A concise analytical model for the static dipole polarizability of ionized atoms and molecules is created for the first time.As input,it requires,alongside the polarizability of neutral counterpart of a given ion,only...A concise analytical model for the static dipole polarizability of ionized atoms and molecules is created for the first time.As input,it requires,alongside the polarizability of neutral counterpart of a given ion,only the charge and elemental composition.This physically motivated semiempirical model is based on a number of established regularities in polarizability of charged monatomic and polyatomic compounds.In order to adjust it,the results of quantum chemistry calculations and gas-phase measurements available for a broad range of ionized multielectron species are employed.To counteract the appreciable bias in the literature data toward polarizability of monoatomic ions,for some molecular ions of general concern the results of the authors'own density functional theory calculations are additionally invoked.A total of 541 data points are used to optimize the model.It is demonstrated that the model we suggested has reasonable(given the substantial uncertainties of the reference data)accuracy in predicting the static isotropic polarizability of arbitrarily charged ions of any size and atomic composition.The resulting polarizability estimates are found to achieve a coefficient of determination of 0.93 for the assembled data set.The created analytic tool is universally applicable and might be advantageous for some applications where there is an urgent need for rapid low-cost evaluation of the static gas-phase polarizability of ionized atoms and molecules.This is especially relevant to constructing the complex models of nonequilibrium chemical kinetics aimed at precisely describing the observable refractive index(dielectric permittivity)of plasma flows.The data sets that support the findings of this study are openly available in Science Data Bank at https://doi.org/10.57760/sciencedb.07526.展开更多
We present a semiempirical analytical model for the static polarizability of electronically excited atoms and molecules,which requires very few readily accessible input data,including the ground-state polarizability,e...We present a semiempirical analytical model for the static polarizability of electronically excited atoms and molecules,which requires very few readily accessible input data,including the ground-state polarizability,elemental composition,ionization potential,and spin multiplicities of excited and ground states.This very simple model formulated in a semiclassical framework is based on a number of observed trends in polarizability of electronically excited compounds.To adjust the model,both accurate theoretical predictions and reliable measurements previously reported elsewhere for a broad range of multielectron species in the gas phase are utilized.For some representative compounds of general concern that have not yet attracted sufficient research interest,the results of our multireference second-order perturbation theory calculations are additionally engaged.We show that the model we developed has reasonable(given the considerable uncertainties in the reference data)accuracy in predicting the static polarizability of electronically excited species of arbitrary size and excitation energy.These findings can be useful for many applications,where there is a need for inexpensive and quick assessments of the static gas-phase polarizability of excited electronic states,in particular,when building the complex nonequilibrium kinetic models to describe the observed optical refractivity(dielectric permittivity)of nonthermal reacting gas flows.展开更多
In chain molecules of 1, 2-PBD, there are two kinds of gauche arrangements, which is the cause of making the spectrum of the secondary carbon in main chain of the polymer split. In such a complex system, the gauche ar...In chain molecules of 1, 2-PBD, there are two kinds of gauche arrangements, which is the cause of making the spectrum of the secondary carbon in main chain of the polymer split. In such a complex system, the gauche arrangements of the secondary carbon and the tertiary carbon occupy an important position. Hence, the contribution of the tertiary carbon to the chemical shifts of the secondary carbon has a decisive effect on the sequence structure distribution. In comparison the contribution of vinyl groups is much less. The γ values are: γ_1=-6.37～-6.41 ppm represents the effect of the tertiary carbon and γ_2=0.0～-1.56 ppm the contribution of vinyl. The mean square errors are 0.364 and 0.166×10^(-2) ppm^2, respectively in the two cases of considering the effect of vinyl and vice versa. In this paper, we discuss the effects of model chain type, chain length and temperature on the bond probability. Meanwhile, it is pointed out that there exist a few cases, which are not in accord with the usual distribution in calculation of bond probability. Moreover, the chain structure of syndiotactic 1, 2-PBD is studied in detail with DEPT pulse technique.展开更多
The relationship between bond valence and bond covalency in RMn2O5 (R = La, Pr, Nd.Sm, Eu) has been investigated by a semiempirical method. This method is the generalization of thedielectric description theory of Phil...The relationship between bond valence and bond covalency in RMn2O5 (R = La, Pr, Nd.Sm, Eu) has been investigated by a semiempirical method. This method is the generalization of thedielectric description theory of Phillips. Van Vechten, Levine and Tanaka scheme. The resultsindicate that larger valences usually result in higher bond covalencies, in good agreement with thepoint that the excess charge in the bonding region is the origin of formation of bond covalency.Other factors, such as oxidation state of elements, only make a small contribution to bondcovalency.展开更多
We report in this paper energy positions of the 2P˚_2s^(2)2p^(2)(^(1)D)nd 2P,2P˚_2s^(2)2p^(2)(^(1)D)nd 2S,2P˚_2s^(2)2p^(2)(^(1)D)ns^(2)D,2P˚_2s^(2)2p^(2)(^(1)S)nd ^(2)D,and 2P˚_2s^(2)2p^(3)(^(3)P)np ^(2)D Rydberg seri...We report in this paper energy positions of the 2P˚_2s^(2)2p^(2)(^(1)D)nd 2P,2P˚_2s^(2)2p^(2)(^(1)D)nd 2S,2P˚_2s^(2)2p^(2)(^(1)D)ns^(2)D,2P˚_2s^(2)2p^(2)(^(1)S)nd ^(2)D,and 2P˚_2s^(2)2p^(3)(^(3)P)np ^(2)D Rydberg series in the photoionization spectra originating from 2P˚metastable state of O+ions.Calculations are performed up to n=30 using the Modified Orbital Atomic Theory(MAOT).The present results are compared to the experimental data of Aguilar which are the only available values.The accurate data presented in this work may be a useful guideline for future experimental and other theoretical studies.展开更多
The semiempirical calculations were performed to discuss the effects of different substituents on the optical properties of a series of substituted benzonitriles and their corresponding oligomers. The substituents loc...The semiempirical calculations were performed to discuss the effects of different substituents on the optical properties of a series of substituted benzonitriles and their corresponding oligomers. The substituents located in para, meta and ortho-position of the benzenoid ring involve a large range of delta-pi electron-donor-acceptor capability. Theoretical analysis shows that the optical property is affected by the steric and electronic characteristics of the substituents on the benzenoid ring, moreover, the third-order polarizability regularly varies with the polymerization degrees.展开更多
The energy loss and stopping power of ^(4)He ions in mylar foils were determined in a transmission geometry.The experimental stopping power data were compared to the previous measurements at higher energies.At lower e...The energy loss and stopping power of ^(4)He ions in mylar foils were determined in a transmission geometry.The experimental stopping power data were compared to the previous measurements at higher energies.At lower energies,no previous measurements exist.The present results were also compared to the commonly used semiempirically theoretical predictions by Ziegler and Manoyan,and significant deviations were observed.展开更多
The two-photon absorption induced lasing spectrum shows that the synthesized ASPBPh4, trans-4- [p- (N-methyl-N- (hydroxyethyl)amino) styryl]-N-methylpyridinium, has a distinct ef- ficiency of laser frequency up-conver...The two-photon absorption induced lasing spectrum shows that the synthesized ASPBPh4, trans-4- [p- (N-methyl-N- (hydroxyethyl)amino) styryl]-N-methylpyridinium, has a distinct ef- ficiency of laser frequency up-conversion. This nonlinear optical property of such a kind of com- pounds is related to two-photon absorption (TPA). In our work, we used the intermediate ne- glect of differential overlap (INDO) plus single-excitation configuration interaction (SCI) method to get the basic properties of the molecule, and calculated the second hyperpolarizability and the cross section of two-photon absorption by means of sum-over-state (SOS) expression. The rela- tionship between the structure and the properties is discussed.展开更多
Based on Miedema's semiempirical formation enthalpy model for binary alloys, free volume theory and ageneral solution model, a new model for prediction of activity interaction coefficient ε is proposed. The calcu...Based on Miedema's semiempirical formation enthalpy model for binary alloys, free volume theory and ageneral solution model, a new model for prediction of activity interaction coefficient ε is proposed. The calculatedresults are better in agreement with the experimental values than the two previous models. The related theories andmodels are discussed according to the degree of agreement with experimental values.展开更多
We report in this paper energy positions of the 2D<sup>0</sup>_2s<sup>2</sup>2p<sup>2</sup>(<sup>1</sup>D)nd(<sup>2</sup>F);2D<sup>0</sup>_2s<...We report in this paper energy positions of the 2D<sup>0</sup>_2s<sup>2</sup>2p<sup>2</sup>(<sup>1</sup>D)nd(<sup>2</sup>F);2D<sup>0</sup>_2s<sup>2</sup>2p<sup>2</sup>(<sup>1</sup>D)nd(<sup>2</sup>D);2D<sup>0</sup>_2s<sup>2</sup>2p<sup>2</sup>(<sup>1</sup>D)nd(<sup>2</sup>P);2D<sup>0</sup>_2s<sup>2</sup>2p<sup>2</sup>(<sup>1</sup>D)ns(<sup>2</sup>D);2D<sup>0</sup>_2s<sup>2</sup>2p<sup>3</sup>(<sup>3</sup>D)np(<sup>2</sup>P);2D<sup>0</sup>_2s<sup>2</sup>2p<sup>3</sup>(<sup>3</sup>D<sup>0</sup>)np(<sup>2</sup>F), and 4S<sup>0</sup>_2s<sup>2</sup>2p<sup>3</sup>(<sup>5</sup>S<sup>0</sup>)np(<sup>4</sup>P) Rydberg series in the photoionization spectra originating from 2D<sup>0</sup> and 4S<sup>0</sup> metastable states of O<sup>+</sup> ion. Calculations are performed up to n = 20 using the Modified Orbital Atomic Theory (MAOT) [1]. The present results are compared to the experimental data of Aguilar et al. [2] which are the only available values. The accurate data presented in this work may be a useful guideline for future experimental and other theoretical studies.展开更多
The occurrence of Lean Blowout(LBO)is a disadvantage that endangers a stable operation of gas turbines.A determination of LBO limits is essential in the design of gas turbine combustors.A semiempirical model is one of...The occurrence of Lean Blowout(LBO)is a disadvantage that endangers a stable operation of gas turbines.A determination of LBO limits is essential in the design of gas turbine combustors.A semiempirical model is one of the most widely used methods to predict LBO limits.Among the existing semiempirical models for predicting LBO limits,Lefebvre’s LBO model and the Flame Volume(FV)model are particularly suitable for gas turbine combustors.On the basis of Lefebvre’s and FV models,the concept of effective evaporation efficiency is introduced in this paper,and a Flame Volume-Evaporation Efficiency(FV-EE)model is derived and validated.LBO experiments are carried out in a model combustor with 23 different structures and 10 different sprays.The prediction uncertainty of the FV-EE model is less than±13%for all of these 33 structures and sprays,compared with±50%for the FV model and±60%for Lefebvre’s model.Furthermore,the prediction uncertainty of the FV-EE model is also less than±13%for other combustors from available literature.展开更多
基金Project supported by the grant of the Russian Science Foundation(Project No.22-29-00124)。
文摘A concise analytical model for the static dipole polarizability of ionized atoms and molecules is created for the first time.As input,it requires,alongside the polarizability of neutral counterpart of a given ion,only the charge and elemental composition.This physically motivated semiempirical model is based on a number of established regularities in polarizability of charged monatomic and polyatomic compounds.In order to adjust it,the results of quantum chemistry calculations and gas-phase measurements available for a broad range of ionized multielectron species are employed.To counteract the appreciable bias in the literature data toward polarizability of monoatomic ions,for some molecular ions of general concern the results of the authors'own density functional theory calculations are additionally invoked.A total of 541 data points are used to optimize the model.It is demonstrated that the model we suggested has reasonable(given the substantial uncertainties of the reference data)accuracy in predicting the static isotropic polarizability of arbitrarily charged ions of any size and atomic composition.The resulting polarizability estimates are found to achieve a coefficient of determination of 0.93 for the assembled data set.The created analytic tool is universally applicable and might be advantageous for some applications where there is an urgent need for rapid low-cost evaluation of the static gas-phase polarizability of ionized atoms and molecules.This is especially relevant to constructing the complex models of nonequilibrium chemical kinetics aimed at precisely describing the observable refractive index(dielectric permittivity)of plasma flows.The data sets that support the findings of this study are openly available in Science Data Bank at https://doi.org/10.57760/sciencedb.07526.
基金supported by the grant of the Russian Science Foundation(project No.22-29-00124)。
文摘We present a semiempirical analytical model for the static polarizability of electronically excited atoms and molecules,which requires very few readily accessible input data,including the ground-state polarizability,elemental composition,ionization potential,and spin multiplicities of excited and ground states.This very simple model formulated in a semiclassical framework is based on a number of observed trends in polarizability of electronically excited compounds.To adjust the model,both accurate theoretical predictions and reliable measurements previously reported elsewhere for a broad range of multielectron species in the gas phase are utilized.For some representative compounds of general concern that have not yet attracted sufficient research interest,the results of our multireference second-order perturbation theory calculations are additionally engaged.We show that the model we developed has reasonable(given the considerable uncertainties in the reference data)accuracy in predicting the static polarizability of electronically excited species of arbitrary size and excitation energy.These findings can be useful for many applications,where there is a need for inexpensive and quick assessments of the static gas-phase polarizability of excited electronic states,in particular,when building the complex nonequilibrium kinetic models to describe the observed optical refractivity(dielectric permittivity)of nonthermal reacting gas flows.
文摘In chain molecules of 1, 2-PBD, there are two kinds of gauche arrangements, which is the cause of making the spectrum of the secondary carbon in main chain of the polymer split. In such a complex system, the gauche arrangements of the secondary carbon and the tertiary carbon occupy an important position. Hence, the contribution of the tertiary carbon to the chemical shifts of the secondary carbon has a decisive effect on the sequence structure distribution. In comparison the contribution of vinyl groups is much less. The γ values are: γ_1=-6.37～-6.41 ppm represents the effect of the tertiary carbon and γ_2=0.0～-1.56 ppm the contribution of vinyl. The mean square errors are 0.364 and 0.166×10^(-2) ppm^2, respectively in the two cases of considering the effect of vinyl and vice versa. In this paper, we discuss the effects of model chain type, chain length and temperature on the bond probability. Meanwhile, it is pointed out that there exist a few cases, which are not in accord with the usual distribution in calculation of bond probability. Moreover, the chain structure of syndiotactic 1, 2-PBD is studied in detail with DEPT pulse technique.
文摘The relationship between bond valence and bond covalency in RMn2O5 (R = La, Pr, Nd.Sm, Eu) has been investigated by a semiempirical method. This method is the generalization of thedielectric description theory of Phillips. Van Vechten, Levine and Tanaka scheme. The resultsindicate that larger valences usually result in higher bond covalencies, in good agreement with thepoint that the excess charge in the bonding region is the origin of formation of bond covalency.Other factors, such as oxidation state of elements, only make a small contribution to bondcovalency.
文摘We report in this paper energy positions of the 2P˚_2s^(2)2p^(2)(^(1)D)nd 2P,2P˚_2s^(2)2p^(2)(^(1)D)nd 2S,2P˚_2s^(2)2p^(2)(^(1)D)ns^(2)D,2P˚_2s^(2)2p^(2)(^(1)S)nd ^(2)D,and 2P˚_2s^(2)2p^(3)(^(3)P)np ^(2)D Rydberg series in the photoionization spectra originating from 2P˚metastable state of O+ions.Calculations are performed up to n=30 using the Modified Orbital Atomic Theory(MAOT).The present results are compared to the experimental data of Aguilar which are the only available values.The accurate data presented in this work may be a useful guideline for future experimental and other theoretical studies.
文摘The semiempirical calculations were performed to discuss the effects of different substituents on the optical properties of a series of substituted benzonitriles and their corresponding oligomers. The substituents located in para, meta and ortho-position of the benzenoid ring involve a large range of delta-pi electron-donor-acceptor capability. Theoretical analysis shows that the optical property is affected by the steric and electronic characteristics of the substituents on the benzenoid ring, moreover, the third-order polarizability regularly varies with the polymerization degrees.
基金the National Natural Science Foundation of Chinathe Doctoral Program Foundation of Institute of Higher Education and the Postdoctoral Research Foundation.
文摘The energy loss and stopping power of ^(4)He ions in mylar foils were determined in a transmission geometry.The experimental stopping power data were compared to the previous measurements at higher energies.At lower energies,no previous measurements exist.The present results were also compared to the commonly used semiempirically theoretical predictions by Ziegler and Manoyan,and significant deviations were observed.
文摘The two-photon absorption induced lasing spectrum shows that the synthesized ASPBPh4, trans-4- [p- (N-methyl-N- (hydroxyethyl)amino) styryl]-N-methylpyridinium, has a distinct ef- ficiency of laser frequency up-conversion. This nonlinear optical property of such a kind of com- pounds is related to two-photon absorption (TPA). In our work, we used the intermediate ne- glect of differential overlap (INDO) plus single-excitation configuration interaction (SCI) method to get the basic properties of the molecule, and calculated the second hyperpolarizability and the cross section of two-photon absorption by means of sum-over-state (SOS) expression. The rela- tionship between the structure and the properties is discussed.
文摘Based on Miedema's semiempirical formation enthalpy model for binary alloys, free volume theory and ageneral solution model, a new model for prediction of activity interaction coefficient ε is proposed. The calculatedresults are better in agreement with the experimental values than the two previous models. The related theories andmodels are discussed according to the degree of agreement with experimental values.
文摘We report in this paper energy positions of the 2D<sup>0</sup>_2s<sup>2</sup>2p<sup>2</sup>(<sup>1</sup>D)nd(<sup>2</sup>F);2D<sup>0</sup>_2s<sup>2</sup>2p<sup>2</sup>(<sup>1</sup>D)nd(<sup>2</sup>D);2D<sup>0</sup>_2s<sup>2</sup>2p<sup>2</sup>(<sup>1</sup>D)nd(<sup>2</sup>P);2D<sup>0</sup>_2s<sup>2</sup>2p<sup>2</sup>(<sup>1</sup>D)ns(<sup>2</sup>D);2D<sup>0</sup>_2s<sup>2</sup>2p<sup>3</sup>(<sup>3</sup>D)np(<sup>2</sup>P);2D<sup>0</sup>_2s<sup>2</sup>2p<sup>3</sup>(<sup>3</sup>D<sup>0</sup>)np(<sup>2</sup>F), and 4S<sup>0</sup>_2s<sup>2</sup>2p<sup>3</sup>(<sup>5</sup>S<sup>0</sup>)np(<sup>4</sup>P) Rydberg series in the photoionization spectra originating from 2D<sup>0</sup> and 4S<sup>0</sup> metastable states of O<sup>+</sup> ion. Calculations are performed up to n = 20 using the Modified Orbital Atomic Theory (MAOT) [1]. The present results are compared to the experimental data of Aguilar et al. [2] which are the only available values. The accurate data presented in this work may be a useful guideline for future experimental and other theoretical studies.
基金co-supported by the National Science and Technology Major Project,China(No.2017-III-0007-0032)the Key Laboratory Fund,China(No.6142702180306).
文摘The occurrence of Lean Blowout(LBO)is a disadvantage that endangers a stable operation of gas turbines.A determination of LBO limits is essential in the design of gas turbine combustors.A semiempirical model is one of the most widely used methods to predict LBO limits.Among the existing semiempirical models for predicting LBO limits,Lefebvre’s LBO model and the Flame Volume(FV)model are particularly suitable for gas turbine combustors.On the basis of Lefebvre’s and FV models,the concept of effective evaporation efficiency is introduced in this paper,and a Flame Volume-Evaporation Efficiency(FV-EE)model is derived and validated.LBO experiments are carried out in a model combustor with 23 different structures and 10 different sprays.The prediction uncertainty of the FV-EE model is less than±13%for all of these 33 structures and sprays,compared with±50%for the FV model and±60%for Lefebvre’s model.Furthermore,the prediction uncertainty of the FV-EE model is also less than±13%for other combustors from available literature.
