We present a minimal theoretical model for self-sustained oscillations of a thin elastic sheet on a hot plate,induced by thermomechanical coupling.As the plate temperature increases,the sheet’s static deflection beco...We present a minimal theoretical model for self-sustained oscillations of a thin elastic sheet on a hot plate,induced by thermomechanical coupling.As the plate temperature increases,the sheet’s static deflection becomes unstable via a Hopf bifurcation at a critical temperature TC,giving rise to spontaneous periodic motion.Linear stability analysis yields analytical expressions for the critical oscillation temperature TC and the oscillation period at onset.Numerical simulations of the nonlinear equations confirm the bifurcation and reveal how key parameters(stiffness,thermal softening,thermal coupling,etc.)govern the oscillation amplitude and waveform.Finally,we demonstrate that the self-oscillating sheet can perform mechanical work as a heat engine,and we compare its performance to the Carnot efficiency limit.This work provides design principles for thermally driven selfoscillators with potential applications in soft robotics,adaptive structures,and thermal energy harvesting.展开更多
Circularly polarized luminescence(CPL)and two-photon absorption(TPA)materials have garnered considerable attentions due to their minimal energy loss and superior optical penetration[1,2].However,the current challenge ...Circularly polarized luminescence(CPL)and two-photon absorption(TPA)materials have garnered considerable attentions due to their minimal energy loss and superior optical penetration[1,2].However,the current challenge lies in the absence of well-developed strategies for designing materials that combine these two exceptional optical properties.展开更多
Vicinal diamines are key motifs widely-found in many pharmaceuticals and biologically active molecules.An appealing approach for synthesizing these molecules is the amination of enamines,but few examples have been exp...Vicinal diamines are key motifs widely-found in many pharmaceuticals and biologically active molecules.An appealing approach for synthesizing these molecules is the amination of enamines,but few examples have been explored.With the utilization of nitrogen-centered radicals(NCRs),here we present the development of a dual bio-/photo-catalytic system for achieving enantioselective hydroamination of enamides,which can give easy access to diverse enantioenriched vicinal diamines.These reactions progress efficiently under green light excitation and exhibit excellent enantioselectivities(up to>99%enantiomeric excess).Mechanistic studies uncovered the synergistic effect of the enzyme and the externally added organophotoredox catalyst Rhodamine B(RhB).This work demonstrates the effectiveness of photobiocatalysis to generate and control high-energy radical intermediates,addressing a long-standing challenge in chemical synthesis.展开更多
Exploring advanced techniques capable of probing nanometric acoustic waves in nanostructures is critically important for the development of miniaturized acoustic devices.In this study,we probe the optically-excited ac...Exploring advanced techniques capable of probing nanometric acoustic waves in nanostructures is critically important for the development of miniaturized acoustic devices.In this study,we probe the optically-excited acoustic waves in a single silicon nanowire(NW)using the time-resolved(tr-)high-order Laue-zone(HOLZ)lines under convergent-beam electron diffraction(CBED)conditions in an ultrafast transmission electron microscope(UTEM).We devise an experimental scheme to obtain tr-HOLZ lines under off-zone-axis CBED conditions.We also propose a geometric description of HOLZ line formation and use this alternative description to quantitatively evaluate the dynamics of optically-excited silicon NW.Using part of the deformation gradient tensor,our simulations of the dynamics of Si NW reproduce the experimental results.We further discuss the feasibility of a full retrieval of the deformation gradient tensor by using a set of HOLZ lines from three zone axes.Our findings illustrate a strategy for the quantitative access to dynamical acoustic waves optically excited in micro-and nano-structures using UTEM.展开更多
The SiS molecule,which plays a significant role in space,has attracted a great deal of attention for many years.Due to complex interactions among its low-lying electronic states,precise information regarding the molec...The SiS molecule,which plays a significant role in space,has attracted a great deal of attention for many years.Due to complex interactions among its low-lying electronic states,precise information regarding the molecular structure of SiS is limited.To obtain accurate information about the structure of its excited states,the high-precision multireference configuration interaction(MRCI)method has been utilized.This method is used to calculate the potential energy curves(PECs)of the 18Λ–S states corresponding to the lowest dissociation limit of SiS.The core–valence correlation effect,Davidson’s correction and the scalar relativistic effect are also included to guarantee the precision of the MRCI calculation.Based on the calculated PECs,the spectroscopic constants of quasi-bound and bound electronic states are calculated and they are in accordance with previous experimental results.The transition dipole moments(TDMs)and dipole moments(DMs)are determined by the MRCI method.In addition,the abrupt variations of the DMs for the 1^(5)Σ^(+)and 2^(5)Σ^(+)states at the avoided crossing point are attributed to the variation of the electronic configuration.The opacity of SiS at a pressure of 100 atms is presented across a series of temperatures.With increasing temperature,the expanding population of excited states blurs the band boundaries.展开更多
While nickel(II)complexes have been widely used as catalysts for carbon-carbon coupling reactions,the exploration of their photophysical and photochemical properties is still in the infancy.Here,a series of square-pla...While nickel(II)complexes have been widely used as catalysts for carbon-carbon coupling reactions,the exploration of their photophysical and photochemical properties is still in the infancy.Here,a series of square-planar Ni(II)complexes[(diNHC)NiX2]bearing chelating benzimidazole-based bis(N-heterocyclic carbene)ligands and varying anionic coligands(1,X=Cl;2,X=Br;3,X=I)are synthesized and structurally characterized.In solid state,both 1 and 2 exhibit orange-red photoluminescence under ambient conditions.The photophysical and electrochemical measurements along with density functional theory(DFT)calculations reveal that the low-energy emissions can be attributed to singlet excited states with ligand-to-ligand charge-transfer(LLCT)character.This work suggests that strong-field N-heterocyclic carbene ligands play a crucial role to achieve the luminescence of Ni(II)complexes.展开更多
Strong empirical and phenomenological indications exist for large sea-quark admixtures in the low-lying excited baryons.Investigating the low-lying excited baryon ∑^(*)(1/2^(-))is important for determining the nature...Strong empirical and phenomenological indications exist for large sea-quark admixtures in the low-lying excited baryons.Investigating the low-lying excited baryon ∑^(*)(1/2^(-))is important for determining the nature of the low-lying excited baryons.We review the experimental and theoretical progress on the studies of the ∑^(*)(1/2^(-)).展开更多
The F+H_(2)reaction has long been a benchmark system in reaction dynamics.We report here a combined experimental and theoretical study on the F+H_(2)(v=1,j=1)reaction at a collision energy of 0.62 kcal/mol.The rotatio...The F+H_(2)reaction has long been a benchmark system in reaction dynamics.We report here a combined experimental and theoretical study on the F+H_(2)(v=1,j=1)reaction at a collision energy of 0.62 kcal/mol.The rotational state-resolved differential cross sections(DCSs)as well as the integral cross sections(ICSs)were obtained by the crossed beam experiment and the quantum dynamical calculation.It is found that the rotationally excited state F+H_(2)(v=1,j=1)reaction produces rotationally hotter but vibrationally colder products,compared with the rotational ground state reaction at the same total energy.The stereodynamics of the F+H_(2)(v=1,j=1)reaction is also analyzed theoretically,showing that minor differences exist for the reactants initially prepared in different spatial alignments.展开更多
In this paper,we investigate the existence of strange nonchaotic attractors(SNAs)in a slender rigid rocking block under quasi-periodic forcing with two frequencies.We find that an SNA can exist between a quasi-periodi...In this paper,we investigate the existence of strange nonchaotic attractors(SNAs)in a slender rigid rocking block under quasi-periodic forcing with two frequencies.We find that an SNA can exist between a quasi-periodic attractor and a chaotic attractor,or between two chaotic attractors.In particular,we demonstrate that a torus doubling bifurcation of a quasi-periodic attractor can result in SNAs via the fractal route before transforming into chaotic attractors.This phenomenon is rarely reported in quasiperiodically forced discontinuous differential equations and vibro-impact systems.The properties of SNAs are verified by the Lyapunov exponent,rational approximation,phase sensitivity,power spectrum,and separation of nearby trajectories.展开更多
SiO is a wide-spread molecule found in interstellar space.Previous research has primarily focused on its spectroscopy,while its photodissociation dynamics is elusive to study due to high dissociation energy.Using time...SiO is a wide-spread molecule found in interstellar space.Previous research has primarily focused on its spectroscopy,while its photodissociation dynamics is elusive to study due to high dissociation energy.Using time-sliced ion velocity imaging technique,we observed the Si(^(3)P)+O(^(3)P)photodissociation process resulting from the excitation of highly vibrationally excited SiO(X^(1)Σ^(+),υ=13-18)molecules to the SiO(A^(1)Π,E^(1)Σ^(+))states at 193 nm.The vibrationally excited SiO molecules were generated via laser ablation of silicon rod with the collision of the oxygen molecular beam acting as carrier gas and reaction gas.The bond dissociation energy D_(e)(Si-O)is determined to be 67253±110 cm^(-1)(8.34±0.01 eV)based on the kinetic energy distribution spectrum.The SiO photodissociation study has deepened our understanding of the mechanisms of silicon chemistry for silica-rich rocky meteors as they burn in the Earth's atmosphere,and the dissociation of SiO from ablation of meteoroids following ultraviolet photon absorption.展开更多
Carbazole-core multi-branched chromophores 9-ethyl- 3, 6-bis （ 2- { 4- [ 5- （4-tert-butyl-phenyl） - [ 1, 3, 4 ] oxadiazol-2-yl ] - phenyl }-vinyl） -carbazole（3） and 9-ethyl-3-（ 2- {4-[ 5-（4-tert-butyl- phenyl...Carbazole-core multi-branched chromophores 9-ethyl- 3, 6-bis （ 2- { 4- [ 5- （4-tert-butyl-phenyl） - [ 1, 3, 4 ] oxadiazol-2-yl ] - phenyl }-vinyl） -carbazole（3） and 9-ethyl-3-（ 2- {4-[ 5-（4-tert-butyl- phenyl） -[ 1, 3, 4 ] oxadiazol-2-yl ] -phenyl }-vinyl ） -carbazole （ 2 ） are synthesized through Wittig reaction and characterized by nuclear magnetic resonance（NMR）and infrared（IR）. The two- photon absorption properties of chromophores are investigated. These chromophores exhibit large two-photon absorption crosssections and strong blue two-photon excited fluorescence. The cooperative enhancement of two-photon absorption（TPA） in the multi-branched structures is observed. This enhancement is partly attributed to the electronic coupling between the branches. The electronic push-pull structures in the arm and their cooperative effects help the extended charge transfer for TPA.展开更多
Recently, the quantum description of electromagnetic waves in conducting media has been performed. It has been demonstrated that in particular case, the Hamiltonian of the corresponding field can be expressed by Caldi...Recently, the quantum description of electromagnetic waves in conducting media has been performed. It has been demonstrated that in particular case, the Hamiltonian of the corresponding field can be expressed by Caldirola–Kanai Hamiltonian. In this paper, using the associated annihilation and creation operators of the above-mentioned quantized field, the time-and conductivity-dependent squeezed vacuum and one-photon squeezed states as well as their superpositions, and also the time-and conductivity-dependent excited even and odd coherent states are produced. Also,using a few well-known nonclassicality criteria, the time evolution of nonclassicality features of the above classes of obtained states, in addition to the influence of medium conductivity on them are demonstrated, numerically. It has been shown that the nonclassicality indicators may be adjusted by tuning the conductivity of media.展开更多
The electronic structure of methanol/TiO2（ll0） interface has been studied by photoemis- sion spectroscopy. The pronounced resonance which appears at 5.5 eV above the Fermi level in two-photon photoemission spectrosc...The electronic structure of methanol/TiO2（ll0） interface has been studied by photoemis- sion spectroscopy. The pronounced resonance which appears at 5.5 eV above the Fermi level in two-photon photoemission spectroscopy （2PPE） is associated with the photocatalyzed dissociation of methanol at fivefold coordinated Ti sites （Ti5c） on TiO2 （110） surface [Chem- ical Science 1, 575 （2010）]. To check whether this resonance signal arises from initial or intermediate states, photon energy dependent 2PPE and comparison between one-photon photoemission spectroscopy and 2PPE have been performed. Both results consistently sug- gest the resonance signal originates from the initially unoccupied intermediate states, i.e., excited states. Dispersion measurements suggest the excited state is localized. Time-resolved studies show the lifetime of the excited state is 24 fs. This work presents comprehensive char- acterization of the excited states on methanol/TiO2（110） interface, and provides elaborate experimental data for the development of theoretical methods in reproducing the excited states on TiO2 surfaces and interfaces.展开更多
A surface femtosecond two-photon photoemission （2PPE） spectrometer devoted to the study of ultrafast excited electron dynamics and photochemical kinetics on metal and metal oxide surfaces has been constructed. Low e...A surface femtosecond two-photon photoemission （2PPE） spectrometer devoted to the study of ultrafast excited electron dynamics and photochemical kinetics on metal and metal oxide surfaces has been constructed. Low energy photoelectrons are measured using a hemispherical electron energy analyzer with an imaging detector that allows us to detect the energy and the angular distributions of the photoelectrons simultaneously. A Mach-Zehnder interferom- eter was built for the time-resolved 2PPE （TR-2PPE） measurement to study ultrafast surface excited electron dynamics, which was demonstrated on the Cu（111） surface. A scheme for measuring time-dependent 2PPE （TD-2PPE） spectra has also been developed for studies of surface photochemistry. This technique has been applied to a preliminary study on the photochemical kinetics on ethanol/TiO2（110）. We have also shown that the ultrafast dynamics of photoinduced surface excited resonances can be investigated in a reliable way by combining the TR-2PPE and TD-2PPE techniques.展开更多
The excited state intramolecular proton transfer （ESIPT） coupled charge transfer of baicalein has been investigated using steady-state spectroscopic experiment and quantum chemistry calculations. The absence of the ...The excited state intramolecular proton transfer （ESIPT） coupled charge transfer of baicalein has been investigated using steady-state spectroscopic experiment and quantum chemistry calculations. The absence of the absorption peak from S1 excited state both in the experi-mental and calculated absorption spectra indicates that S1 is a dark state. The dark excited state S1 results in the very weak fluorescence of solid baicalein in the experiment. The fron- tier molecular orbital and the charge difference densities of baicalein show clearly that the S1 state is a charge-transfer state whereas the S2 state is a locally excited state. The only one stationary point on the potential energy profile of excited state suggests that the ESIPT reaction of baicalein is a barrierless process.展开更多
Herein we have employed high-level multi-reference CASSCF and MS-CASPT2 electronic structure methods to systematically study the photochemical mechanism of intramolecularly hydrogen-bonded 2-（2＇-hydroxyphenyl）-4-me...Herein we have employed high-level multi-reference CASSCF and MS-CASPT2 electronic structure methods to systematically study the photochemical mechanism of intramolecularly hydrogen-bonded 2-（2＇-hydroxyphenyl）-4-methyloxazole. At the CASSCF level, we have optimized minima, conical intersections, minimum-energy reaction paths relevant to the excited-state intramolecular proton transfer （ESIPT）, rotation, photoisomerization, and the excited-state deactivation pathways. The energies of all structures and paths are refined by the MS-CASPT2 method. On the basis of the present results, we found that the ESIPT process in a conformer with the OH... N hydrogen bond is essentially barrierless process; whereas, the ESIPT process is inhibited in the other conformer with the OH... O hydrogen bond. The central single-bond rotation of the S1 enol species is energetically unfavorable due to a large barrier. In addition, the excited-state deactivation of the S1 keto species, as a result of the ultrafast ESIPT, is very efficient because of the existence of two easily-approached keto S1/S0 conical intersections. In stark contrast to the S1 keto species, the decay of the S1 enol species is almostly blocked. The present theoretical study contributes valuable knowledge to the understanding of photochemistry of similar intramolecularly hydrogen-bonded molecular and biological systems.展开更多
This paper considers the dynamical behavior of a Duffing-Mathieu type system with a cubic single-well potential during the principal parametric resonance. Both the cases of constant and time-dependent excitation ampli...This paper considers the dynamical behavior of a Duffing-Mathieu type system with a cubic single-well potential during the principal parametric resonance. Both the cases of constant and time-dependent excitation amplitude are used to observe the variation of the extent and the rate of the erosion in safe basins. It is evident that the appearance of fractal basin boundaries heralds the onset of the losing of structural integrity. The minimum value of control parameter to prevent the basin from erosion is given along with the excitation amplitude varying. The results show the time-dependence of excitation amplitude can be used to control the extent and the rate of the erosion and delay the first occurrence of heteroclinic tangency.展开更多
We study the H＋CH4/CD4-＋H2/HD＋CH3/CD3 reactions using the time sliced velocity map ion imaging technique. Ion images of the CH3/CD3 products were measured by the （2＋1） resonance enhanced multi-photon ionization ...We study the H＋CH4/CD4-＋H2/HD＋CH3/CD3 reactions using the time sliced velocity map ion imaging technique. Ion images of the CH3/CD3 products were measured by the （2＋1） resonance enhanced multi-photon ionization （REMPI） detection method. Besides the CH3/CD3 products in the ground state, ion images of the vibrationally excited CH3/CD3 products were also observed at two collision energies of 0.72 and 1.06 eV. It is shown that the angular distribution of the products CH3/CD3 in vibrationally excited states gradually vary from backward scattering to sideways scattering as the collision energy increases. Compared to the CH3/CD3 products in the ground state, the CH3/CD3 products in vibrationally excited states tend to be more sideways scattered, indicating that larger impact parameters play a more important role in the vibrationally excited product channels.展开更多
Geometry and vibrational frequencies of the ground state of Si2O2 molecule are studied using density function theory （DFT） at the level of cc-pvtz and 6-311-k＋G^＊＊. It is found that the optimizing value by B31yp/...Geometry and vibrational frequencies of the ground state of Si2O2 molecule are studied using density function theory （DFT） at the level of cc-pvtz and 6-311-k＋G^＊＊. It is found that the optimizing value by B31yp/cc-pvtz is closer to the experimental data. The excited properties under different external electric fields are also investigated by the time-dependent-DFT method. Transitions from the ground state of Si2O2 molecule to the first singlet state under different external electric fields can take place more easily. The corresponding absorption spectral line is about 360 nm in wavelength and the excitation energy is about 3.4 eV.展开更多
This paper investigates the excited states of Si3O molecule by using the single-excitation configuration interaction and density functional theory. It finds that the visible light absorption spectrum of Si3O molecule ...This paper investigates the excited states of Si3O molecule by using the single-excitation configuration interaction and density functional theory. It finds that the visible light absorption spectrum of Si3O molecule comprises the yellow and the purple light without external electric field, however all the visible light is included except the green light under the action of external electric field. Oxygen-deficient defects, which also can be found in Si3O molecule, have been used to explain the 1 from silicon-based materials but the microstructures of the materials are still uncertain Our results accord with the experimental values perfectly, this fact suggests that the structure of Si3O molecule is expected to be one of the main basic structures of the materials, so the oxygen-deficient defect structural model for Si3O molecule also has been provided to research the structures of materials.展开更多
基金supported by the Guangdong Basic and Applied Basic Research Foundation(Grant Nos.2025B1515020077 and 2024A15150301-39)the National Natural Science Foundation of China(Grant No.12205138)the Shenzhen Science and Technology Innovation Committee(Grant No.JCYJ2022-0530113206015).
文摘We present a minimal theoretical model for self-sustained oscillations of a thin elastic sheet on a hot plate,induced by thermomechanical coupling.As the plate temperature increases,the sheet’s static deflection becomes unstable via a Hopf bifurcation at a critical temperature TC,giving rise to spontaneous periodic motion.Linear stability analysis yields analytical expressions for the critical oscillation temperature TC and the oscillation period at onset.Numerical simulations of the nonlinear equations confirm the bifurcation and reveal how key parameters(stiffness,thermal softening,thermal coupling,etc.)govern the oscillation amplitude and waveform.Finally,we demonstrate that the self-oscillating sheet can perform mechanical work as a heat engine,and we compare its performance to the Carnot efficiency limit.This work provides design principles for thermally driven selfoscillators with potential applications in soft robotics,adaptive structures,and thermal energy harvesting.
基金supported by NSFC(22271282)the Self-deployment Project Research Program of Haixi Institutes,Chinese Academy of Sciences with the grant number of CXZX-2022-JQ04.
文摘Circularly polarized luminescence(CPL)and two-photon absorption(TPA)materials have garnered considerable attentions due to their minimal energy loss and superior optical penetration[1,2].However,the current challenge lies in the absence of well-developed strategies for designing materials that combine these two exceptional optical properties.
文摘Vicinal diamines are key motifs widely-found in many pharmaceuticals and biologically active molecules.An appealing approach for synthesizing these molecules is the amination of enamines,but few examples have been explored.With the utilization of nitrogen-centered radicals(NCRs),here we present the development of a dual bio-/photo-catalytic system for achieving enantioselective hydroamination of enamides,which can give easy access to diverse enantioenriched vicinal diamines.These reactions progress efficiently under green light excitation and exhibit excellent enantioselectivities(up to>99%enantiomeric excess).Mechanistic studies uncovered the synergistic effect of the enzyme and the externally added organophotoredox catalyst Rhodamine B(RhB).This work demonstrates the effectiveness of photobiocatalysis to generate and control high-energy radical intermediates,addressing a long-standing challenge in chemical synthesis.
基金supported by the Guangxi Natural Science Foundation(Grant No.2024GXNSFDA010014)the National Natural Science Foundation of China(Grant Nos.12364018 and U22A6005)+1 种基金the Guangxi Science and Technology Major Program(Grant No.AA23073019)the Innovation Project of Guangxi Graduate Education(Grant Nos.YCBZ2022049 and YCBZ2023015)。
文摘Exploring advanced techniques capable of probing nanometric acoustic waves in nanostructures is critically important for the development of miniaturized acoustic devices.In this study,we probe the optically-excited acoustic waves in a single silicon nanowire(NW)using the time-resolved(tr-)high-order Laue-zone(HOLZ)lines under convergent-beam electron diffraction(CBED)conditions in an ultrafast transmission electron microscope(UTEM).We devise an experimental scheme to obtain tr-HOLZ lines under off-zone-axis CBED conditions.We also propose a geometric description of HOLZ line formation and use this alternative description to quantitatively evaluate the dynamics of optically-excited silicon NW.Using part of the deformation gradient tensor,our simulations of the dynamics of Si NW reproduce the experimental results.We further discuss the feasibility of a full retrieval of the deformation gradient tensor by using a set of HOLZ lines from three zone axes.Our findings illustrate a strategy for the quantitative access to dynamical acoustic waves optically excited in micro-and nano-structures using UTEM.
基金Project supported by the Natural Science Foundation of Heilongjiang Province,China(Grant No.LH2022A026)the National Key Research and Development Program of China(Grant No.2022YFA1602500)+2 种基金the National Natural Science Foundation of China(Grant No.11934004)Fundamental Research Funds in Heilongjiang Province Universities,China(Grant No.145109309)Foundation of National Key Laboratory of Computational Physics(Grant No.6142A05QN22006)。
文摘The SiS molecule,which plays a significant role in space,has attracted a great deal of attention for many years.Due to complex interactions among its low-lying electronic states,precise information regarding the molecular structure of SiS is limited.To obtain accurate information about the structure of its excited states,the high-precision multireference configuration interaction(MRCI)method has been utilized.This method is used to calculate the potential energy curves(PECs)of the 18Λ–S states corresponding to the lowest dissociation limit of SiS.The core–valence correlation effect,Davidson’s correction and the scalar relativistic effect are also included to guarantee the precision of the MRCI calculation.Based on the calculated PECs,the spectroscopic constants of quasi-bound and bound electronic states are calculated and they are in accordance with previous experimental results.The transition dipole moments(TDMs)and dipole moments(DMs)are determined by the MRCI method.In addition,the abrupt variations of the DMs for the 1^(5)Σ^(+)and 2^(5)Σ^(+)states at the avoided crossing point are attributed to the variation of the electronic configuration.The opacity of SiS at a pressure of 100 atms is presented across a series of temperatures.With increasing temperature,the expanding population of excited states blurs the band boundaries.
基金the Natural Science Foundation of China(No.22175191)Y.C.thanks the financial support from CAS-Croucher Funding Scheme for Joint Laboratories and Beijing Municipal Science&Technology Commission(No.Z211100007921020).
文摘While nickel(II)complexes have been widely used as catalysts for carbon-carbon coupling reactions,the exploration of their photophysical and photochemical properties is still in the infancy.Here,a series of square-planar Ni(II)complexes[(diNHC)NiX2]bearing chelating benzimidazole-based bis(N-heterocyclic carbene)ligands and varying anionic coligands(1,X=Cl;2,X=Br;3,X=I)are synthesized and structurally characterized.In solid state,both 1 and 2 exhibit orange-red photoluminescence under ambient conditions.The photophysical and electrochemical measurements along with density functional theory(DFT)calculations reveal that the low-energy emissions can be attributed to singlet excited states with ligand-to-ligand charge-transfer(LLCT)character.This work suggests that strong-field N-heterocyclic carbene ligands play a crucial role to achieve the luminescence of Ni(II)complexes.
基金partly supported by the National Key R&D Program of China(Grant No.2023YFA1606700)partly supported by the National Key R&D Program of China(Grant No.2024YFE0105200)+6 种基金supported by the Natural Science Foundation of Henan(Grant Nos.232300421140 and 222300420554)the National Natural Science Foundation of China(Grant Nos.12475086,12192263,12205075,12175239,12221005,12075288,and 12361141819)the Open Project of Guangxi Key Laboratory of Nuclear Physics and Nuclear Technology(Grant No.NLK2021-08)the Central Government Guidance Funds for Local Scientific and Technological Development,China(Grant No.ZY22096024)the National Key Research and Development Program of China(Grant No.2020YFA0406400)the Chinese Academy of Sciences(Grant No.YSBR-101)the Youth Innovation Promotion Association of CAS。
文摘Strong empirical and phenomenological indications exist for large sea-quark admixtures in the low-lying excited baryons.Investigating the low-lying excited baryon ∑^(*)(1/2^(-))is important for determining the nature of the low-lying excited baryons.We review the experimental and theoretical progress on the studies of the ∑^(*)(1/2^(-)).
基金the National Natural Science Foundation of China(Nos.22288201,22173040,22241301,22103032)the Chinese Academy of Sciences(No.GJJSTD20220001),the Innovation Program for Quantum Scienceand Technology(No.2021ZD0303300)+2 种基金the Guangdong Science and Technology Program(Nos.2019ZT08L455,2019JC01X091)the Shenzhen Science and Technology Innovation Committee(Nos.JCYJ20210324103810029,20220815145746004,and 2021344670)the Shenzhen Science and Technology Program(No.DSYS20200421111001787).
文摘The F+H_(2)reaction has long been a benchmark system in reaction dynamics.We report here a combined experimental and theoretical study on the F+H_(2)(v=1,j=1)reaction at a collision energy of 0.62 kcal/mol.The rotational state-resolved differential cross sections(DCSs)as well as the integral cross sections(ICSs)were obtained by the crossed beam experiment and the quantum dynamical calculation.It is found that the rotationally excited state F+H_(2)(v=1,j=1)reaction produces rotationally hotter but vibrationally colder products,compared with the rotational ground state reaction at the same total energy.The stereodynamics of the F+H_(2)(v=1,j=1)reaction is also analyzed theoretically,showing that minor differences exist for the reactants initially prepared in different spatial alignments.
基金supported by the National Natural Science Foundation of China under grant number 11971019.
文摘In this paper,we investigate the existence of strange nonchaotic attractors(SNAs)in a slender rigid rocking block under quasi-periodic forcing with two frequencies.We find that an SNA can exist between a quasi-periodic attractor and a chaotic attractor,or between two chaotic attractors.In particular,we demonstrate that a torus doubling bifurcation of a quasi-periodic attractor can result in SNAs via the fractal route before transforming into chaotic attractors.This phenomenon is rarely reported in quasiperiodically forced discontinuous differential equations and vibro-impact systems.The properties of SNAs are verified by the Lyapunov exponent,rational approximation,phase sensitivity,power spectrum,and separation of nearby trajectories.
基金supported by the National Natural Science Foundation of China(No.22073019 and No.21327901)the Shanghai Key Laboratory Foundation of Molecular Catalysis and Innovative Materials,and the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning.
文摘SiO is a wide-spread molecule found in interstellar space.Previous research has primarily focused on its spectroscopy,while its photodissociation dynamics is elusive to study due to high dissociation energy.Using time-sliced ion velocity imaging technique,we observed the Si(^(3)P)+O(^(3)P)photodissociation process resulting from the excitation of highly vibrationally excited SiO(X^(1)Σ^(+),υ=13-18)molecules to the SiO(A^(1)Π,E^(1)Σ^(+))states at 193 nm.The vibrationally excited SiO molecules were generated via laser ablation of silicon rod with the collision of the oxygen molecular beam acting as carrier gas and reaction gas.The bond dissociation energy D_(e)(Si-O)is determined to be 67253±110 cm^(-1)(8.34±0.01 eV)based on the kinetic energy distribution spectrum.The SiO photodissociation study has deepened our understanding of the mechanisms of silicon chemistry for silica-rich rocky meteors as they burn in the Earth's atmosphere,and the dissociation of SiO from ablation of meteoroids following ultraviolet photon absorption.
基金The National Natural Science Foundation of China(No.60678042)the Natural Science Foundation of Jiangsu Province(No.BK2006553)the Pre-Research Project of the National Natural Science Foundation supported by Southeast University(No.9207041399)
文摘Carbazole-core multi-branched chromophores 9-ethyl- 3, 6-bis （ 2- { 4- [ 5- （4-tert-butyl-phenyl） - [ 1, 3, 4 ] oxadiazol-2-yl ] - phenyl }-vinyl） -carbazole（3） and 9-ethyl-3-（ 2- {4-[ 5-（4-tert-butyl- phenyl） -[ 1, 3, 4 ] oxadiazol-2-yl ] -phenyl }-vinyl ） -carbazole （ 2 ） are synthesized through Wittig reaction and characterized by nuclear magnetic resonance（NMR）and infrared（IR）. The two- photon absorption properties of chromophores are investigated. These chromophores exhibit large two-photon absorption crosssections and strong blue two-photon excited fluorescence. The cooperative enhancement of two-photon absorption（TPA） in the multi-branched structures is observed. This enhancement is partly attributed to the electronic coupling between the branches. The electronic push-pull structures in the arm and their cooperative effects help the extended charge transfer for TPA.
文摘Recently, the quantum description of electromagnetic waves in conducting media has been performed. It has been demonstrated that in particular case, the Hamiltonian of the corresponding field can be expressed by Caldirola–Kanai Hamiltonian. In this paper, using the associated annihilation and creation operators of the above-mentioned quantized field, the time-and conductivity-dependent squeezed vacuum and one-photon squeezed states as well as their superpositions, and also the time-and conductivity-dependent excited even and odd coherent states are produced. Also,using a few well-known nonclassicality criteria, the time evolution of nonclassicality features of the above classes of obtained states, in addition to the influence of medium conductivity on them are demonstrated, numerically. It has been shown that the nonclassicality indicators may be adjusted by tuning the conductivity of media.
文摘The electronic structure of methanol/TiO2（ll0） interface has been studied by photoemis- sion spectroscopy. The pronounced resonance which appears at 5.5 eV above the Fermi level in two-photon photoemission spectroscopy （2PPE） is associated with the photocatalyzed dissociation of methanol at fivefold coordinated Ti sites （Ti5c） on TiO2 （110） surface [Chem- ical Science 1, 575 （2010）]. To check whether this resonance signal arises from initial or intermediate states, photon energy dependent 2PPE and comparison between one-photon photoemission spectroscopy and 2PPE have been performed. Both results consistently sug- gest the resonance signal originates from the initially unoccupied intermediate states, i.e., excited states. Dispersion measurements suggest the excited state is localized. Time-resolved studies show the lifetime of the excited state is 24 fs. This work presents comprehensive char- acterization of the excited states on methanol/TiO2（110） interface, and provides elaborate experimental data for the development of theoretical methods in reproducing the excited states on TiO2 surfaces and interfaces.
文摘A surface femtosecond two-photon photoemission （2PPE） spectrometer devoted to the study of ultrafast excited electron dynamics and photochemical kinetics on metal and metal oxide surfaces has been constructed. Low energy photoelectrons are measured using a hemispherical electron energy analyzer with an imaging detector that allows us to detect the energy and the angular distributions of the photoelectrons simultaneously. A Mach-Zehnder interferom- eter was built for the time-resolved 2PPE （TR-2PPE） measurement to study ultrafast surface excited electron dynamics, which was demonstrated on the Cu（111） surface. A scheme for measuring time-dependent 2PPE （TD-2PPE） spectra has also been developed for studies of surface photochemistry. This technique has been applied to a preliminary study on the photochemical kinetics on ethanol/TiO2（110）. We have also shown that the ultrafast dynamics of photoinduced surface excited resonances can be investigated in a reliable way by combining the TR-2PPE and TD-2PPE techniques.
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.61137005 and No.10974023）, the Program for Liaoning Excellent Talents in University （No.LJQ2012002）, and the Program for New Century Excellent Talents in University （No.NCET-12-0077）.
文摘The excited state intramolecular proton transfer （ESIPT） coupled charge transfer of baicalein has been investigated using steady-state spectroscopic experiment and quantum chemistry calculations. The absence of the absorption peak from S1 excited state both in the experi-mental and calculated absorption spectra indicates that S1 is a dark state. The dark excited state S1 results in the very weak fluorescence of solid baicalein in the experiment. The fron- tier molecular orbital and the charge difference densities of baicalein show clearly that the S1 state is a charge-transfer state whereas the S2 state is a locally excited state. The only one stationary point on the potential energy profile of excited state suggests that the ESIPT reaction of baicalein is a barrierless process.
文摘Herein we have employed high-level multi-reference CASSCF and MS-CASPT2 electronic structure methods to systematically study the photochemical mechanism of intramolecularly hydrogen-bonded 2-（2＇-hydroxyphenyl）-4-methyloxazole. At the CASSCF level, we have optimized minima, conical intersections, minimum-energy reaction paths relevant to the excited-state intramolecular proton transfer （ESIPT）, rotation, photoisomerization, and the excited-state deactivation pathways. The energies of all structures and paths are refined by the MS-CASPT2 method. On the basis of the present results, we found that the ESIPT process in a conformer with the OH... N hydrogen bond is essentially barrierless process; whereas, the ESIPT process is inhibited in the other conformer with the OH... O hydrogen bond. The central single-bond rotation of the S1 enol species is energetically unfavorable due to a large barrier. In addition, the excited-state deactivation of the S1 keto species, as a result of the ultrafast ESIPT, is very efficient because of the existence of two easily-approached keto S1/S0 conical intersections. In stark contrast to the S1 keto species, the decay of the S1 enol species is almostly blocked. The present theoretical study contributes valuable knowledge to the understanding of photochemistry of similar intramolecularly hydrogen-bonded molecular and biological systems.
基金the National Science Foundation of ChinaPSF of China
文摘This paper considers the dynamical behavior of a Duffing-Mathieu type system with a cubic single-well potential during the principal parametric resonance. Both the cases of constant and time-dependent excitation amplitude are used to observe the variation of the extent and the rate of the erosion in safe basins. It is evident that the appearance of fractal basin boundaries heralds the onset of the losing of structural integrity. The minimum value of control parameter to prevent the basin from erosion is given along with the excitation amplitude varying. The results show the time-dependence of excitation amplitude can be used to control the extent and the rate of the erosion and delay the first occurrence of heteroclinic tangency.
文摘We study the H＋CH4/CD4-＋H2/HD＋CH3/CD3 reactions using the time sliced velocity map ion imaging technique. Ion images of the CH3/CD3 products were measured by the （2＋1） resonance enhanced multi-photon ionization （REMPI） detection method. Besides the CH3/CD3 products in the ground state, ion images of the vibrationally excited CH3/CD3 products were also observed at two collision energies of 0.72 and 1.06 eV. It is shown that the angular distribution of the products CH3/CD3 in vibrationally excited states gradually vary from backward scattering to sideways scattering as the collision energy increases. Compared to the CH3/CD3 products in the ground state, the CH3/CD3 products in vibrationally excited states tend to be more sideways scattered, indicating that larger impact parameters play a more important role in the vibrationally excited product channels.
基金Project supported by the National Natural Science Foundation of China (Grant No. 10774039)the Natural Science Foundation of Henan Province,China (Grant No. 092300410249)+1 种基金the Natural Science Foundation of the Education Bureau of Henan Province,China (Grant No. 2010A140008)the Foundation for University Young Core Instructors of Henan Province,China (Grant No. 2009GGJS-044)
文摘Geometry and vibrational frequencies of the ground state of Si2O2 molecule are studied using density function theory （DFT） at the level of cc-pvtz and 6-311-k＋G^＊＊. It is found that the optimizing value by B31yp/cc-pvtz is closer to the experimental data. The excited properties under different external electric fields are also investigated by the time-dependent-DFT method. Transitions from the ground state of Si2O2 molecule to the first singlet state under different external electric fields can take place more easily. The corresponding absorption spectral line is about 360 nm in wavelength and the excitation energy is about 3.4 eV.
基金Project supported by the Foundation for University Young Core Instructors of Henan Province,China(Grant No.2009GGJS-044)the Natural Science Foundation of the Education Bureau of Henan Province,China(Grant No.2010A140008)+1 种基金the Natural Science Foundation of Henan Province,China(Grant No.092300410249)the Natural Science Foundation of the Education Bureau of Henan Province,China(Grant No.2010A140008)
文摘This paper investigates the excited states of Si3O molecule by using the single-excitation configuration interaction and density functional theory. It finds that the visible light absorption spectrum of Si3O molecule comprises the yellow and the purple light without external electric field, however all the visible light is included except the green light under the action of external electric field. Oxygen-deficient defects, which also can be found in Si3O molecule, have been used to explain the 1 from silicon-based materials but the microstructures of the materials are still uncertain Our results accord with the experimental values perfectly, this fact suggests that the structure of Si3O molecule is expected to be one of the main basic structures of the materials, so the oxygen-deficient defect structural model for Si3O molecule also has been provided to research the structures of materials.
