponds to direct S0-react reconstitution, which involves the first S1 decay by partial hydrogen atom transfer. （2） The second stepwise mechanism can be viewed as a full hydrogen atom transfer followed by a partial hydrogen atom back transfer, electron transfer （near S1/S0 or S0-TS） and finally a proton transfer to S0-react. （3） On the triplet surface, the surface crossing to the singlet state would be clearly much efficient at the T1/S0 region due to the large SOC value of 8.3 cm^-1. The S0-react decay route from T1/S0 was studied with an intrinsic reaction coordinate （IRC） calculation at the CASSCF level, resulting in the S0-React minimum.
基金Supported by the "QingLan" Talent Engineering Funds by Tianshui Normal University
文摘The potential energy surface crossings for 1,2-dithiete have been investigated using the complete active space self-consistent field (CASSCF) method and simple group theory. Using the full Pauli-Breit spin-orbit coupling (SOC) operator $$ (\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\frown}$}}{H} _{SO} ) $$ which consists of the one-electron $$ (\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\frown}$}}{H} _{SO1} ) $$ and two-electron $$ (\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\frown}$}}{H} _{SO2} ) $$ terms, we estimate the strengths of the SOC (198.37 cm?1 when symmetry is imposed, and 211.35 cm?1 with no symmetry constraints), which plays an essential role in the spin transitions between different spin states. The calculations show that the photolysis of 1,3-dithiol-2-one leads to the formation of trans-dithioglyoxal (trans-MinS0) as a primary product which subsequently gives a secondary product identified as thiolthioketene. Our calculated results are in close agreement with the experimental observations.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.2017YFA0402300,11464042,11564036,11774292,and 11464040)the Basic Scientific Research Foundation for Institution of Higher Learning of Gansu Province,China
文摘Electron-impact single ionization cross sections for W^q＋（q = 4–5） were calculated using the flexible atomic code（FAC） in the level-to-level distorted-wave method, considering the explicit branching ratio. The calculated cross sections are compared with the available theoretical and experiment results in detail. In the case of the contribution from the same channles as the available theoretical results, all of the calculated ionization cross sections agree with the experimental measured cross sections. But the present calculated results are larger than the experimental measurement when all channels contributions are included. Some important channels excitation autoionization（EA） contributions, such as the excitation to higher higher nl subshell from 4 f and 5[s,p], were not included into the available theoretical calculation. In general, the distorted-wave（DW） results are overestimated.
基金the Natural Science Education Foundation of Gansu Province (GrantNo. 07-08-12)
文摘The optimized geometries of the complexes between HnY (n=2, 3; Y=O, S, N) and LiNH2 have been calculated at the B3LYP/6-311++G** and MP2/6-311++G** levels. Three stable complexes were obtained. Frequency analysis showed that the enlarged 2N―4Li presents the abnormal blue shift in three complexes. The calculated binding energy with basis set super-position error (BSSE) and zero-point vibrational energy (ZPE) corrections of complex I―III is _58.65, _31.66 and _69.59 kJ·mol-1 (MP2), respectively. Natural bond orbital theory (NBO) analysis has been performed, and the results revealed that the H2O…LiNH2 (complex I) and H3N…LiNH2 (complex III) are formed with coexisting σ-s and n-s type lithium bond interactions, complexⅡis formed with π-s type lithium bond interaction between HnY (n=2,3; Y=O, N) and LiNH2, and H2S…LiNH2 (complex II) is formed with n-s type lithium bond interaction between H2S and LiNH2. Natural resonance theory (NRT) and atom in molecule (AIM) theory have also been studied to investigate the bond order and topological properties of the lithium bond structures.
基金the Natural Science Education Foundation of Gansu Province, China (Grant No. 021-22)
文摘The spin-forbidden reaction 1HNO(1A')+OH-→3NO-(3Σ-)+H2O has been extensively explored using various CASSCF active spaces with MP2 corrections in several basis sets. Natural bond orbital (NBO) analysis, together with the NBO energetic (deletion) analysis, indicates that the two isomers have nearly equal total energy and could compete with each other in the title reaction. More significantly, the singlet/triplet surface crossing regions have been examined and the spinorbit coupling (SOC) and energetics have been computed. The computational results indicate that the SOC is very large at the crossing point T1/S0 trans (ca.40.9 cm-1). Moreover, the T1/S0 trans has a low energy of 10.67 kcal/mol relative to that of trans-S0. Therefore, the surface crossing to the triplet state seems much more efficient at the T1/S0 trans region along the minimum energy path (MEP), However, The values of single (P1ISC) and double (P2ISC) passes estimated at T1/S0 trans show that the ISC occurs with a little probability.
基金Supported by the State Key Basic Research and Development Programme of China under Grant No G2000077400, the National Natural Science Foundation of China under Grant Nos 10435080, 105350101, 10447006 and 10575075, the Knowledge Innovation Project of Chinese Academy of Sciences under Grant No KJCX2-SW-N02.
文摘Based on both very obvious isospin effect of the neutron-proton number ratio of nucleon emissions （n/p）nud on symmetry potential and （n/p）nucl＇s sensitive dependence on symmetry potential in the nuclear reactions induced by halo-neutron projectiles, compared to the same mass stable projectile, probing symmetry potential is investigated within the isospin-dependent quantum molecular dynamics with isospin and momentum-dependent interactions for different symmetry potentials U;ym and U2^sym. It is found that the neutron-halo projectile induces very obvious increase of （n/p）nucl and strengthens the dependence of （n/p） l on the symmetry potential for all the beam energies and impact parameters, compared to the same mass stable projectile under the same incident channel condition. Therefore （n/p）nucl induced by the neutron-halo projectile is a more favourable probe than the normal neutron-rich and neutron-poor projectiles for extracting the symmetry potential.
