Charge-neutral method(CNM)is extensively used in investigating the performance of catalysts and the mechanism of N_(2)electrochemical reduction(NRR).However,disparities remain between the predicted potentials required...Charge-neutral method(CNM)is extensively used in investigating the performance of catalysts and the mechanism of N_(2)electrochemical reduction(NRR).However,disparities remain between the predicted potentials required for NRR by the CNM methods and those observed experimentally,as the CNM method neglects the charge effect from the electrode potential.To address this issue,we employed the constant electrode potential(CEP)method to screen atomic transition metal-N-graphene(M_(1)/N-graphene)as NRR electrocatalysts and systematically investigated the underlying catalytic mechanism.Among eight types of M_(1)/N-graphene(M_(1)=Mo,W,Fe,Re,Ni,Co,V,Cr),W_(1)/N-graphene emerges as the most promising NRR electrocatalyst with a limiting potential as low as−0.13 V.Additionally,the W_(1)/N-graphene system consistently maintains a positive charge during the reaction due to its Fermi level being higher than that of the electrode.These results better match with the actual circumstances compared to those calculated by conventional CNM method.Thus,our work not only develops a promising electrocatalyst for NRR but also deepens the understanding of the intrinsic electrocatalytic mechanism.展开更多
Electric double layer(EDL)is a critical topic in electrochemistry and largely determines the working performance of lithium batteries.However,atomic insights into the EDL structures on heteroatom-modified graphite ano...Electric double layer(EDL)is a critical topic in electrochemistry and largely determines the working performance of lithium batteries.However,atomic insights into the EDL structures on heteroatom-modified graphite anodes and EDL evolution with electrode potential are very lacking.Herein,a constant-potential molecular dynamics(CPMD)method is proposed to probe the EDL structure under working conditions,taking N-doped graphite electrodes and carbonate electrolytes as an example.An interface model was developed,incorporating the electrode potential and atom electronegativities.As a result,an insightful atomic scenario for the EDL structure under varied electrode potentials has been established,which unveils the important role of doping sites in regulating both the EDL structures and the following electrochemical reactions at the atomic level.Specifically,the negatively charged N atoms repel the anions and adsorb Li~+at high and low potentials,respectively.Such preferential adsorption suggests that Ndoped graphite can promote Li~+desolvation and regulate the location of Li~+deposition.This CPMD method not only unveils the mysterious function of N-doping from the viewpoint of EDL at the atomic level but also applies to probe the interfacial structure on other complicated electrodes.展开更多
Focusing on revealing the origin of high ammonia yield rate on Cu via nitrate reduction(NO3RR),we herein applied constant potential method via grand-canonical density functional theory(GC-DFT)with implicit continuum s...Focusing on revealing the origin of high ammonia yield rate on Cu via nitrate reduction(NO3RR),we herein applied constant potential method via grand-canonical density functional theory(GC-DFT)with implicit continuum solvation model to predict the reaction energetics of NO3RR on pure copper surface in alkaline media.The potential-dependent mechanism on the most prevailing Cu(111)and the minor(100)and(110)facets were established,in consideration of NO_(2)_(−),NO,NH_(3),NH_(2)OH,N_(2),and N_(2)O as the main products.The computational results show that the major Cu(111)is the ideal surface to produce ammonia with the highest onset potential at 0.06 V(until−0.37 V)and the highest optimal potential at−0.31 V for ammonia production without kinetic obstacles in activation energies at critical steps.For other minor facets,the secondary Cu(100)shows activity to ammonia from−0.03 to−0.54 V with the ideal potential at−0.50 V,which requires larger overpotential to overcome kinetic activation energy barriers.The least Cu(110)possesses the longest potential range for ammonia yield from−0.27 to−1.12 V due to the higher adsorption coverage of nitrate,but also with higher tendency to generate di-nitrogen species.Experimental evaluations on commercial Cu/C electrocatalyst validated the accuracy of our proposed mechanism.The most influential(111)surface with highest percentage in electrocatalyst determined the trend of ammonia production.In specific,the onset potential of ammonia production at 0.1 V and emergence of yield rate peak at−0.3 V in experiments precisely located in the predicted potentials on Cu(111).Four critical factors for the high ammonia yield and selectivity on Cu surface via NO3RR are summarized,including high NO3RR activity towards ammonia on the dominant Cu(111)facet,more possibilities to produce ammonia along different pathways on each facet,excellent ability for HER inhibition and suitable surface size to suppress di-nitrogen species formation at high nitrate coverage.Overall,our work provides comprehensive potential-dependent insights into the reaction details of NO3RR to ammonia,which can serve as references for the future development of NO3RR electrocatalysts,achieving higher activity and selectivity by maximizing these characteristics of copper-based materials.展开更多
Electrochemical nitrate reduction(eNO_(3)RR)and nitric oxide reduction(eNORR)to ammonia have emerged as promising and sustainable alternatives to the traditional Haber-Bosch method for ammonia production,particularly ...Electrochemical nitrate reduction(eNO_(3)RR)and nitric oxide reduction(eNORR)to ammonia have emerged as promising and sustainable alternatives to the traditional Haber-Bosch method for ammonia production,particularly within the recently proposed reverse artificial nitrogen cycle route:N_(2)→NO_(x)→NH_(3).Notably,experimental studies have demonstrated that eNORR exhibits superior performance over eNO_(3)RR on Cu6Sn5 catalysts.However,the fundamental mechanisms underlying this difference remain poorly understood.Herein,we performed systematic theoretical calculations to explore the reaction pathways,electronic structure effects,and potential-dependent Faradic efficiency associated with ammonia production via these two distinct electrochemical pathways(eNORR and eNO_(3)RR)on Cu6Sn5.By implementing an advanced‘adaptive electric field controlled constant potential(EFC-CP)’methodology combined with microkinetic modeling,we successfully reproduced the experimental observations and identified the key factors affecting ammonia production in both reaction pathways.It was found that eNORR outperforms eNO_(3)RR because it circumvents the ^(*)NO_(2) dissociation and ^(*)NO_(2) desorption steps,leading to distinct surface coverage of key intermediates between the two pathways.Furthermore,the reaction rates were found to exhibit a pronounced dependence on the surface coverage of ^(*)NO in eNORR and ^(*)NO_(2) in eNO_(3)RR.Specifically,the facile desorption of ^(*)NO_(2) on the Cu6Sn5 surface in eNO_(3)RR limits the attainable surface coverage of ^(*)NO,thereby impeding its performance.In contrast,the eNORR can maintain a high surface coverage of adsorbed ^(*)NO species,contributing to its enhanced ammonia production performance.These fundamental insights provide valuable guidance for the rational design of catalysts and the optimization of reaction routes,facilitating the development of more efficient,sustainable,and scalable techniques for ammonia production.展开更多
Metal-nitrogen-carbon catalysts(M-N-C)with single-atom active site are highly efficient catalysts for electrochemical CO_(2)reduction reactions(CO_(2)RR).Abundant M-N-C catalysts have been developed,and the coordinate...Metal-nitrogen-carbon catalysts(M-N-C)with single-atom active site are highly efficient catalysts for electrochemical CO_(2)reduction reactions(CO_(2)RR).Abundant M-N-C catalysts have been developed,and the coordinated adjacent nitrogen atoms as first-shell environment have been the focus of research of activity-tuning.However,the effect of second-shell carbon environment around the metal-nitrogen moiety is still unclear.Moreover,it is confusing for the discrepancy between the experimental onset potential of around–0.2 V(vs.reversible hydrogen electrode,RHE,unless otherwise noted)and theoretical predictions of–0.5 V or higher by the widely-used computational hydrogen electrode(CHE)model.Herein,using the explicit solvent model and constant potential method(CPM),the electrochemical interface on Fe-N-C is simulated for CO_(2)RR.It reveals that the*COOH formation is facilitated in water solvent environment,while the CO_(2)adsorption is potential-dependent.The predicted onset potential of around–0.2 V on Fe-N-C is consistent with experimental results.The sp2 non-hexatomic defects introduced into second-shell carbon environment are significantly influential for the CO_(2)RR.The double five-seven ring(5577)defect is the most active,compared to that with triple five-seven ring(55577)or five-eight ring(58)defects.The highly flexible structure and altered density of states of Fe site induced by 5775 defects are key to CO_(2)adsorption.This study provides new insights into the role of second-shell carbon environment for effective CO_(2)RR,and underlines the importance of CPM and solvent environment in accurate simulation for electrochemical interface.展开更多
Elucidation the relationship between electrode potentials and heterogeneous electrocatalytic reactions has attracted widespread attention.Herein we construct the well-defined Mn single-atom(MnSA)catalyst with four N-c...Elucidation the relationship between electrode potentials and heterogeneous electrocatalytic reactions has attracted widespread attention.Herein we construct the well-defined Mn single-atom(MnSA)catalyst with four N-coordination through a simple thermal pyrolysis preparation method to investigate the electrode potential micro-environments effect on carbon dioxide reduction reactions(CO_(2)RR)and oxygen reduction reactions(ORR).MnSA catalysts generate higher CO production Faradaic efficiency of exceeding 90%at-0.9 V for CO_(2)RR and higher H_(2)O_(2)yield from 0.1 to 0.6 V with excellent ORR activity.Density functional theory(DFT)calculations based on constant potential models were performed to study the mechanism of MnSA on CO_(2)RR.The thermodynamic energy barrier of CO_(2)RR is lowest at-0.9 V vs.reversible hydrogen electrode(RHE).Similar DFT calculations on the H_(2)O_(2)yield of ORR showed that the H_(2)O_(2)yield at 0.2 V was higher.This study provides a reasonable explanation for the role of electrode potential micro-environments.展开更多
This article studied the europium electroreduction kinetic properties in the Sm-Eu-Gd chloride system by using an electrolytic cell with membrane and constant potential method.The results indicate that within the para...This article studied the europium electroreduction kinetic properties in the Sm-Eu-Gd chloride system by using an electrolytic cell with membrane and constant potential method.The results indicate that within the parameter range of this study the europium reduction speed up with the increase of the system's temperature,the stirring intensity,feed concentration and the cathod area,and with the decrease of the cathodic potential.As the feed acidity increases,the reduction rate decreases.An empirical formula for europium's electroreduction kinetics in this experimental condition is also given.展开更多
Porous silicon(PS) was found to emit visible luminescence at room temperature. This phenomenon implies a potential application of silicon in optoelectronics. The luminescence of PS can be improved by doping with rare ...Porous silicon(PS) was found to emit visible luminescence at room temperature. This phenomenon implies a potential application of silicon in optoelectronics. The luminescence of PS can be improved by doping with rare earth elements. A new electrochemical doping approach, constant potential electrolysis, and a new electrolyte system for doping of porous silicon with holmium were reported. By this approach and system, the doping products were well controlled, and Ho doped PS(HDPS) was found to emit much intenser visible photoluminescence with blue shift in wavelength and higher luminescence stability at room temperature than that for corresponding PS wafer. The effects of various kinds of holmium compounds, solvents, applied voltage, concentration of holmium nitrate and doping time on photoluminescence of HDPS were investigated, and the optimum doping conditions were fixed. The luminescence mechanisms for PS and HDPS were discussed.展开更多
Cd F molecule, which plays an important role in a great variety of research fields, has long been subject to numerous researchers. Due to the unstable nature and heavy atom Cd containing in the Cd F molecule, electron...Cd F molecule, which plays an important role in a great variety of research fields, has long been subject to numerous researchers. Due to the unstable nature and heavy atom Cd containing in the Cd F molecule, electronic states of the molecule have not been well studied. In this paper, high accurate ab initio calculations on the Cd F molecule have been performed at the multi-reference configuration interaction level including Davidson correction（MRCI ＋ Q）. Adiabatic potential energy curves（PECs） of the 14 low-lying Λ–S states correlating with the two lowest dissociation limits Cd（~1S_g） ＋ F（~2P_u） and Cd（~3P_u） ＋ F（~2P_u） have been constructed. For the bound Λ–S and ？ states, the dominant electronic configurations and spectroscopic constants are obtained,and the calculated spectroscopic constants of bound states are consistent with previous experimental results. The dipole moments（DMs） of 2 Σ＋ and 2Π are determined, and the spin–orbit（SO） matrix elements between each pair of X2Σ＋, 22Σ＋, 12Π, and 22Π are obtained. The results indicate that the sudden changes of DMs and SO matrix elements arise from the variation of the electronic configurations around the avoided crossing region. Moreover,the Franck–Condon factors（FCFs）, the transition dipole moments（TDMs）, and radiative lifetimes of low-lying states-the ground state X2Σ＋are determined. Finally, the transitional properties of 22Π–X2Σ＋and 22Σ＋–X2Σ＋are studied. Based on our computed spectroscopic information of Cd F, the feasibility and challenge for laser cooling of Cd F molecule are discussed.展开更多
Standard electrode potentials E° of Ag-AgC1 electrode in molality scale and acidity constants of glyeine pK_1° at constant molality of NaCl (1.0 mol·kg^(-1)) in 5 and 15 mass% glucose-water mixed solven...Standard electrode potentials E° of Ag-AgC1 electrode in molality scale and acidity constants of glyeine pK_1° at constant molality of NaCl (1.0 mol·kg^(-1)) in 5 and 15 mass% glucose-water mixed solvents over a range of temperatures from 278.15 to 318.15 K were determined from precise emf measurements.The dependence of acidity constant on temperature is given as a function of the thermodynamic temperature T by an empirical equation, pK_1° =A_1(K/T)-A_2+A_3(T/K).The corresponding thermodynamic quantities of the first dissociation process of glycine were calculated and the effects of both tho solvent and the salt on them were also discussed.展开更多
基金Natural Science Foundation of Guangdong Province(No.2024A1515011094(C.Q Sun))National Natural Science Foundation of China(Nos.12304243(H.X.Fang),12150100(B.Wang))is gratefully acknowledged。
文摘Charge-neutral method(CNM)is extensively used in investigating the performance of catalysts and the mechanism of N_(2)electrochemical reduction(NRR).However,disparities remain between the predicted potentials required for NRR by the CNM methods and those observed experimentally,as the CNM method neglects the charge effect from the electrode potential.To address this issue,we employed the constant electrode potential(CEP)method to screen atomic transition metal-N-graphene(M_(1)/N-graphene)as NRR electrocatalysts and systematically investigated the underlying catalytic mechanism.Among eight types of M_(1)/N-graphene(M_(1)=Mo,W,Fe,Re,Ni,Co,V,Cr),W_(1)/N-graphene emerges as the most promising NRR electrocatalyst with a limiting potential as low as−0.13 V.Additionally,the W_(1)/N-graphene system consistently maintains a positive charge during the reaction due to its Fermi level being higher than that of the electrode.These results better match with the actual circumstances compared to those calculated by conventional CNM method.Thus,our work not only develops a promising electrocatalyst for NRR but also deepens the understanding of the intrinsic electrocatalytic mechanism.
基金supported by the National Natural Science Foundation of China(T2322015,22209094,22209093,and 22109086)the National Key Research and Development Program(2021YFB2500300)+2 种基金the Open Research Fund of CNMGE Platform&NSCC-TJOrdos-Tsinghua Innovative&Collaborative Research Program in Carbon Neutralitythe Tsinghua University Initiative Scientific Research Program。
文摘Electric double layer(EDL)is a critical topic in electrochemistry and largely determines the working performance of lithium batteries.However,atomic insights into the EDL structures on heteroatom-modified graphite anodes and EDL evolution with electrode potential are very lacking.Herein,a constant-potential molecular dynamics(CPMD)method is proposed to probe the EDL structure under working conditions,taking N-doped graphite electrodes and carbonate electrolytes as an example.An interface model was developed,incorporating the electrode potential and atom electronegativities.As a result,an insightful atomic scenario for the EDL structure under varied electrode potentials has been established,which unveils the important role of doping sites in regulating both the EDL structures and the following electrochemical reactions at the atomic level.Specifically,the negatively charged N atoms repel the anions and adsorb Li~+at high and low potentials,respectively.Such preferential adsorption suggests that Ndoped graphite can promote Li~+desolvation and regulate the location of Li~+deposition.This CPMD method not only unveils the mysterious function of N-doping from the viewpoint of EDL at the atomic level but also applies to probe the interfacial structure on other complicated electrodes.
基金supported by is supported by the Shanghai Municipal Science and Technology Major Projectthe support from Shanghai Super Postdoctoral Incentive Program
文摘Focusing on revealing the origin of high ammonia yield rate on Cu via nitrate reduction(NO3RR),we herein applied constant potential method via grand-canonical density functional theory(GC-DFT)with implicit continuum solvation model to predict the reaction energetics of NO3RR on pure copper surface in alkaline media.The potential-dependent mechanism on the most prevailing Cu(111)and the minor(100)and(110)facets were established,in consideration of NO_(2)_(−),NO,NH_(3),NH_(2)OH,N_(2),and N_(2)O as the main products.The computational results show that the major Cu(111)is the ideal surface to produce ammonia with the highest onset potential at 0.06 V(until−0.37 V)and the highest optimal potential at−0.31 V for ammonia production without kinetic obstacles in activation energies at critical steps.For other minor facets,the secondary Cu(100)shows activity to ammonia from−0.03 to−0.54 V with the ideal potential at−0.50 V,which requires larger overpotential to overcome kinetic activation energy barriers.The least Cu(110)possesses the longest potential range for ammonia yield from−0.27 to−1.12 V due to the higher adsorption coverage of nitrate,but also with higher tendency to generate di-nitrogen species.Experimental evaluations on commercial Cu/C electrocatalyst validated the accuracy of our proposed mechanism.The most influential(111)surface with highest percentage in electrocatalyst determined the trend of ammonia production.In specific,the onset potential of ammonia production at 0.1 V and emergence of yield rate peak at−0.3 V in experiments precisely located in the predicted potentials on Cu(111).Four critical factors for the high ammonia yield and selectivity on Cu surface via NO3RR are summarized,including high NO3RR activity towards ammonia on the dominant Cu(111)facet,more possibilities to produce ammonia along different pathways on each facet,excellent ability for HER inhibition and suitable surface size to suppress di-nitrogen species formation at high nitrate coverage.Overall,our work provides comprehensive potential-dependent insights into the reaction details of NO3RR to ammonia,which can serve as references for the future development of NO3RR electrocatalysts,achieving higher activity and selectivity by maximizing these characteristics of copper-based materials.
文摘Electrochemical nitrate reduction(eNO_(3)RR)and nitric oxide reduction(eNORR)to ammonia have emerged as promising and sustainable alternatives to the traditional Haber-Bosch method for ammonia production,particularly within the recently proposed reverse artificial nitrogen cycle route:N_(2)→NO_(x)→NH_(3).Notably,experimental studies have demonstrated that eNORR exhibits superior performance over eNO_(3)RR on Cu6Sn5 catalysts.However,the fundamental mechanisms underlying this difference remain poorly understood.Herein,we performed systematic theoretical calculations to explore the reaction pathways,electronic structure effects,and potential-dependent Faradic efficiency associated with ammonia production via these two distinct electrochemical pathways(eNORR and eNO_(3)RR)on Cu6Sn5.By implementing an advanced‘adaptive electric field controlled constant potential(EFC-CP)’methodology combined with microkinetic modeling,we successfully reproduced the experimental observations and identified the key factors affecting ammonia production in both reaction pathways.It was found that eNORR outperforms eNO_(3)RR because it circumvents the ^(*)NO_(2) dissociation and ^(*)NO_(2) desorption steps,leading to distinct surface coverage of key intermediates between the two pathways.Furthermore,the reaction rates were found to exhibit a pronounced dependence on the surface coverage of ^(*)NO in eNORR and ^(*)NO_(2) in eNO_(3)RR.Specifically,the facile desorption of ^(*)NO_(2) on the Cu6Sn5 surface in eNO_(3)RR limits the attainable surface coverage of ^(*)NO,thereby impeding its performance.In contrast,the eNORR can maintain a high surface coverage of adsorbed ^(*)NO species,contributing to its enhanced ammonia production performance.These fundamental insights provide valuable guidance for the rational design of catalysts and the optimization of reaction routes,facilitating the development of more efficient,sustainable,and scalable techniques for ammonia production.
文摘Metal-nitrogen-carbon catalysts(M-N-C)with single-atom active site are highly efficient catalysts for electrochemical CO_(2)reduction reactions(CO_(2)RR).Abundant M-N-C catalysts have been developed,and the coordinated adjacent nitrogen atoms as first-shell environment have been the focus of research of activity-tuning.However,the effect of second-shell carbon environment around the metal-nitrogen moiety is still unclear.Moreover,it is confusing for the discrepancy between the experimental onset potential of around–0.2 V(vs.reversible hydrogen electrode,RHE,unless otherwise noted)and theoretical predictions of–0.5 V or higher by the widely-used computational hydrogen electrode(CHE)model.Herein,using the explicit solvent model and constant potential method(CPM),the electrochemical interface on Fe-N-C is simulated for CO_(2)RR.It reveals that the*COOH formation is facilitated in water solvent environment,while the CO_(2)adsorption is potential-dependent.The predicted onset potential of around–0.2 V on Fe-N-C is consistent with experimental results.The sp2 non-hexatomic defects introduced into second-shell carbon environment are significantly influential for the CO_(2)RR.The double five-seven ring(5577)defect is the most active,compared to that with triple five-seven ring(55577)or five-eight ring(58)defects.The highly flexible structure and altered density of states of Fe site induced by 5775 defects are key to CO_(2)adsorption.This study provides new insights into the role of second-shell carbon environment for effective CO_(2)RR,and underlines the importance of CPM and solvent environment in accurate simulation for electrochemical interface.
基金supported by the National Natural Science Foundation of China(Nos.52073214 and 22075211)Guangxi Natural Science Fund for Distinguished Young Scholars(No.2024GXNSFFA010008).
文摘Elucidation the relationship between electrode potentials and heterogeneous electrocatalytic reactions has attracted widespread attention.Herein we construct the well-defined Mn single-atom(MnSA)catalyst with four N-coordination through a simple thermal pyrolysis preparation method to investigate the electrode potential micro-environments effect on carbon dioxide reduction reactions(CO_(2)RR)and oxygen reduction reactions(ORR).MnSA catalysts generate higher CO production Faradaic efficiency of exceeding 90%at-0.9 V for CO_(2)RR and higher H_(2)O_(2)yield from 0.1 to 0.6 V with excellent ORR activity.Density functional theory(DFT)calculations based on constant potential models were performed to study the mechanism of MnSA on CO_(2)RR.The thermodynamic energy barrier of CO_(2)RR is lowest at-0.9 V vs.reversible hydrogen electrode(RHE).Similar DFT calculations on the H_(2)O_(2)yield of ORR showed that the H_(2)O_(2)yield at 0.2 V was higher.This study provides a reasonable explanation for the role of electrode potential micro-environments.
基金The project was supported by the National Natural Science Foundation of China
文摘This article studied the europium electroreduction kinetic properties in the Sm-Eu-Gd chloride system by using an electrolytic cell with membrane and constant potential method.The results indicate that within the parameter range of this study the europium reduction speed up with the increase of the system's temperature,the stirring intensity,feed concentration and the cathod area,and with the decrease of the cathodic potential.As the feed acidity increases,the reduction rate decreases.An empirical formula for europium's electroreduction kinetics in this experimental condition is also given.
文摘Porous silicon(PS) was found to emit visible luminescence at room temperature. This phenomenon implies a potential application of silicon in optoelectronics. The luminescence of PS can be improved by doping with rare earth elements. A new electrochemical doping approach, constant potential electrolysis, and a new electrolyte system for doping of porous silicon with holmium were reported. By this approach and system, the doping products were well controlled, and Ho doped PS(HDPS) was found to emit much intenser visible photoluminescence with blue shift in wavelength and higher luminescence stability at room temperature than that for corresponding PS wafer. The effects of various kinds of holmium compounds, solvents, applied voltage, concentration of holmium nitrate and doping time on photoluminescence of HDPS were investigated, and the optimum doping conditions were fixed. The luminescence mechanisms for PS and HDPS were discussed.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11604052,11404180,and 11574114)the Natural Science Foundation of Heilongjiang Province,China(Grant No.A2015010)+3 种基金the Natural Science Foundation of Anhui Province,China(Grant No.1608085MA10)the International Science&Technology Cooperation Program of Anhui Province,China(Grant No.1403062027)the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province,China(Grant No.2015095)the Natural Science Foundation of Jilin Province,China(Grant No.20150101003JC)
文摘Cd F molecule, which plays an important role in a great variety of research fields, has long been subject to numerous researchers. Due to the unstable nature and heavy atom Cd containing in the Cd F molecule, electronic states of the molecule have not been well studied. In this paper, high accurate ab initio calculations on the Cd F molecule have been performed at the multi-reference configuration interaction level including Davidson correction（MRCI ＋ Q）. Adiabatic potential energy curves（PECs） of the 14 low-lying Λ–S states correlating with the two lowest dissociation limits Cd（~1S_g） ＋ F（~2P_u） and Cd（~3P_u） ＋ F（~2P_u） have been constructed. For the bound Λ–S and ？ states, the dominant electronic configurations and spectroscopic constants are obtained,and the calculated spectroscopic constants of bound states are consistent with previous experimental results. The dipole moments（DMs） of 2 Σ＋ and 2Π are determined, and the spin–orbit（SO） matrix elements between each pair of X2Σ＋, 22Σ＋, 12Π, and 22Π are obtained. The results indicate that the sudden changes of DMs and SO matrix elements arise from the variation of the electronic configurations around the avoided crossing region. Moreover,the Franck–Condon factors（FCFs）, the transition dipole moments（TDMs）, and radiative lifetimes of low-lying states-the ground state X2Σ＋are determined. Finally, the transitional properties of 22Π–X2Σ＋and 22Σ＋–X2Σ＋are studied. Based on our computed spectroscopic information of Cd F, the feasibility and challenge for laser cooling of Cd F molecule are discussed.
基金Project supported by the National Natural Science Foundation of China.
文摘Standard electrode potentials E° of Ag-AgC1 electrode in molality scale and acidity constants of glyeine pK_1° at constant molality of NaCl (1.0 mol·kg^(-1)) in 5 and 15 mass% glucose-water mixed solvents over a range of temperatures from 278.15 to 318.15 K were determined from precise emf measurements.The dependence of acidity constant on temperature is given as a function of the thermodynamic temperature T by an empirical equation, pK_1° =A_1(K/T)-A_2+A_3(T/K).The corresponding thermodynamic quantities of the first dissociation process of glycine were calculated and the effects of both tho solvent and the salt on them were also discussed.
