The isotope effects of XF （X=H, D） on the population transfer process via two-photon resonance excitation are investigated by solving the time-dependent SchrSdinger equation. The vibrational levels v=0 and 2 of the ...The isotope effects of XF （X=H, D） on the population transfer process via two-photon resonance excitation are investigated by solving the time-dependent SchrSdinger equation. The vibrational levels v=0 and 2 of the ground electronic state are taken to be the initial and target states, respectively, for the two molecular systems. The influences of the field peak amplitude and pulse duration on the population transfer process are discussed in detail. The pulse duration is required to be longer than 860 fs for the DF molecule to achieve a relatively high transfer probability （more than 80%）, while the one for the HF molecule is just required to be longer than 460 fs. Moreover, the intermediate level v=1 and the higher level v=3 may play more important roles in the two-photon resonance process for the DF molecule, compared to the roles in the process for the HF molecule.展开更多
Quasi-classical trajectory （QCT） calculations are employed to study the dynamic properties for H（D）＋OF reactions on the adiabatic potential energy surface （PES） of the 1^3A″ triplet state. Obvious differences ...Quasi-classical trajectory （QCT） calculations are employed to study the dynamic properties for H（D）＋OF reactions on the adiabatic potential energy surface （PES） of the 1^3A″ triplet state. Obvious differences between the reaction probabilities for J=0, integral cross sections for J≠0, branch ratios of the product and internuclear distances as well as product rotational alignments between the title reactions axe found. These differences are attributed mainly to the different reduced masses of the reactants and the different zero-point energies （ZPEs） of the transition state.展开更多
This paper is directed to study the isotope effects of some superconducting materials that have a strong coupling coefficient <i>λ</i> > 1.5, and focuses on new superconducting materials whose critical...This paper is directed to study the isotope effects of some superconducting materials that have a strong coupling coefficient <i>λ</i> > 1.5, and focuses on new superconducting materials whose critical temperature is close to room temperature, specifically LaH<sub>10</sub>-LaD<sub>10</sub> and H<sub>3</sub>S-D<sub>3</sub>S systems. The Eliashberg-McMillan (EM) model and the recent Gor’kov-Kresin (GK) model for evaluating the isotope effects coefficient α were examined for these systems. The predicted values of α as a function of pressure, as compared to experimental values led to inference that these two models, despite their importance and simplicity, cannot be considered complete. These models can be used to calculate isotope effect of most superconducting materials with strong coupling coefficients but with critical reliability. The significance of studying the isotope effect lies in the possibility of identifying the interatomic forces that control the properties of superconducting materials such as electrons-mediated phonons and Coulomb interactions.展开更多
We present a quantum dynamics study on the isotope effects of hydro-gen transfer isomerization in the formic acid dimer,and this is achieved by multidimensional dy-namics calculations with an efficient quantum mechani...We present a quantum dynamics study on the isotope effects of hydro-gen transfer isomerization in the formic acid dimer,and this is achieved by multidimensional dy-namics calculations with an efficient quantum mechanical theoretical scheme developed by our group,on a full-dimensional neural network ab initio potential energy surface.The ground-state and fundamental tun-neling splittings for four deuterium isotopologues of formic acid dimer are considered,and the calculated results are in very good general agreement with the avail-able experimental measurements.Strong isotope effects are revealed,the mode-specific funda-mental excitation effects on the tunneling rate are evidently influenced by the deuterium sub-stitution of H atom with the substitution on the OH bond being more effective than on the CH bond.Our studies are helpful for acquiring a better understanding of isotope effects in the double-hydrogen transfer processes.展开更多
To figure out the influence of isotope effect on product polarizations of the N(2D)+D2 reactive system and its isotope variants,quasi-classical trajectory(QCT)calculation was performed on Ho's potential energy sur...To figure out the influence of isotope effect on product polarizations of the N(2D)+D2 reactive system and its isotope variants,quasi-classical trajectory(QCT)calculation was performed on Ho's potential energy surface(PES)of 2A″state.Product polarizations such as product distributions of P(θr),P(φr)and P(θr,φr),as well as the generalized polarization-dependent differential cross sections(PDDCSs)were discussed and compared in detail among the four product channels of the title reactions.Both the intermolecular and intramolecular isotope effects were proved to be influential on product polarizations.展开更多
Theoretical studies of the diffusionalisotope effect in solids are still stuck in the 1960s and 1970s.With the development of high spatial resolution mass spectrometers,isotopic data of mineral grains are rapidly accu...Theoretical studies of the diffusionalisotope effect in solids are still stuck in the 1960s and 1970s.With the development of high spatial resolution mass spectrometers,isotopic data of mineral grains are rapidly accumulated.To dig up information from these data,molecularlevel theoretical models are urgently needed.Based on the microscopic definition of the diffusion coe fficient(D),a new theoretical framework for calculating the diffusional isotope effect(DIE(v))(intermsofD*/D)forvacancy-mediated impurity diffusion in solids is provided based on statistical mechanics formalism.The newly derived equation shows that theDIE(v)can be easily calculated as long as the vibration frequencies of isotope-substituted solids are obtained.The calculatedDIE(v)values of^(199)Au/^(195)Au and^(60)Co/^(57)Co during diffusion in Cu and Au metals are all within 1%of errors compared to the experimental data,which shows that this theoretical model is reasonable and precise.展开更多
Solvent and kinetic isotope effects in the reaction of oxidative deamination of L-alanine, catalyzed by L-alanine dehydrogenase, AIaDH, （EC 1.4.1.1） were determined using a non-competitive spectroscopic method. The ...Solvent and kinetic isotope effects in the reaction of oxidative deamination of L-alanine, catalyzed by L-alanine dehydrogenase, AIaDH, （EC 1.4.1.1） were determined using a non-competitive spectroscopic method. The progress of the reaction was monitored spectrophotometrically by measuring the increasing absorbance of the reduced form of NADH at 340 nm. L-alanine, stereospecifically labeled with deuterium was synthesized by enzymatic reductive amination of pyruvate in presence of [（4R）-2H]-NADH, which was obtained by deuterium transfer from deuteriated formic acid to NAD~ catalyzed by FDH （formate dehydrogenase） （EC 1.2.1.2）. [2-2H]-L-alanine, the product of enzymatic synthesis catalyzed by AIaDH, was obtained with 75% deuterium enrichment and values of isotopic effects were approximated to the values corresponding to 100% of deuterium incorporation. The enzyme AIaDH isolated from Bacillus subtilis shows pro-R stereospecificity, what indicates that hydrogen is exclusively transferred from pro-R position at C-4 of the nicotinamide ring of NADH to C-2 of pyruvate to form L-alanine. Some intrinsic mechanistic details of enzymatic oxidative deamination of L-alanine were discussed using determined numerical values of kinetic and solvent isotope effects on Vmax and Vmax,│KM展开更多
The planar oxygen isotope effect on Tc observed in copper oxide superconductors is remarkable in that it increases from near nil at optimal doping to a value twice that derived from BCS theory in the underdoped region...The planar oxygen isotope effect on Tc observed in copper oxide superconductors is remarkable in that it increases from near nil at optimal doping to a value twice that derived from BCS theory in the underdoped region. This behavior is quantitatively followed by a formula proposed by Kresin and Wolf in 1994 for polarons along the c-axis. Herein it is revisited in a more transparent way, and it is pointed out that the heterogeneity of pairing is relevant and has to be taken into account to explain the unusual planar isotope effects on Tc in underdoped cuprates.展开更多
We describe a computational approach,incorporating quantum mechanics into enzyme kinetics modeling with a special emphasis on computation of kinetic isotope effects.Two aspects are highlighted:(1) the potential energy...We describe a computational approach,incorporating quantum mechanics into enzyme kinetics modeling with a special emphasis on computation of kinetic isotope effects.Two aspects are highlighted:(1) the potential energy surface is represented by a combined quantum mechanical and molecular mechanical(QM/MM) potential in which the bond forming and breaking processes are modeled by electronic structure theory,and(2) a free energy perturbation method in path integral simulation is used to determine both kinetic isotope effects(KIEs).In this approach,which is called the PI-FEP/UM method,a light(heavy) isotope is mutated into a heavy(light) counterpart in centroid path integral simulations.The method is illustrated in the study of primary and secondary KIEs in two enzyme systems.In the case of nitroalkane oxidase,the enzymatic reaction exhibits enhanced quantum tunneling over that of the uncatalyzed process in water.In the dopa delarboxylase reaction,there appears to be distinguishable primary carbon-13 and secondary deuterium KIEs when the internal proton tautomerism is in the N-protonated or in the O-protonated positions.These examples show that the incorporation of quantum mechanical effects in enzyme kinetics modeling offers an opportunity to accurately and reliably model the mechanisms and free energies of enzymatic reactions.展开更多
Aqueous rechargeable Li/Na-ion batteries have shown promise for sustainable large-scale energy storage due to their safety,low cost,and environmental benignity.However,practical applications of aqueous batteries are p...Aqueous rechargeable Li/Na-ion batteries have shown promise for sustainable large-scale energy storage due to their safety,low cost,and environmental benignity.However,practical applications of aqueous batteries are plagued by water's intrinsically narrow electrochemical stability window,which results in low energy density.In this perspective article,we review several strategies to broaden the electrochemical window of aqueous electrolytes and realize high-energy aqueous batteries.Specifically,we highlight our recent findings on stabilizing aqueous Li storage electrochemistry using a deuterium dioxide-based aqueous electrolyte,which shows significant hydrogen isotope effects that trigger a wider electrochemical window and inhibit detrimental parasitic processes.展开更多
The shell effects on the particle evaporation prior to fission for three Pb isotopes, ^204Pb, ^208Pb, and ^212pb,as well as three Sn isotopes, ^128Sn, ^132Sn, and ^136Sn, are explored by a diffusion model. Calculation...The shell effects on the particle evaporation prior to fission for three Pb isotopes, ^204Pb, ^208Pb, and ^212pb,as well as three Sn isotopes, ^128Sn, ^132Sn, and ^136Sn, are explored by a diffusion model. Calculations show that the magnitude of shell effects in the emission of particles changes with the neutron-to-proton ratio N/Z of these fissioning nuclei, and this change is affected significantly by the spin and excitation energy of the system. It is shown that high angular momentum enhances the dependence of shell effects on the N/Z while high excitation energy weakens such a dependence.展开更多
The isotope effect on zonal flows(ZFs)and turbulence remains a key issue that is not completely solved in fusion plasmas.This paper presents the first experimental results of the ab initio prediction of causal relatio...The isotope effect on zonal flows(ZFs)and turbulence remains a key issue that is not completely solved in fusion plasmas.This paper presents the first experimental results of the ab initio prediction of causal relation between geodesic acoustic mode(GAM)and ambient turbulence at different isotope masses in the edge of HL-2A tokamak,where transfer entropy method based on information-theoretical approach is utilized as a quantified indicator of causality.Analysis shows that GAM is more pronounced in deuterium plasmas than in hydrogen,leading to a lower heat transport as well as more peaked profiles in the former situation.The causal impact of GAM on conductive heat flux component is stronger than on the convective component,which is resulted from a larger causal influence of zonal flow on temperature fluctuation.While a stronger GAM in deuterium plasmas has larger influence on all flux components,the relative change in temperature fluctuation and coefficient is more obvious when the ion mass varies.These findings not only offer an in-depth understanding of the real causality between zonal flow and turbulence in the present isotope experiments,but also provide useful ways for the physical understandings of transport and zonal flow dynamics in future deuterium-tritium fusion plasmas.展开更多
The two-body fragmentation dynamics of water isotopologues dications(H_(2)O^(2+),HOD^(2+),and D_(2)O^(2+))induced by200 eV electron impact is investigated.Two fragment ions and an emitted electron are detected in coin...The two-body fragmentation dynamics of water isotopologues dications(H_(2)O^(2+),HOD^(2+),and D_(2)O^(2+))induced by200 eV electron impact is investigated.Two fragment ions and an emitted electron are detected in coincidence,and their momentum vectors are determined by employing a reaction microscope.The complete kinematical information of four two-body fragmentation channels of H^(+)+OH+,H^(+)+OD^(+),D^(+)+OH^(+),and D^(+)+OD+is obtained.By analyzing the projectile energy-loss spectrum,the initial electronic state of the two-body dissociation channel is determined.Upon examining the kinetic energy release(KER)distributions of the four fragmentation channels,a clear difference is found between the two-body fragmentation channel H^(+)+OD+and the other three channels.The isotopic effect in the two-body fragmentation is demonstrated by the analysis of the relative yields of the two-body fragmentation channels originating from different isotopologues,which shows preferential cleavage of the O-H bond over the O-D bond.These results provide deeper insight into the microscopic dynamic mechanisms in water radiolysis.展开更多
The isotope effect on the stereodynamic properties in the title reaction is investigated by a quasi-classical trajectory （QCT） method on the 11At potential energy surface at a collision energy of 23.06 kcal/mol. The...The isotope effect on the stereodynamic properties in the title reaction is investigated by a quasi-classical trajectory （QCT） method on the 11At potential energy surface at a collision energy of 23.06 kcal/mol. The angular distributions P（φr ）, P（θr）, P（θr, φr）, and the polarization-dependent generalized differential cross sections are calculated, which demonstrate the observable influences on the rotational polarization of the product by the isotopic substitution of H with D.展开更多
The vector correlations in Ca＋HCl, Ca＋DCl, and Ca＋TCl reactions have been investigated by means of the quasi-classical trajectory calculations on PES constructed by means of multireference configuration interaction...The vector correlations in Ca＋HCl, Ca＋DCl, and Ca＋TCl reactions have been investigated by means of the quasi-classical trajectory calculations on PES constructed by means of multireference configuration interaction. The distributions of P（θr）, P（Фr） and the PDDCSs of （2π/σ）（dσ00/dωt）, （2π/σ）（dσ20/dωt）, （2π/σ）（dσ22＋/dωt）, （2π/σ）（dσ21-/dωt） have been calculated based on the surface. The remarkable isotopic effects in the reactions are observed, and the mechanism which may be ascribed to different mass factors is discussed.展开更多
Based on the two-dimensional kinetic ablation theory of the hydrogen pellet ablation developed by Kuteev [B.V. Kuteev, Nuclear Fusion, 35 (1995) 431], an algorithm of erosion speed and ablation rate calculations for L...Based on the two-dimensional kinetic ablation theory of the hydrogen pellet ablation developed by Kuteev [B.V. Kuteev, Nuclear Fusion, 35 (1995) 431], an algorithm of erosion speed and ablation rate calculations for Li, Be, and B impurity pellets in reactor-relevant plasma has been derived. Results show compatibilities of lithium pellet injection used in α-particle diagnostics are positive in comparison with other solid impurity pellets (e.g. Be, B and C). Using the 2-D Kuteev lentil model, including kinetic effects, we find that currently existing pellet injection techniques will not meet core-fueling requirements for ITER-FEAT. A pressure as high as 254 MPa must be applied to a pellet accelerator with a 200 cm-long single-stage pneumatic gun, in order to accelerate a pellet with a radius rpo = 0.5 cm to a velocity of vpo, 24 × 105 cm/s penetrating 100 cm into the ITER plasma core. Comparisons of pellet velocity- and radius-dependent penetration depth between the Neutral Gas Shielding and the Kuteev's models are made. However, we find that the isotopic effects can lead to a 33% lower pellet speed for solid DT, compared to an identical H2 pellet penetrating the same length in ITER-FEAT plasma, and our calculations show that HFS injection will much improve core fueling efficiency.展开更多
Theoretical studies of the dynamics of the reactions O（3p）＋H2/HD（ν=0, j=0）→OH＋H have been performed with quasi-classical trajectory method （QCT） on an ab initio potential surface for the lowest triplet elect...Theoretical studies of the dynamics of the reactions O（3p）＋H2/HD（ν=0, j=0）→OH＋H have been performed with quasi-classical trajectory method （QCT） on an ab initio potential surface for the lowest triplet electronic state of H2O（aA＂）. The QCT-calculated integral cross sections are in good agreement with the earlier time-dependent quantum mechanics results. The state-resolved rotational distributions reveal that the product OH rotational distributions for O＋HD have a preference for populating highly internally excited states compared with the O＋H2 reaction. Distributions of differential cross sections show that directions of scattering are strongly dependent on the choice of quantum state. The polarization dependent generalized differential cross-sections and the distributions were calculated and a pronounced isotopic effect is revealed. The calculated results indicate that the product polarization is very sensitive to the mass factor.展开更多
The impact of the mass isotope on plasma conflnement and transport properties has been investigated in Ohmically-heated hydrogen and deuterium plasmas in the HL-2 A tokamak.Experimental results show that under similar...The impact of the mass isotope on plasma conflnement and transport properties has been investigated in Ohmically-heated hydrogen and deuterium plasmas in the HL-2 A tokamak.Experimental results show that under similar discharge parameters the deuterium plasma has better conflnement and lower turbulent transport than the hydrogen one,and concomitantly,it is found that the magnitude of geodesic acoustic mode zonal flows,the tilting angle of the Reynolds stress tensor and the turbulence correlation lengths are all larger in the edge region of the deuterium plasma.The results provide direct experimental evidence on the importance of the nonlinear energy coupling between ambient turbulence and zonal flows for governing the isotope effects in fusion plasmas.展开更多
Several important equilibrium Si isotope fractionation factors among minerals,organic molecules and the H_4SiO_4 solution are complemented to facilitate the explanation of the distributions of Si isotopes in Earth'...Several important equilibrium Si isotope fractionation factors among minerals,organic molecules and the H_4SiO_4 solution are complemented to facilitate the explanation of the distributions of Si isotopes in Earth's surface environments.The results reveal that,in comparison to aqueous H_4SiO_4,heavy Si isotopes will be significantly enriched in secondary silicate minerals.On the contrary,quadra-coordinated organosilicon complexes are enriched in light silicon isotope relative to the solution.The extent of ^(28)Si-enrichment in hyper-coordinated organosilicon complexes was found to be the largest.In addition,the large kinetic isotope effect associated with the polymerization of monosilicic acid and dimer was calculated,and the results support the previous statement that highly ^(28)Sienrichment in the formation of amorphous quartz precursor contributes to the discrepancy between theoretical calculations and field observations.With the equilibrium Si isotope fractionation factors provided here,Si isotope distributions in many of Earth's surface systems can be explained.For example,the change of bulk soil δ^(30)Si can be predicted as a concave pattern with respect to the weathering degree,with the minimum value where allophane completely dissolves and the total amount of sesquioxides and poorly crystalline minerals reaches their maximum.When,under equilibrium conditions,the well-crystallized clays start to precipitate from the pore solutions,the bulk soil δ^(30)Si will increase again and reach a constant value.Similarly,the precipitation of crystalline smectite and the dissolution of poorly crystalline kaolinite may explain the δ^(30)Si variations in the ground water profile.The equilibrium Si isotope fractionations among the quadracoordinated organosilicon complexes and the H_4SiO_4solution may also shed light on the Si isotope distributions in the Si-accumulating plants.展开更多
The Rayleigh distillation isotope fractionation(RDIF) model is one of the most popular methods used in isotope geochemistry. Numerous isotope signals observed in geologic processes have been interpreted with this mode...The Rayleigh distillation isotope fractionation(RDIF) model is one of the most popular methods used in isotope geochemistry. Numerous isotope signals observed in geologic processes have been interpreted with this model. The RDIF model provides a simple mathematic solution for the reservoir-limited equilibrium isotope fractionation effect. Due to the reservoir effect, tremendously large isotope fractionations will always be produced if the reservoir is close to being depleted. However, in real situations, many prerequisites assumed in the RDIF model are often difficult to meet. For instance, it requires the relocated materials, which are removed step by step from one reservoir to another with different isotope compositions(i.e., with isotope fractionation), to be isotopically equilibrated with materials in the first reservoir simultaneously. This ‘‘quick equilibrium requirement’’ is indeed hard to meet if the first reservoir is sufficiently large or the removal step is fast. The whole first reservoir will often fail to re-attain equilibrium in time before the next removal starts.This problem led the RDIF model to fail to interpret isotope signals of many real situations. Here a diffusion-coupled and Rayleigh-like(i.e., reservoir-effect included) separation process is chosen to investigate this problem. We find that the final isotope fractionations are controlled by both the diffusion process and the reservoir effects via the disequilibrium separation process. Due to its complexity, we choose to use a numerical simulation method to solve this problem by developing specific computing codes for the working model.According to our simulation results, the classical RDIF model only governs isotope fractionations correctly at the final stages of separation when the reservoir scale(or thickness of the system) is reduced to the order of magnitude of the quotient of the diffusivity and the separation rate. The RDIF model fails in other situations and the isotope fractionations will be diffusion-limited when the reservoir is relatively large, or the separation rate is fast. We find that the effect of internal isotope distribution inhomogeneity caused by diffusion on the Rayleigh-like separation process is significant and cannot be ignored. This method can be applied to study numerous geologic and planetary processes involving diffusion-limited disequilibrium separation processes including partial melting,evaporation, mineral precipitation, core segregation, etc.Importantly, we find that far more information can be extracted through analyzing isotopic signals of such ‘‘disequilibrium’’processes than those of fully equilibrated ones, e.g., reservoir size and the separation rate. Such information may provide a key to correctly interpreting many isotope signals observed from geochemical and cosmochemical processes.展开更多
文摘The isotope effects of XF （X=H, D） on the population transfer process via two-photon resonance excitation are investigated by solving the time-dependent SchrSdinger equation. The vibrational levels v=0 and 2 of the ground electronic state are taken to be the initial and target states, respectively, for the two molecular systems. The influences of the field peak amplitude and pulse duration on the population transfer process are discussed in detail. The pulse duration is required to be longer than 860 fs for the DF molecule to achieve a relatively high transfer probability （more than 80%）, while the one for the HF molecule is just required to be longer than 460 fs. Moreover, the intermediate level v=1 and the higher level v=3 may play more important roles in the two-photon resonance process for the DF molecule, compared to the roles in the process for the HF molecule.
基金Project supported by the National Natural Science Foundation of China (Grant No.10574083)the Natural Science Foundation of Shandong Province of China (Grant No.Y2006A23)+1 种基金the National Basic Research Program of China (Grant No.2006CB806000)the Open Fund of the State Key Laboratory of High Field Laser Physics (Shanghai Institute of Optics and Fine Mechanics)
文摘Quasi-classical trajectory （QCT） calculations are employed to study the dynamic properties for H（D）＋OF reactions on the adiabatic potential energy surface （PES） of the 1^3A″ triplet state. Obvious differences between the reaction probabilities for J=0, integral cross sections for J≠0, branch ratios of the product and internuclear distances as well as product rotational alignments between the title reactions axe found. These differences are attributed mainly to the different reduced masses of the reactants and the different zero-point energies （ZPEs） of the transition state.
文摘This paper is directed to study the isotope effects of some superconducting materials that have a strong coupling coefficient <i>λ</i> > 1.5, and focuses on new superconducting materials whose critical temperature is close to room temperature, specifically LaH<sub>10</sub>-LaD<sub>10</sub> and H<sub>3</sub>S-D<sub>3</sub>S systems. The Eliashberg-McMillan (EM) model and the recent Gor’kov-Kresin (GK) model for evaluating the isotope effects coefficient α were examined for these systems. The predicted values of α as a function of pressure, as compared to experimental values led to inference that these two models, despite their importance and simplicity, cannot be considered complete. These models can be used to calculate isotope effect of most superconducting materials with strong coupling coefficients but with critical reliability. The significance of studying the isotope effect lies in the possibility of identifying the interatomic forces that control the properties of superconducting materials such as electrons-mediated phonons and Coulomb interactions.
基金supported by the National Natural Sci-ence Foundation of China(No.21973098 and No.22133003)the Beijing National Laboratory for Molecular SciencesJianwei Cao acknowledges the Youth Innovation Promotion Association CAS(No.2018045).
文摘We present a quantum dynamics study on the isotope effects of hydro-gen transfer isomerization in the formic acid dimer,and this is achieved by multidimensional dy-namics calculations with an efficient quantum mechanical theoretical scheme developed by our group,on a full-dimensional neural network ab initio potential energy surface.The ground-state and fundamental tun-neling splittings for four deuterium isotopologues of formic acid dimer are considered,and the calculated results are in very good general agreement with the avail-able experimental measurements.Strong isotope effects are revealed,the mode-specific funda-mental excitation effects on the tunneling rate are evidently influenced by the deuterium sub-stitution of H atom with the substitution on the OH bond being more effective than on the CH bond.Our studies are helpful for acquiring a better understanding of isotope effects in the double-hydrogen transfer processes.
基金Supported by the National Natural Science Foundation of China(No.10874096)
文摘To figure out the influence of isotope effect on product polarizations of the N(2D)+D2 reactive system and its isotope variants,quasi-classical trajectory(QCT)calculation was performed on Ho's potential energy surface(PES)of 2A″state.Product polarizations such as product distributions of P(θr),P(φr)and P(θr,φr),as well as the generalized polarization-dependent differential cross sections(PDDCSs)were discussed and compared in detail among the four product channels of the title reactions.Both the intermolecular and intramolecular isotope effects were proved to be influential on product polarizations.
基金suppor ted by Chinese NSF projects(42173021,41873024,42130114)the strategic priority research program(B)of CAS(XDB41000000)+1 种基金the preresearch Project on Civil Aerospace Technologies No.D020202 funded by the Chinese National Space Administration(CNSA)Guizhou Provincial 2021 Science and Technology Subsidies(No.GZ2021SIG)。
文摘Theoretical studies of the diffusionalisotope effect in solids are still stuck in the 1960s and 1970s.With the development of high spatial resolution mass spectrometers,isotopic data of mineral grains are rapidly accumulated.To dig up information from these data,molecularlevel theoretical models are urgently needed.Based on the microscopic definition of the diffusion coe fficient(D),a new theoretical framework for calculating the diffusional isotope effect(DIE(v))(intermsofD*/D)forvacancy-mediated impurity diffusion in solids is provided based on statistical mechanics formalism.The newly derived equation shows that theDIE(v)can be easily calculated as long as the vibration frequencies of isotope-substituted solids are obtained.The calculatedDIE(v)values of^(199)Au/^(195)Au and^(60)Co/^(57)Co during diffusion in Cu and Au metals are all within 1%of errors compared to the experimental data,which shows that this theoretical model is reasonable and precise.
文摘Solvent and kinetic isotope effects in the reaction of oxidative deamination of L-alanine, catalyzed by L-alanine dehydrogenase, AIaDH, （EC 1.4.1.1） were determined using a non-competitive spectroscopic method. The progress of the reaction was monitored spectrophotometrically by measuring the increasing absorbance of the reduced form of NADH at 340 nm. L-alanine, stereospecifically labeled with deuterium was synthesized by enzymatic reductive amination of pyruvate in presence of [（4R）-2H]-NADH, which was obtained by deuterium transfer from deuteriated formic acid to NAD~ catalyzed by FDH （formate dehydrogenase） （EC 1.2.1.2）. [2-2H]-L-alanine, the product of enzymatic synthesis catalyzed by AIaDH, was obtained with 75% deuterium enrichment and values of isotopic effects were approximated to the values corresponding to 100% of deuterium incorporation. The enzyme AIaDH isolated from Bacillus subtilis shows pro-R stereospecificity, what indicates that hydrogen is exclusively transferred from pro-R position at C-4 of the nicotinamide ring of NADH to C-2 of pyruvate to form L-alanine. Some intrinsic mechanistic details of enzymatic oxidative deamination of L-alanine were discussed using determined numerical values of kinetic and solvent isotope effects on Vmax and Vmax,│KM
文摘The planar oxygen isotope effect on Tc observed in copper oxide superconductors is remarkable in that it increases from near nil at optimal doping to a value twice that derived from BCS theory in the underdoped region. This behavior is quantitatively followed by a formula proposed by Kresin and Wolf in 1994 for polarons along the c-axis. Herein it is revisited in a more transparent way, and it is pointed out that the heterogeneity of pairing is relevant and has to be taken into account to explain the unusual planar isotope effects on Tc in underdoped cuprates.
基金supported in part by the National Institutes of Health (GM46736)
文摘We describe a computational approach,incorporating quantum mechanics into enzyme kinetics modeling with a special emphasis on computation of kinetic isotope effects.Two aspects are highlighted:(1) the potential energy surface is represented by a combined quantum mechanical and molecular mechanical(QM/MM) potential in which the bond forming and breaking processes are modeled by electronic structure theory,and(2) a free energy perturbation method in path integral simulation is used to determine both kinetic isotope effects(KIEs).In this approach,which is called the PI-FEP/UM method,a light(heavy) isotope is mutated into a heavy(light) counterpart in centroid path integral simulations.The method is illustrated in the study of primary and secondary KIEs in two enzyme systems.In the case of nitroalkane oxidase,the enzymatic reaction exhibits enhanced quantum tunneling over that of the uncatalyzed process in water.In the dopa delarboxylase reaction,there appears to be distinguishable primary carbon-13 and secondary deuterium KIEs when the internal proton tautomerism is in the N-protonated or in the O-protonated positions.These examples show that the incorporation of quantum mechanical effects in enzyme kinetics modeling offers an opportunity to accurately and reliably model the mechanisms and free energies of enzymatic reactions.
基金This work was supported by the National Key R&D Program of China(Grant No 2019YFA0705602)the Basic Science Center Project of National Natural Science Foundation of China(Grant No.51788104)+2 种基金the CAS Project for Young Scientists in Basic Research(Grant YSBR-058)the National Natural Science Foundation of China(Grant Nos.21975266,52172252 and 22209188)the Beijing Natural Science Foundation(Grant No.JQ22005).
文摘Aqueous rechargeable Li/Na-ion batteries have shown promise for sustainable large-scale energy storage due to their safety,low cost,and environmental benignity.However,practical applications of aqueous batteries are plagued by water's intrinsically narrow electrochemical stability window,which results in low energy density.In this perspective article,we review several strategies to broaden the electrochemical window of aqueous electrolytes and realize high-energy aqueous batteries.Specifically,we highlight our recent findings on stabilizing aqueous Li storage electrochemistry using a deuterium dioxide-based aqueous electrolyte,which shows significant hydrogen isotope effects that trigger a wider electrochemical window and inhibit detrimental parasitic processes.
基金国家自然科学基金，Teaching and Researching Foundation for the Excellent Teachers of Southeast University
文摘The shell effects on the particle evaporation prior to fission for three Pb isotopes, ^204Pb, ^208Pb, and ^212pb,as well as three Sn isotopes, ^128Sn, ^132Sn, and ^136Sn, are explored by a diffusion model. Calculations show that the magnitude of shell effects in the emission of particles changes with the neutron-to-proton ratio N/Z of these fissioning nuclei, and this change is affected significantly by the spin and excitation energy of the system. It is shown that high angular momentum enhances the dependence of shell effects on the N/Z while high excitation energy weakens such a dependence.
基金supported by the National MCF Energy Research and Development Program(Grant Nos.2024YFE03190001,2024YFE03190004,2022YFE03030001,and 2019YFE03030002)the National Natural Science Foundation of China(Grant Nos.12405257,12475215,and 12475219)+2 种基金the Natural Science Foundation of Sichuan Province,China(Grant Nos.2023NSFSC1289 and 2025ZNSFSC0066)the Nuclear Technology Research and Development Program(Grant No.HJSYF2024(02))the Innovation Program of Southwestern Institute of Physics(Grant No.202301XWCX001)。
文摘The isotope effect on zonal flows(ZFs)and turbulence remains a key issue that is not completely solved in fusion plasmas.This paper presents the first experimental results of the ab initio prediction of causal relation between geodesic acoustic mode(GAM)and ambient turbulence at different isotope masses in the edge of HL-2A tokamak,where transfer entropy method based on information-theoretical approach is utilized as a quantified indicator of causality.Analysis shows that GAM is more pronounced in deuterium plasmas than in hydrogen,leading to a lower heat transport as well as more peaked profiles in the former situation.The causal impact of GAM on conductive heat flux component is stronger than on the convective component,which is resulted from a larger causal influence of zonal flow on temperature fluctuation.While a stronger GAM in deuterium plasmas has larger influence on all flux components,the relative change in temperature fluctuation and coefficient is more obvious when the ion mass varies.These findings not only offer an in-depth understanding of the real causality between zonal flow and turbulence in the present isotope experiments,but also provide useful ways for the physical understandings of transport and zonal flow dynamics in future deuterium-tritium fusion plasmas.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.12325406,92261201,12404305,11974272)the Shannxi Province Natural Science Fundamental Research Project(Grant Nos.2023JC-XJ-03 and 23JSQ013)the Fundamental Research Funds for the Central Universities(Grant No.xzy022024040)。
文摘The two-body fragmentation dynamics of water isotopologues dications(H_(2)O^(2+),HOD^(2+),and D_(2)O^(2+))induced by200 eV electron impact is investigated.Two fragment ions and an emitted electron are detected in coincidence,and their momentum vectors are determined by employing a reaction microscope.The complete kinematical information of four two-body fragmentation channels of H^(+)+OH+,H^(+)+OD^(+),D^(+)+OH^(+),and D^(+)+OD+is obtained.By analyzing the projectile energy-loss spectrum,the initial electronic state of the two-body dissociation channel is determined.Upon examining the kinetic energy release(KER)distributions of the four fragmentation channels,a clear difference is found between the two-body fragmentation channel H^(+)+OD+and the other three channels.The isotopic effect in the two-body fragmentation is demonstrated by the analysis of the relative yields of the two-body fragmentation channels originating from different isotopologues,which shows preferential cleavage of the O-H bond over the O-D bond.These results provide deeper insight into the microscopic dynamic mechanisms in water radiolysis.
基金Project supported by the National Natural Science Foundation of China(Grant No.11004107)the Scientific Research Innovation Projects of Jiangsu Province for University Graduate Students,China(Grant No.CXZZ13 0201)
文摘The isotope effect on the stereodynamic properties in the title reaction is investigated by a quasi-classical trajectory （QCT） method on the 11At potential energy surface at a collision energy of 23.06 kcal/mol. The angular distributions P（φr ）, P（θr）, P（θr, φr）, and the polarization-dependent generalized differential cross sections are calculated, which demonstrate the observable influences on the rotational polarization of the product by the isotopic substitution of H with D.
基金This work was supported by the National Natural Science Foundation of China （No. 10974078, No. 11174117,No. 10674114, and No. 10874104） and the Research Fund for the Doctoral Program of Higher Education of China （No.20093704110001）.
文摘The vector correlations in Ca＋HCl, Ca＋DCl, and Ca＋TCl reactions have been investigated by means of the quasi-classical trajectory calculations on PES constructed by means of multireference configuration interaction. The distributions of P（θr）, P（Фr） and the PDDCSs of （2π/σ）（dσ00/dωt）, （2π/σ）（dσ20/dωt）, （2π/σ）（dσ22＋/dωt）, （2π/σ）（dσ21-/dωt） have been calculated based on the surface. The remarkable isotopic effects in the reactions are observed, and the mechanism which may be ascribed to different mass factors is discussed.
文摘Based on the two-dimensional kinetic ablation theory of the hydrogen pellet ablation developed by Kuteev [B.V. Kuteev, Nuclear Fusion, 35 (1995) 431], an algorithm of erosion speed and ablation rate calculations for Li, Be, and B impurity pellets in reactor-relevant plasma has been derived. Results show compatibilities of lithium pellet injection used in α-particle diagnostics are positive in comparison with other solid impurity pellets (e.g. Be, B and C). Using the 2-D Kuteev lentil model, including kinetic effects, we find that currently existing pellet injection techniques will not meet core-fueling requirements for ITER-FEAT. A pressure as high as 254 MPa must be applied to a pellet accelerator with a 200 cm-long single-stage pneumatic gun, in order to accelerate a pellet with a radius rpo = 0.5 cm to a velocity of vpo, 24 × 105 cm/s penetrating 100 cm into the ITER plasma core. Comparisons of pellet velocity- and radius-dependent penetration depth between the Neutral Gas Shielding and the Kuteev's models are made. However, we find that the isotopic effects can lead to a 33% lower pellet speed for solid DT, compared to an identical H2 pellet penetrating the same length in ITER-FEAT plasma, and our calculations show that HFS injection will much improve core fueling efficiency.
文摘Theoretical studies of the dynamics of the reactions O（3p）＋H2/HD（ν=0, j=0）→OH＋H have been performed with quasi-classical trajectory method （QCT） on an ab initio potential surface for the lowest triplet electronic state of H2O（aA＂）. The QCT-calculated integral cross sections are in good agreement with the earlier time-dependent quantum mechanics results. The state-resolved rotational distributions reveal that the product OH rotational distributions for O＋HD have a preference for populating highly internally excited states compared with the O＋H2 reaction. Distributions of differential cross sections show that directions of scattering are strongly dependent on the choice of quantum state. The polarization dependent generalized differential cross-sections and the distributions were calculated and a pronounced isotopic effect is revealed. The calculated results indicate that the product polarization is very sensitive to the mass factor.
基金partially supported by National Natural Science Foundation of China(Nos.11820101004,11875017,12075079 and 51821005)partially supported by the National Key R&D Program of China(No.2019YFE03020000)+2 种基金the National Magnetic Conflnement Fusion Science Program of China(No.2018YFE0310300)the Science and Technology Plan Project in Sichuan Province of China(No.2020YFSY0047)Sichuan International Science and Technology Innovation Cooperation Project(No.2021YFH0066)。
文摘The impact of the mass isotope on plasma conflnement and transport properties has been investigated in Ohmically-heated hydrogen and deuterium plasmas in the HL-2 A tokamak.Experimental results show that under similar discharge parameters the deuterium plasma has better conflnement and lower turbulent transport than the hydrogen one,and concomitantly,it is found that the magnitude of geodesic acoustic mode zonal flows,the tilting angle of the Reynolds stress tensor and the turbulence correlation lengths are all larger in the edge region of the deuterium plasma.The results provide direct experimental evidence on the importance of the nonlinear energy coupling between ambient turbulence and zonal flows for governing the isotope effects in fusion plasmas.
基金the funding support from the 973 Program(2014CB440904)CAS/SAFEA International Partnership Program for Creative Research Teams(Intraplate Mineralization Research Team,KZZD-EW-TZ-20)Chinese NSF projects(41173023,41225012,41490635,41530210)
文摘Several important equilibrium Si isotope fractionation factors among minerals,organic molecules and the H_4SiO_4 solution are complemented to facilitate the explanation of the distributions of Si isotopes in Earth's surface environments.The results reveal that,in comparison to aqueous H_4SiO_4,heavy Si isotopes will be significantly enriched in secondary silicate minerals.On the contrary,quadra-coordinated organosilicon complexes are enriched in light silicon isotope relative to the solution.The extent of ^(28)Si-enrichment in hyper-coordinated organosilicon complexes was found to be the largest.In addition,the large kinetic isotope effect associated with the polymerization of monosilicic acid and dimer was calculated,and the results support the previous statement that highly ^(28)Sienrichment in the formation of amorphous quartz precursor contributes to the discrepancy between theoretical calculations and field observations.With the equilibrium Si isotope fractionation factors provided here,Si isotope distributions in many of Earth's surface systems can be explained.For example,the change of bulk soil δ^(30)Si can be predicted as a concave pattern with respect to the weathering degree,with the minimum value where allophane completely dissolves and the total amount of sesquioxides and poorly crystalline minerals reaches their maximum.When,under equilibrium conditions,the well-crystallized clays start to precipitate from the pore solutions,the bulk soil δ^(30)Si will increase again and reach a constant value.Similarly,the precipitation of crystalline smectite and the dissolution of poorly crystalline kaolinite may explain the δ^(30)Si variations in the ground water profile.The equilibrium Si isotope fractionations among the quadracoordinated organosilicon complexes and the H_4SiO_4solution may also shed light on the Si isotope distributions in the Si-accumulating plants.
基金supported by the Strategic Priority Research Program (B) of CAS (No. XDB41000000)Pre-research Project on Civil Aerospace Technologies No. D020202 funded by the Chinese National Space Administration (CNSA) and Chinese NSF projects (No. 42130114)。
文摘The Rayleigh distillation isotope fractionation(RDIF) model is one of the most popular methods used in isotope geochemistry. Numerous isotope signals observed in geologic processes have been interpreted with this model. The RDIF model provides a simple mathematic solution for the reservoir-limited equilibrium isotope fractionation effect. Due to the reservoir effect, tremendously large isotope fractionations will always be produced if the reservoir is close to being depleted. However, in real situations, many prerequisites assumed in the RDIF model are often difficult to meet. For instance, it requires the relocated materials, which are removed step by step from one reservoir to another with different isotope compositions(i.e., with isotope fractionation), to be isotopically equilibrated with materials in the first reservoir simultaneously. This ‘‘quick equilibrium requirement’’ is indeed hard to meet if the first reservoir is sufficiently large or the removal step is fast. The whole first reservoir will often fail to re-attain equilibrium in time before the next removal starts.This problem led the RDIF model to fail to interpret isotope signals of many real situations. Here a diffusion-coupled and Rayleigh-like(i.e., reservoir-effect included) separation process is chosen to investigate this problem. We find that the final isotope fractionations are controlled by both the diffusion process and the reservoir effects via the disequilibrium separation process. Due to its complexity, we choose to use a numerical simulation method to solve this problem by developing specific computing codes for the working model.According to our simulation results, the classical RDIF model only governs isotope fractionations correctly at the final stages of separation when the reservoir scale(or thickness of the system) is reduced to the order of magnitude of the quotient of the diffusivity and the separation rate. The RDIF model fails in other situations and the isotope fractionations will be diffusion-limited when the reservoir is relatively large, or the separation rate is fast. We find that the effect of internal isotope distribution inhomogeneity caused by diffusion on the Rayleigh-like separation process is significant and cannot be ignored. This method can be applied to study numerous geologic and planetary processes involving diffusion-limited disequilibrium separation processes including partial melting,evaporation, mineral precipitation, core segregation, etc.Importantly, we find that far more information can be extracted through analyzing isotopic signals of such ‘‘disequilibrium’’processes than those of fully equilibrated ones, e.g., reservoir size and the separation rate. Such information may provide a key to correctly interpreting many isotope signals observed from geochemical and cosmochemical processes.
