Density functional theory (DFT) B3LYP at 6-31G* level is employed to optimize the structures of the molecules bridged through n-vertex bis-substituted carborane (n=5, 6, 7) and combined with finite field (FF) formalis...Density functional theory (DFT) B3LYP at 6-31G* level is employed to optimize the structures of the molecules bridged through n-vertex bis-substituted carborane (n=5, 6, 7) and combined with finite field (FF) formalism to calculate the second-order NLO properties. The results indicate that the structures of n-vertex bis-substituted carborane (n=5, 6, 7) are changed due to bridged donor and acceptor moieties. The distances between two C atoms are becoming longer. And the stability and dipole moment are in- fluenced by changing substituted positions of C atoms. The isomers with the substituents connecting with C atoms of lower coordination number have better stability and larger values of polarizability. One-dimensional structure of the molecules bridged through n-vertex bis-substituted carborane (n=5, 6, 7) is in favor of intramolecular charge-transfer. Meanwhile, the isomer with a larger change of dipole moment has larger value of second-order NLO properties during the charge-transfer process.展开更多
The second-order nonlinear optical (NLO) properties of 5,10,15-triphenylcorrole (TPC), 5,10,15,20-tetraphenylporphyrin (TPP) and L-amino acid bridged bis-corroles 1,2,3 and 4 have been calculated by using TDHF/P...The second-order nonlinear optical (NLO) properties of 5,10,15-triphenylcorrole (TPC), 5,10,15,20-tetraphenylporphyrin (TPP) and L-amino acid bridged bis-corroles 1,2,3 and 4 have been calculated by using TDHF/PM3 method based on the RHF/6-31G (TPC and TPP) or semiempirical PM3 (1, 2, 3, 4) optimized geometries. Calculation results showed TPC and TPP have C1 and D2h symmetry, respectively when N-H protons are localized on the nitrogen atoms. TPC is the second-order NLO active chromophore due to the cancellation of centrosymmetrical structure and its first hyperpolarizability β increases to 11.524×10^-30 esu. Under electrical dipole approximation, βvalues of bis-corroles 1, 2, 3 and 4 vary from 9.831×10^-30 to 14.221×10^-30 esu, and no much improvement in the first hyperpolarizability was observed as compared to TPC monomer.However, β values of bis-corroles 1, 2, 3 and 4 are improved by about 4 times as compared to their bis-porphyrin counterparts. The analysis of β components indicates that β of this kind of bis-corroles is mainly contributed from its radial component βr. With the variation of amino acid side chains, βHRS, β,βxyz, βr and βa of bis-corroles change remarkably. Chiral L-amino acid bridged bis-corroles 2, 3 and 4 have a right-handed helix structure, and their chiral component βxyz matches βxyz ∝ r^2 ζ/L^4 (helix parameters), showing the second-order chiral NLO response of these bis-corroles could be described by one-electron helical model theory. It was found that the radial component βr of chiral helix bis-corroles also matches βr ∝ r^2 ζ/L^4.展开更多
In this paper,a stochastic second-order two-scale(SSOTS)method is proposed for predicting the non-deterministic mechanical properties of composites with random interpenetrating phase.Firstly,based on random morphology...In this paper,a stochastic second-order two-scale(SSOTS)method is proposed for predicting the non-deterministic mechanical properties of composites with random interpenetrating phase.Firstly,based on random morphology description functions(RMDF),the randomness of the material properties of the constituents as well as the correlation among these random properties are fully characterized through the topologies of the constituents.Then,by virtue of multiscale asymptotic analysis,the random effective quantities such as stiffness parameters and strength parameters along with their numerical computation formulae are derived by a SSOTS strategy combined with the Monte-Carlo method.Finally,the SSOTS method developed in this paper shows an excellent computational accuracy,and therefore present an important advance towards computationally efficient multiscale modeling frameworks considering microstructure uncertainties.展开更多
A new non-metal 3-D borophosphate compound formulated as(NH4)2[B2P2O8(OH)2](1)has been synthesized by a solvothermal method and characterized by elemental analysis,energy-dispersive X-ray spectroscopy(EDS),IR spectrum...A new non-metal 3-D borophosphate compound formulated as(NH4)2[B2P2O8(OH)2](1)has been synthesized by a solvothermal method and characterized by elemental analysis,energy-dispersive X-ray spectroscopy(EDS),IR spectrum and single-crystal X-ray diffraction.The borophosphate(NH4)2[B2P2O8(OH)2]crystallizes in the cubic system,space group P213 with Z=2,a=b=c=7.586(4)?,V=436.6(4)?3,Mr=281.64,Dc=2.127 g/cm^3,λ=0.71073?,μ=0.551 mm^-1,F(000)=284,R=0.0277 and wR=0.0758 for 262 observed reflections with I>2σ(I)and S=1.082.Its structure is constructed by the connection of PO4 and BO3(OH)tetrahedra to form a 3-D anionic framework containing 4-and 8-membered rings(MRs),with two NH4+cations located in the channels of the 8-membered rings.The N–H…O hydrogen bonds are observed in its packing structure and enhanced the stability of crystal structure.In addition,its thermal stability,UV spectrum and second-order NLO properties have been also investigated.展开更多
The design and the synthesis of two conjugated donor acceptor imidazole derivatives(1, 2) were carried out for second order nonlinear optics. The thermal properties, the transparency and second order nonlinear opti...The design and the synthesis of two conjugated donor acceptor imidazole derivatives(1, 2) were carried out for second order nonlinear optics. The thermal properties, the transparency and second order nonlinear optical properties of the molecules were investigated. The experimental results indicate that a good nonlinearity transparency thermal stability trade off is achieved for them.展开更多
A series of CdS nanoparticles with different surfaces were prepared by colloidal chemical method and reverse micelle method. Their second-order nonlinear optical (NLO) properties were experimentally studied in solutio...A series of CdS nanoparticles with different surfaces were prepared by colloidal chemical method and reverse micelle method. Their second-order nonlinear optical (NLO) properties were experimentally studied in solution by newly developed hyper-Rayleigh scattering (HRS) technique. The results show that 'per particle' first-order hyperpolarizability beta values are sensitive To the synthetic method and the surface chemical modification.展开更多
Second order nonlinear optical active 2,3-dichloro-5,6-dicyanopyrazine (DCDCP) and its monoamine-substituted derivatives had been synthesized. Their facile synthesis, high melt point, high incidence af substantial SHG...Second order nonlinear optical active 2,3-dichloro-5,6-dicyanopyrazine (DCDCP) and its monoamine-substituted derivatives had been synthesized. Their facile synthesis, high melt point, high incidence af substantial SHG activity and increased transparency inthe blue and near infrared make this class compounds appealling for further investigation.展开更多
The organic imine and their metal complexes were synthesized and characterized by IR, UV and NMR. The third order non linear optical properties of the compounds were investigated. The measurements of second hyperpolar...The organic imine and their metal complexes were synthesized and characterized by IR, UV and NMR. The third order non linear optical properties of the compounds were investigated. The measurements of second hyperpolarizabilites were performed using single beam Z-scan technique with 8 ns laser pulses. Ligand and its Copper, Zinc and Nickel complexes show good third order non linearity whereas Manganese complex did not show any activity.展开更多
DFT B3LYP/LANL2DZ method was employed to calculate electron properties and the second-order nonlinear optical(NLO) respond of platinum(Ⅱ) complexes which have been synthesized by Weinstein group.4,7-diphenyl-1,10-phe...DFT B3LYP/LANL2DZ method was employed to calculate electron properties and the second-order nonlinear optical(NLO) respond of platinum(Ⅱ) complexes which have been synthesized by Weinstein group.4,7-diphenyl-1,10-phenanthroline shows the ability to push electron in these complexes.Metal Pt plays a balancing charge role.Comparing complex 1b-6b with complex a,the βvec value of complex 1b-5b is larger than one of complex a,while the βvec value of complex 6b is smaller than one of com-plex a.In these seven complexes,the βvec values of complexes increase with decreasing of the energy difference between HOMO and LUMO.Moreover,the electron transfers from deeper layer occupied orbitals to empty orbitals have a distinct contribution to second-order NLO coefficient.展开更多
In this paper,a statistical cluster-based simulation channel model with a finite number of sinusoids is proposed for depicting the multiple-input multiple-output(MIMO)communications in vehicleto-everything(V2X)environ...In this paper,a statistical cluster-based simulation channel model with a finite number of sinusoids is proposed for depicting the multiple-input multiple-output(MIMO)communications in vehicleto-everything(V2X)environments.In the proposed sum-of-sinusoids(SoS)channel model,the waves that emerge from the transmitter undergo line-of-sight(LoS)and non-line-of-sight(NLoS)propagation to the receiver,which makes the model suitable for describing numerous V2X wireless communication scenarios for sixth-generation(6G).We derive expressions for the real and imaginary parts of the complex channel impulse response(CIR),which characterize the physical propagation characteristics of V2X wireless channels.The statistical properties of the real and imaginary parts of the complex CIRs,i.e.,autocorrelation functions(ACFs),Doppler power spectral densities(PSDs),cross-correlation functions(CCFs),and variances of ACFs and CCFs,are derived and discussed.Simulation results are generated and match those predicted by the underlying theory,demonstrating the accuracy of our derivation and analysis.The proposed framework and underlying theory arise as an efficient tool to investigate the statistical properties of 6G MIMO V2X communication systems.展开更多
The external electric field is a special strategy for generating novel structures.In this work,the intermolecular bonding and nonlinear optical properties are affected by applying an applied electric field of 0 to 9.7...The external electric field is a special strategy for generating novel structures.In this work,the intermolecular bonding and nonlinear optical properties are affected by applying an applied electric field of 0 to 9.77 V·nm^(-1)along the bonding direction of dimer of olympicenyl radical(OLY2).The results showed that the distance between molecular layers was lengthened gradually,and the 2e/20c bonds were weakened or even completely broken(the critical electric field is 9.77 V·nm^(-1))with the increase of the external electric field strength.Moreover,the introduction of an external electric field caused significant changes in the electronic properties of the OLY2,which induced charge transfer between inter-layer monomers,and enhanced the interlayer electrostatic interactions.Therefore,the external electric field not only regulates the interlayer interactions of molecules,but also causes the symmetric molecules to produce strong polarity,producing a large NLO response in OLY2.展开更多
The dynamic first hyperpolarizabilities of a series of 1,10-phenanthroline Ru(II) complexes were carried out using density functional theory (DFT). The results indicate that these complexes have large second-order...The dynamic first hyperpolarizabilities of a series of 1,10-phenanthroline Ru(II) complexes were carried out using density functional theory (DFT). The results indicate that these complexes have large second-order nonlinear optical (NLO) responses. Specially, complex 6b has a maximal first hyperpolarizability βtot value. The first hyperpolarizabilities can be tuned by changing the ancillary ligand, introducing electron-acceptor group NO2 and/or increasing r-conjugation on phenanthroline. Calculations on absorption spectra demonstrate that the second-order NLO responses of complexes in series a are ascribed to the intraligand charge transfer (ILCT), while the complexes in series b exhibit metal-to-ligand charge transfer (MLCT) and lig- and-to-ligand charge transfer (LLCT) transition at relatively low-energy absorptions.展开更多
Time dependent density functional theory (TDDFT) has been applied to calculate the electronic structure and second order nonlinear optical (NLO) properties of some organic molecules. The two dimensional (2 D) cha...Time dependent density functional theory (TDDFT) has been applied to calculate the electronic structure and second order nonlinear optical (NLO) properties of some organic molecules. The two dimensional (2 D) charge transfer characteristics of calculated molecules were studied and compared with corresponding experimental results. All the theoretical results agree well with the measurement. For 2 D molecule with two fold symmetry, the dominant charge transfer is off diagonal, while for three fold symmetry 2 D molecule, the dominant charge transfer is not only between branches and central group but also among branches.展开更多
基金Supported by the Foundation of Jilin Provincial Excellent Youth (Grant No. 20050107)Youth Science Foundation of Northeast Normal University (Grant No. 111494117)
文摘Density functional theory (DFT) B3LYP at 6-31G* level is employed to optimize the structures of the molecules bridged through n-vertex bis-substituted carborane (n=5, 6, 7) and combined with finite field (FF) formalism to calculate the second-order NLO properties. The results indicate that the structures of n-vertex bis-substituted carborane (n=5, 6, 7) are changed due to bridged donor and acceptor moieties. The distances between two C atoms are becoming longer. And the stability and dipole moment are in- fluenced by changing substituted positions of C atoms. The isomers with the substituents connecting with C atoms of lower coordination number have better stability and larger values of polarizability. One-dimensional structure of the molecules bridged through n-vertex bis-substituted carborane (n=5, 6, 7) is in favor of intramolecular charge-transfer. Meanwhile, the isomer with a larger change of dipole moment has larger value of second-order NLO properties during the charge-transfer process.
基金Supported by the NNSFC (20476034), Research Grants Council of Hongkong and SRF for ROCS, State Education Ministry
文摘The second-order nonlinear optical (NLO) properties of 5,10,15-triphenylcorrole (TPC), 5,10,15,20-tetraphenylporphyrin (TPP) and L-amino acid bridged bis-corroles 1,2,3 and 4 have been calculated by using TDHF/PM3 method based on the RHF/6-31G (TPC and TPP) or semiempirical PM3 (1, 2, 3, 4) optimized geometries. Calculation results showed TPC and TPP have C1 and D2h symmetry, respectively when N-H protons are localized on the nitrogen atoms. TPC is the second-order NLO active chromophore due to the cancellation of centrosymmetrical structure and its first hyperpolarizability β increases to 11.524×10^-30 esu. Under electrical dipole approximation, βvalues of bis-corroles 1, 2, 3 and 4 vary from 9.831×10^-30 to 14.221×10^-30 esu, and no much improvement in the first hyperpolarizability was observed as compared to TPC monomer.However, β values of bis-corroles 1, 2, 3 and 4 are improved by about 4 times as compared to their bis-porphyrin counterparts. The analysis of β components indicates that β of this kind of bis-corroles is mainly contributed from its radial component βr. With the variation of amino acid side chains, βHRS, β,βxyz, βr and βa of bis-corroles change remarkably. Chiral L-amino acid bridged bis-corroles 2, 3 and 4 have a right-handed helix structure, and their chiral component βxyz matches βxyz ∝ r^2 ζ/L^4 (helix parameters), showing the second-order chiral NLO response of these bis-corroles could be described by one-electron helical model theory. It was found that the radial component βr of chiral helix bis-corroles also matches βr ∝ r^2 ζ/L^4.
基金partially supported by China Postdoctoral Science Foundation(2018M643573)National Natural Science Foundation of Shaanxi Province(2019JQ-048)+2 种基金National Natural Science Foundation of China(51739007,61971328,11301392 and 11961009)of ChinaShanghai Peak Discipline Program for Higher Education Institutions(ClassⅠ)–Civil EngineeringFundamental Research Funds for the Central Universities(No.22120180529)。
文摘In this paper,a stochastic second-order two-scale(SSOTS)method is proposed for predicting the non-deterministic mechanical properties of composites with random interpenetrating phase.Firstly,based on random morphology description functions(RMDF),the randomness of the material properties of the constituents as well as the correlation among these random properties are fully characterized through the topologies of the constituents.Then,by virtue of multiscale asymptotic analysis,the random effective quantities such as stiffness parameters and strength parameters along with their numerical computation formulae are derived by a SSOTS strategy combined with the Monte-Carlo method.Finally,the SSOTS method developed in this paper shows an excellent computational accuracy,and therefore present an important advance towards computationally efficient multiscale modeling frameworks considering microstructure uncertainties.
基金Supported by the National Natural Science Foundation of China(No.21601095)
文摘A new non-metal 3-D borophosphate compound formulated as(NH4)2[B2P2O8(OH)2](1)has been synthesized by a solvothermal method and characterized by elemental analysis,energy-dispersive X-ray spectroscopy(EDS),IR spectrum and single-crystal X-ray diffraction.The borophosphate(NH4)2[B2P2O8(OH)2]crystallizes in the cubic system,space group P213 with Z=2,a=b=c=7.586(4)?,V=436.6(4)?3,Mr=281.64,Dc=2.127 g/cm^3,λ=0.71073?,μ=0.551 mm^-1,F(000)=284,R=0.0277 and wR=0.0758 for 262 observed reflections with I>2σ(I)and S=1.082.Its structure is constructed by the connection of PO4 and BO3(OH)tetrahedra to form a 3-D anionic framework containing 4-and 8-membered rings(MRs),with two NH4+cations located in the channels of the 8-membered rings.The N–H…O hydrogen bonds are observed in its packing structure and enhanced the stability of crystal structure.In addition,its thermal stability,UV spectrum and second-order NLO properties have been also investigated.
基金Supported by the Natural Science Foundation of Hubei ProvinceChina(No.2 0 0 0 J15 6 )
文摘The design and the synthesis of two conjugated donor acceptor imidazole derivatives(1, 2) were carried out for second order nonlinear optics. The thermal properties, the transparency and second order nonlinear optical properties of the molecules were investigated. The experimental results indicate that a good nonlinearity transparency thermal stability trade off is achieved for them.
基金National Natural Science Foundation of China! (No.59582005)
文摘A series of CdS nanoparticles with different surfaces were prepared by colloidal chemical method and reverse micelle method. Their second-order nonlinear optical (NLO) properties were experimentally studied in solution by newly developed hyper-Rayleigh scattering (HRS) technique. The results show that 'per particle' first-order hyperpolarizability beta values are sensitive To the synthetic method and the surface chemical modification.
文摘Second order nonlinear optical active 2,3-dichloro-5,6-dicyanopyrazine (DCDCP) and its monoamine-substituted derivatives had been synthesized. Their facile synthesis, high melt point, high incidence af substantial SHG activity and increased transparency inthe blue and near infrared make this class compounds appealling for further investigation.
文摘The organic imine and their metal complexes were synthesized and characterized by IR, UV and NMR. The third order non linear optical properties of the compounds were investigated. The measurements of second hyperpolarizabilites were performed using single beam Z-scan technique with 8 ns laser pulses. Ligand and its Copper, Zinc and Nickel complexes show good third order non linearity whereas Manganese complex did not show any activity.
基金Supported by Program for Changjiang Scholars and Innovative Research Team in University, the Foundation of Jilin Provincial Excellent Youth (Grant No. 20050107)Youth Science Foundation of Northeast Normal University (Grant No. 111494117)
文摘DFT B3LYP/LANL2DZ method was employed to calculate electron properties and the second-order nonlinear optical(NLO) respond of platinum(Ⅱ) complexes which have been synthesized by Weinstein group.4,7-diphenyl-1,10-phenanthroline shows the ability to push electron in these complexes.Metal Pt plays a balancing charge role.Comparing complex 1b-6b with complex a,the βvec value of complex 1b-5b is larger than one of complex a,while the βvec value of complex 6b is smaller than one of com-plex a.In these seven complexes,the βvec values of complexes increase with decreasing of the energy difference between HOMO and LUMO.Moreover,the electron transfers from deeper layer occupied orbitals to empty orbitals have a distinct contribution to second-order NLO coefficient.
基金supported by National Natural Science Foundation of China(NSFC)(No.62101274 and 62101275)Natural Science Foundation of Jiangsu Province(BK20210640)Open Research Fund of National Mobile Communications Research Laboratory Southeast University under Grant 2021D03。
文摘In this paper,a statistical cluster-based simulation channel model with a finite number of sinusoids is proposed for depicting the multiple-input multiple-output(MIMO)communications in vehicleto-everything(V2X)environments.In the proposed sum-of-sinusoids(SoS)channel model,the waves that emerge from the transmitter undergo line-of-sight(LoS)and non-line-of-sight(NLoS)propagation to the receiver,which makes the model suitable for describing numerous V2X wireless communication scenarios for sixth-generation(6G).We derive expressions for the real and imaginary parts of the complex channel impulse response(CIR),which characterize the physical propagation characteristics of V2X wireless channels.The statistical properties of the real and imaginary parts of the complex CIRs,i.e.,autocorrelation functions(ACFs),Doppler power spectral densities(PSDs),cross-correlation functions(CCFs),and variances of ACFs and CCFs,are derived and discussed.Simulation results are generated and match those predicted by the underlying theory,demonstrating the accuracy of our derivation and analysis.The proposed framework and underlying theory arise as an efficient tool to investigate the statistical properties of 6G MIMO V2X communication systems.
基金Foundation of Science and Technology Department of Jilin Province(20230101043JC).
文摘The external electric field is a special strategy for generating novel structures.In this work,the intermolecular bonding and nonlinear optical properties are affected by applying an applied electric field of 0 to 9.77 V·nm^(-1)along the bonding direction of dimer of olympicenyl radical(OLY2).The results showed that the distance between molecular layers was lengthened gradually,and the 2e/20c bonds were weakened or even completely broken(the critical electric field is 9.77 V·nm^(-1))with the increase of the external electric field strength.Moreover,the introduction of an external electric field caused significant changes in the electronic properties of the OLY2,which induced charge transfer between inter-layer monomers,and enhanced the interlayer electrostatic interactions.Therefore,the external electric field not only regulates the interlayer interactions of molecules,but also causes the symmetric molecules to produce strong polarity,producing a large NLO response in OLY2.
基金supported by the National Natural Science Foundation of China (20873017)the Natural Science Foundation of Jilin Province (20101154)
文摘The dynamic first hyperpolarizabilities of a series of 1,10-phenanthroline Ru(II) complexes were carried out using density functional theory (DFT). The results indicate that these complexes have large second-order nonlinear optical (NLO) responses. Specially, complex 6b has a maximal first hyperpolarizability βtot value. The first hyperpolarizabilities can be tuned by changing the ancillary ligand, introducing electron-acceptor group NO2 and/or increasing r-conjugation on phenanthroline. Calculations on absorption spectra demonstrate that the second-order NLO responses of complexes in series a are ascribed to the intraligand charge transfer (ILCT), while the complexes in series b exhibit metal-to-ligand charge transfer (MLCT) and lig- and-to-ligand charge transfer (LLCT) transition at relatively low-energy absorptions.
文摘Time dependent density functional theory (TDDFT) has been applied to calculate the electronic structure and second order nonlinear optical (NLO) properties of some organic molecules. The two dimensional (2 D) charge transfer characteristics of calculated molecules were studied and compared with corresponding experimental results. All the theoretical results agree well with the measurement. For 2 D molecule with two fold symmetry, the dominant charge transfer is off diagonal, while for three fold symmetry 2 D molecule, the dominant charge transfer is not only between branches and central group but also among branches.