Spectroscopy and molecule opacity investigation on excited states of SiS

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.

Two-proton radioactivity from excited states of proton-rich nuclei within Coulomb and Proximity Potential Model

In the present work,we extend the Coulomb and Proximity Potential Model(CPPM)to study two-proton(2p)radioactivity from excited states while the proximity potential is chosen as AW95 proposed by Aage Withner in 1995.Demonstration reveals that the theoretical results acquired by CPPM exhibit a high level of consistency with prior theoretical models such as the unified fission model(UFM),generalized liquid-drop model(GLDM)and effective liquid-drop model(ELDM).Furthermore,within the CPPM,we predicted the half-lives of potential 2p radioactive nuclei for which experimental data are currently unavailable.The predicted results were then assessed,compared with UFM,ELDM and GLDM models,and examined in detail.

Secondary electron emission and photoemission from a negative electron affinity semiconductor with large mean escape depth of excited electrons

The formulae for parameters of a negative electron affinity semiconductor(NEAS)with large mean escape depth of secondary electrons A(NEASLD)are deduced.The methods for obtaining parameters such asλ,B,E_(pom)and the maximumδandδat 100.0 keV≥E_(po)≥1.0 keV of a NEASLD with the deduced formulae are presented(B is the probability that an internal secondary electron escapes into the vacuum upon reaching the emission surface of the emitter,δis the secondary electron yield,E_(po)is the incident energy of primary electrons and E_(pom)is the E_(po)corresponding to the maximumδ).The parameters obtained here are analyzed,and it can be concluded that several parameters of NEASLDs obtained by the methods presented here agree with those obtained by other authors.The relation between the secondary electron emission and photoemission from a NEAS with large mean escape depth of excited electrons is investigated,and it is concluded that the presented method of obtaining A is more accurate than that of obtaining the corresponding parameter for a NEAS with largeλ_(ph)(λ_(ph)being the mean escape depth of photoelectrons),and that the presented method of calculating B at E_(po)>10.0 keV is more widely applicable for obtaining the corresponding parameters for a NEAS with largeλ_(ph).

Directional Chiral Optical Emission by Electron-Beam-Excited Nano-Antenna

Manipulating directional chiral optical emissions on a nanometer scale is significant for material science research. The electron-beam-excited nanoantenna provides a favorable platform to tune optical emissions at the deep subwavelength scale. Here we present an L-shaped electron-beam-excited nanoantenna(LENA) with two identical orthogonal arms. By selecting different electron-beam impacting sites on the LENA, either the lefthanded circularly polarized(LCP) or the right-handed circularly polarized(RCP) emission can be excited. The LCP and RCP emissions possess different emission directionality, and the emission wavelength depends on the arm length of the LENA. Further, we show a combined nanoantenna with two LENAs of different arm lengths.Induced by the electron beam, LCP and RCP lights emit simultaneously from the nanoantenna with different wavelengths to different directions. This approach is suggested to be informative for investigating electron-photon interaction and electron-beam spectroscopy in nanophotonics.

Role of excited states in helium-like ions on high-order harmonic generation

We theoretically investigate high-order harmonic generation(HHG) of helium(He), lithium cation(Li+), and beryllium dication(Be2+) using the time-dependent Hartree–Fock method to solve the three-dimensional time-dependent Schr ¨odinger equation. It is found that the intensity of the HHG increases significantly from a certain harmonic order below the ionization threshold, and the initial position of the enhancement does not depend on the intensity or the wavelength of the driving laser field. Further analysis shows that excited states play an important role on this enhancement,consistent with the excited-state tunneling mechanism [Phys. Rev. Lett. 116 123901(2016)]. Our results unambiguously show that excited-state tunneling is essential for understanding the enhancement of HHG. Accordingly, a four-step model is herein proposed to illustrate the multiphoton excitation effect in helium-like ions, which enriches the physics of HHG enhancement.

A TD-DFT Study for the Excited State Calculations of Microhydration of N-Acetyl-Phenylalaninylamide (NAPA)

Investigating the impact of microhydration on the excited-states and electronic excitation properties of biomolecules has remained one of the important yet challenging aspects of science because of the complexity of developing models. However, with the advent of computational chemistry methods such as TD-DFT, many useful insights about the electronic excitation energy and excited-state nature of biomolecules can be explored. Accordingly, in our study, we have incorporated the TD-DFT/wB97XD/cc-pVTZ method to study the excited state properties of N-acetyl phenylalanine amide (NAPA-A(H2O) n) (n = 1 to 4) clusters from ground to the tenth lowest gaseous singlet excited state. We found that the C=O bond length gradually increases both in N-terminal amide and C-terminal amide after the sequential addition of water molecules because of intermolecular H-bonding and this intermolecular H-bonding becomes weaker after the sequential addition of H2O molecules. The UV absorption maxima of NAPA-A (H2O)n (n = 1 - 4) clusters consisted of two peaks that are S5←S0 (1st absorption) and S6←S0 (2nd absorption) excitations. The first absorption maxima were blue-shifted with the increase in oscillator strength. This means that strong H-bonds reduce the charge transfer and make clusters more rigid. On the other hand, the second absorption maxima were red-shifted with the decrease in oscillator strength. In the ECD spectra, the negative bands indicate the presence of an amide bond and L-configuration of micro hydrated NAPA-A clusters. Finally, our calculated absorption and fluorescence energy confirm that all the NAPA-A (H2O) n (n = 0 - 4) clusters revert to the ground state from the fluorescent state by emitting around 5.490 eV of light.

A simple semiempirical model for the static polarizability of electronically excited atoms and molecules

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.

Multi-branched carbazole derivatives for two-photon absorption and two-photon excited fluorescence

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.

Characterization of the Excited State on Methanol/Ti02（110） Interface

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.

A Surface Femtosecond Two-Photon Photoemission Spectrometer for Excited Electron Dynamics and Time-Dependent Photochemical Kinetics

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.

Experimental and Theoretical Investigation on Excited State Intramolecular Proton Transfer Coupled Charge Transfer Reaction of Baicalein

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.

Excited-State Proton Transfer and Decay in Hydrogen-Bonded Oxazole System： MS-CASPT2//CASSCF Study

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.

CONTROLLING EROSION OF SAFE BASIN IN NONLINEAR PARAMETRICALLY EXCITED SYSTEMS

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.

Crossed Molecular Beam Study of H＋CH4 and H＋CD4 Reactions： Vibrationally Excited CH3/CD3 Product Channels

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.

Si_2O_2 molecule:structure of ground state and the excited properties under different external electric fields

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.

Si _3O cluster:excited properties under external electric field and oxygen-deficient defect models

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.

Behaviours of the excited states 1s^2 np along lithium isoelectronic sequence from Z=11 to 20

Based on the obtained energy values of 1s^2np （n≤ 9） states for lithium-like systems from Z=11 to 20 （by the authors of this paper： Hu M H and Wang Z W 2004 Chin. Phys. 13 662）, this paper determines the quantum defects, as slowly varying function of energy, of this Rydberg series. Using them as input, it can predict the energies of any highly excited states below the ionization threshold for this series a^cording to the quantum defect theory. The regularities of variation for quantum defects of the series along this isoelectronic sequence are physically analysed and discussed. The screening parameters, which are equal to the effective screening charge of the core-electrons, are also obtained.

Complex dynamics of a harmonically excited structure coupled with a nonlinear energy sink

Nonlinear behaviors are investigated for a structure coupled with a nonlinear energy sink. The structure is linear and subject to a harmonic excitation, modeled as a forced single-degree-of-freedom oscillator. The nonlinear energy sink is modeled as an oscillator consisting of a mass,a nonlinear spring, and a linear damper. Based on the numerical solutions, global bifurcation diagrams are presented to reveal the coexistence of periodic and chaotic motions for varying nonlinear energy sink mass and stiffness. Chaos is numerically identified via phase trajectories, power spectra,and Poincaré maps. Amplitude-frequency response curves are predicted by the method of harmonic balance for periodic steady-state responses. Their stabilities are analyzed.The Hopf bifurcation and the saddle-node bifurcation are determined. The investigation demonstrates that a nonlinear energy sink may create dynamic complexity.

Neutron Halos in the Excited States of Spherical Nuclei Near the β-Stable Line

The newly discovered neutron halos in the excited states of nuclei 12B, 13C, and 209pb are studied by therelativistic mean-field theory. The calculated binding energies are very close to the experimental ones. The experimentally extracted root-mean-square radii of the last neutron with different occupations in nuclei are well reproduced bycalculations. New candidates for the neutron halos in excited states are predicted and are useful for further search ofneutron halos in the excited states of stable nuclei.

Stability and local bifurcation of parameter-excited vibration of pipes conveying pulsating fluid under thermal loading

The parametric excited vibration of a pipe under thermal loading may occur because the fluid is often transported heatedly. The effects of thermal loading on the pipe stability and local bifurcations have rarely been studied. The stability and the local bifurcations of the lateral parametric resonance of the pipe induced by the pulsating fluid velocity and the thermal loading are studied. A mathematical model for a simply supported pipe is developed according to the Hamilton principle. Two partial differential equations describing the lateral and longitudinal vibration are obtained. The singularity theory is utilized to anMyze the stability and the bifurcation of the system solutions. The transition sets and the bifurcation diagrams are obtained both in the unfolding parameter space and the physical parameter space, which can reveal the relationship between the thermal field parameter and the dynamic behaviors of the pipe. The frequency response and the relationship between the critical thermal rate and the pulsating fluid velocity are obtained. The numerical results demonstrate the accuracy of the single-mode expansion of the solution and the stability and local bifurcation analyses. It also confirms the existence of the chaos. The presented work can provide valuable information for the design of the pipeline and the controllers to prevent the structural instability.