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.

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.

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.

Role of excited states in the elliptically polarized harmonic generation

We theoretically investigate the contribution of the excited state to the ellipticity of the harmonics from H＋ at different orientation angles irradiated by a linearly polarized laser pulse. It is found that the first excited state has a significant influence to the ellipticity of the harmonics, and the contribution of higher excited states to the ellipticity can be neglected. Moreover, the conclusion is not dependent on the laser intensity.

Two-proton radioactivity of the excited state within the Gamow-like and modified Gamow-like models

In this study,we systematically investigated the two-proton(2p)radioactivity half-lives from the excited state of nuclei near the proton drip line within the Gamowlike model(GLM)and modified Gamow-like model(MGLM).The calculated results were highly consistent with the theoretical values obtained using the unified fission model[Chin.Phys.C 45,124105(2021)],effective liquid drop model,and generalized liquid drop model[Acta Phys.Sin 71,062301(2022)].Furthermore,utilizing the GLM and MGLM,we predicted the 2p radioactivity halflives from the excited state for some nuclei that are not yet available experimentally.Simultaneously,by analyzing the calculated results from these theoretical models,it was found that the half-lives are strongly dependent on Qand l.

Excited state refraction of C_(70)/toluene studied by using 4f coherent imaging system with phase object

Dynamic nonlinearities of C70/toluene solution are measured and analysed by an improved picosecond timeresolved pump-probe system based on a nonlinear imaging technique with phase object. The photophysical parameters are determined by the five-level model, which is adopted to interpret the experimental data. The change of refraction index per unit density of the excited state obtained by a numerically simulation is a critical factor to determine the nonlinear behaviour of C70 in picosecond time regime.

Time-dependent Density Functional Theory Study on the Electronically Excited States of N-Methylformamide in Aqueous Solution

Excited-state hydrogen-bonding dynamics of N-methylformamide （NMF） in water has been investigated by time-dependent density functional theory （TDDFT） method. The ground-state geometry optimizations were calculated by density functional theory （DFT） method, while the electronic transition energies and corresponding oscillation strengths of the low-lying electronically excited states of isolated NMF, water monomers and the hydrogen-bonded NMF-H 2 O were calculated by TDDFT method. According to Zhao＇s rule on the excited-state hydrogen bonding dynamics, our results demonstrate that the intermolecular hydrogen bond C=O···O-H is strengthened and weakened in different electronically excited states. The hydrogen bond strengthening and weakening in the electronically excited state plays an important role in the photophysics of NMF in solutions.

Temperature and hydrogen-like impurity effects on the excited state of the strong coupling bound polaron in a CsI quantum pseudodot

With hydrogen-like impurity（HLI） located in the center of Cs I quantum pseudodot（QPD） and by using the variational method of Pekar type（VMPT）, we investigate the first-excited state energy（FESE）, excitation energy and transition frequency of the strongly-coupled bound polaron in the present paper. Temperature effects on bound polaron properties are calculated by employing the quantum statistical theory（QST）. According to the present work＇s numerical results, the FESE, excitation energy and transition frequency decay（amplify） with raising temperature in the regime of lower（higher）temperature. They are decreasing functions of Coulomb impurity potential strength.

Variational Calculation of the Doubly-Excited States Nsnp of He-Like Ions via the Modified Atomic Orbitals Theory

In this paper, we have declined the formalism of the method of the Modified Atomic Orbital Theory (MAOT) applied to the calculations of energies of doubly excited states 2snp, 3snp, and 4snp Helium-like systems. Then we also applied the variational procedure of the Modified Atomic Orbital Theory to the computations of total energies, excitation energies of doubly-excited states 2snp, 3snp, 4snp types of Helium-like systems. The results obtained in this work are in good agreement with the experimental and theoretical values available.

Electron excitation from ground state to first excited state:Bohmian mechanics method

The excitation process of electrons from the ground state to the first excited state via the resonant laser pulse is investigated by the Bohmian mechanics method. It is found that the Bohmian particles far away from the nucleus are easier to be excited and are excited firstly, while the Bohmian particles in the ground state is subject to a strong quantum force at a certain moment, being excited, to the first excited state instantaneously. A detailed analysis for one of the trajectories is made, and finally we present the space and energy distribution of 2000 Bohmian particles at several typical instants and analyze their dynamical process at these moments.

Ultrafast Excited State Dynamics of Biliverdin Dimethyl Ester Coordinate with Zinc Ions

As one of the biological endogenous pigments,biliverdin(BV)and its dimethyl ester(BVE)have extremely weak uorescence in solution with quantum yield less than 0.01%.However,the situation reverses with the addition of zinc ions.The strength for uorescence of BVE-Zn^2+ complex is greatly enhanced and uorescence quantum yield can increase to5%.Herein,we studied ultrafast excited state dynamics of BVE-Zn^2+ complex in ethanol,npropanol,and DMSO solutions in order to reveal the mechanism of uorescence quantum yield enhancement.The results show that BVE can form a stable coordination complex with zinc with 1:1 stoichiometry in solution.BVE is structurally and energetically more stable in the complex.Using picosecond time-resolve uorescence and femtosecond transient absorption spectroscopy,we show that smaller non-radiative rate constant of BVE-Zn^2+ complex in DMSO is the key to increasing its uorescence quantum yield and the excited state decay mechanism is also revealed.These results provide valuable information about the uorescence property change after BVE binding to metal ions and may provide a guidance for the study of phytochromes or other uorescence proteins in which BV/BVE acts as chromophores.

Dynamics of the reaction of O with H_2 and its isotopic variants in different rotational excited states

Scalar properties and vector correlations of the reactions of O＋H2 →OH＋H, O＋HD→OH＋D, O＋DH→OD＋H, and O＋D2 -＋OD＋D at collision energies of 25 and 34.6 kcal/mole have been studied via the quasi-classical-trajectory （QCT） method based on a BMS1 potential energy surface （PES）. The generalized polarization-dependent differential cross section and the distributions of the dihedral angle at the collision energy of 34.6 kacl/mole are presented. The calculated results indicate that both the reagent rotational angular momentum and the mass factor have a significant influence on the scalar properties and vector correlations of the title reactions.

Mechanism of Excited State Double Proton Transfer in 2-Amino-3-Methoxypyridine and Acetic Acid Complex

The excited-state double-proton transfer （ESDPT） mechanism of 2-amino-3-methoxypyridine and acetic acid com- plex is studied by the density functional theory （DFT） and time-dependent DFT with CAM-B3LYP functional. The complex is connected through two different types of inter-molecular hydrogen bonds. After photo-excitation, both hydrogen bonds get strengthened, which can facilitate the ESDPT reaction. The scanned potential energy curve along the proton transfer coordinate indicates that the ESDPT reaction proceeds in a stepwise pattern.

Iterative solutions for low lying excited states of a class of SchrSdinger equation

The convergent iterative procedure for solving the groundstate Schrodinger equation is extended to derive the excitation energy and the wavefunction of the low-lying excited states. The method is applied to the one-dimensional quartic potential problem. The results show that the iterative solution converges rapidly when the coupling g is not too small.

Uncommon Emissions from Higher Excited State ~5D_J of Eu^(3+) in Rare-Earth Sr_2CeO_4 Host

Undoped and Eu3+-doped Sr2CeO4 luminescent materials were prepared by sol-gel method. The structure and uncommon photoluminescence of Sr2CeO4∶Eu3+ phosphors were investigated in detail by powder X-ray diffraction (XRD), Raman spectrum, and photoluminescence spectrum, respectively. The XRD results demonstrate that the as-prepared Sr2CeO4 phosphor is single phase and well crystallized. For Sr2CeO4∶Eu3+ phosphor, its excitation spectrum consists of a broad intense band from host and Eu3+-O2-charge transfer and a number of small peaks from Eu3+ ion. The broad emission band originated from Sr2CeO4 host and Eu3+ emission lines in the blue, green, and red regions coexist. Not only the characteristic transition lines from the lowest excited 5D0 level of Eu3+ but also those from higher energy levels 5DJ (J=1, 2) of Eu3+ ions are observed. These unusual luminescence properties result from the low vibration energy of Sr2CeO4 host-lattice and different energy transfer process from host to activator.

The theory and experiment of solute migration caused by excited state absorptions

Nonsymmetrical transition from reverse-saturable absorption （RSA） to saturable absorption （SA） caused by excited state absorption induced mass transport of the CuPcTs dissolved in dimethyl sulfoxide is observed in an open aperture Z-scan experiment with a 21-ps laser pulse. The nonsymmetrical transition from RSA to SA is ascribed neither to saturation of excited state absorption nor to thermal induced mass transport, the so-called Sorer effect. In our consideration, strong nonlinear absorption causes the rapid accumulation of the non-uniform kinetic energy of the solute molecules. The non-uniform kinetic field in turn causes the migration of the solute molecules. Additionally, an energy-gradient-induced mass transport theory is presented to interpret the experimental results, and the theoretical calculations are also taken to fit our experimental results.

Variational-integral perturbation corrections of some lower excited states for hydrogen atoms in magnetic fields

A variational-integral perturbation method（VIPM） is established by combining the variational perturbation with the integral perturbation.The first-order corrected wave functions are constructed,and the second-order energy corrections for the ground state and several lower excited states are calculated by applying the VIPM to the hydrogen atom in a strong uniform magnetic field.Our calculations demonstrated that the energy calculated by the VIPM only shows a negative value,which indicates that the VIPM method is more accurate than the other methods.Our study indicated that the VIPM can not only increase the accuracy of the results but also keep the convergence of the wave functions.

Theoretical investigation on the excited state intramolecular proton transfer in Me_2N substituted flavonoid by the time-dependent density functional theory method

Time-dependent density functional theory（TDDFT） method is used to investigate the details of the excited state intramolecular proton transfer（ESIPT） process and the mechanism for temperature effect on the Enol＊/Keto＊emission ratio for the Me2N-substited flavonoid（MNF） compound. The geometric structures of the S0 and S1 states are denoted as the Enol, Enol＊, and Keto＊. In addition, the absorption and fluorescence peaks are also calculated. It is noted that the calculated large Stokes shift is in good agreement with the experimental result. Furthermore, our results confirm that the ESIPT process happens upon photoexcitation, which is distinctly monitored by the formation and disappearance of the characteristic peaks of infrared（IR） spectra involved in the proton transfer and in the potential energy curves. Besides, the calculations of highest occupied molecular orbital（HOMO） and lowest unoccupied molecular orbital（LUMO） reveal that the electronegativity change of proton acceptor due to the intramolecular charge redistribution in the S1 state induces the ESIPT. Moreover, the thermodynamic calculation for the MNF shows that the Enol＊/Keto＊emission ratio decreasing with temperature increasing arises from the barrier lowering of ESIPT.