The stereochemically active lone pairs around post-transition metal atoms play an important role in determining distorted lattice structure and optical response.The lone pair electrons are characterized by crystal orb...The stereochemically active lone pairs around post-transition metal atoms play an important role in determining distorted lattice structure and optical response.The lone pair electrons are characterized by crystal orbitals,electron localization function(ELF)and partial density of states(PDOS).Birefringence is evaluated by means of a Born effective charge approach based on modern polarization theory.The origin of the different responses of birefringence and second-harmonic generation(SHG)is explored,as well as the effect of spin-orbit coupling(SOC)on the band structure and optical properties is explored.The study of this paper can help to deeply understand the lone pairs and their contribution to optical property.展开更多
We present a combined experimental and theoretical study on the electronic structure and bonding characteristics of the CuO^(-)anion.On the experimental side,high resolution photoelectron imaging has allowed the detec...We present a combined experimental and theoretical study on the electronic structure and bonding characteristics of the CuO^(-)anion.On the experimental side,high resolution photoelectron imaging has allowed the detection of new features of the low-lying states of the CuO^(-).Supporting MRCI+Q calculations with inclusion of complex spin-orbit coupling effects have yielded complemented assignments of the photoelectron spectra obtained in the present and previous experiments to low-lying spin-orbit mixed states,which also reveal strong multiconfiguration correlation effects in CuO^(-).Analyses on the experimentally measured photoelectron angular distributions indicate that,the Cu-O bond in the X^(1)Σ^(+)state can be characterized by mixed ionic and covalent interactions,with the ionic character being more dominant,while the a^(3)Пstate can be characterized by a typical ionic bond.Our results provide a renewed understanding in the interplay of ionic-covalent bonding characters in the diatomic CuO^(-)anion.展开更多
基金supported by the National Natural Science Foundation of the People's Republic of China“Mechanistic study of the influence of ns^(2) cation intrinsic properties and coordination environment on birefringence and frequency doubling effects”(12264047),“The study of the mechanism of the influence of lead-oxygen polyhedra and their coordination environments on the gain of the frequency doubling effect”(11864040)Tianshan Talent Project of Xinjiang Uygur Autonomous Region of China“Design,synthesis and photofunctional study of novel rare earth phosphate materials”(2022TSYCJU0004)。
文摘The stereochemically active lone pairs around post-transition metal atoms play an important role in determining distorted lattice structure and optical response.The lone pair electrons are characterized by crystal orbitals,electron localization function(ELF)and partial density of states(PDOS).Birefringence is evaluated by means of a Born effective charge approach based on modern polarization theory.The origin of the different responses of birefringence and second-harmonic generation(SHG)is explored,as well as the effect of spin-orbit coupling(SOC)on the band structure and optical properties is explored.The study of this paper can help to deeply understand the lone pairs and their contribution to optical property.
基金supported by the National Natural Science Foudation of China(No.22173089,and No.22103075)the National Key R&D Program of China(No.2021YFA0716801)Innovation Program for Quantum Science and Technology(2021ZD0300301).
文摘We present a combined experimental and theoretical study on the electronic structure and bonding characteristics of the CuO^(-)anion.On the experimental side,high resolution photoelectron imaging has allowed the detection of new features of the low-lying states of the CuO^(-).Supporting MRCI+Q calculations with inclusion of complex spin-orbit coupling effects have yielded complemented assignments of the photoelectron spectra obtained in the present and previous experiments to low-lying spin-orbit mixed states,which also reveal strong multiconfiguration correlation effects in CuO^(-).Analyses on the experimentally measured photoelectron angular distributions indicate that,the Cu-O bond in the X^(1)Σ^(+)state can be characterized by mixed ionic and covalent interactions,with the ionic character being more dominant,while the a^(3)Пstate can be characterized by a typical ionic bond.Our results provide a renewed understanding in the interplay of ionic-covalent bonding characters in the diatomic CuO^(-)anion.
