Adiabatic Potential Energy Surfaces and Photodissociation Mechanisms for Highly Excited States of H_(2)O

Full-dimensional adiabatic potential energy surfaces of the electronic ground state X and nine excited states A,I,B,C,D,D',D'',E' and F of H_(2)O molecule are developed at the level of internally contracted multireference configuration interaction with the Davidson correction.The potential energy surfaces are fitted by using Gaussian process regression combining permutation invariant polynomials.With a large selected active space and extra diffuse basis set to describe these Rydberg states,the calculated vertical excited energies and equilibrium geometries are in good agreement with the previous theoretical and experimental values.Compared with the well-investigated photodissociation of the first three low-lying states,both theoretical and experimental studies on higher states are still limited.In this work,we focus on all the three channels of the highly excited state,which are directly involved in the vacuum ultraviolet photodissociation of water.In particular,some conical intersections of D-E',E'-F,A-I and I-C states are clearly illustrated for the first time based on the newly developed potential energy surfaces(PESs).The nonadiabatic dissociation pathways for these excited states are discussed in detail,which may shed light on the photodissociation mechanisms for these highly excited states.

Quasiclassical Trajectory Study of Collisional Energy Transfer between Highly Excited C_6F_6 and N_2 ,O_2 and Ground State C_6F_6

Quasiclassical trajectory calculation (QCT) is used frequently for studying collisional energy transfer between highly vibrationally excited molecules and bath gases. In this paper, the QCT of the energy transfer between highly vibrationally excited C6F6 and N2 ,O2 and ground state C6F6 were performed. The results indicate that highly vibrationally excited C6F6 transferred vibrational energy to vibrational distribution of N2, O2 and ground state C6F6, so they are V-V energy transfer. Especially it is mainly V-V resonance energy transfer between excited C6F6 and ground state C6F6, excited C6F6 transfers more vibrational energy to ground state C6F6 than to N2 and O2 . The values of QCT , -〈DEvib〉of excited C6F6 are smaller than those of experiments.

Modified Atomic Orbital Calculations of Energy of the(2s^(2)^(1)S)Ground-State,the(2p^(2)^(1)D);(3d^(2)^(1)G)and(4f^(2)^(1)I)Doubly Excited States of Helium Isoelectronic Sequence from H-to Ca^(18+)

We report in this paper the ground-state energy 2s^(2)^(1)S and total energies of doubly excited states 2p^(2)^(1)D,3d^(2)^(1)D,4f^(2)^(1)I of the Helium isoelectronic sequence from H-to Ca^(18+).Calculations are performed using the Modified Atomic Orbital Theory(MAOT)in the framework of a variational procedure.The purpose of this study required a mathematical development of the Hamiltonian applied to Slater-type wave function[1]combining with Hylleraas-type wave function[2].The study leads to analytical expressions which are carried out under special MAXIMA computational program.This first proposed MAOT variational procedure,leads to accurate results in good agreement as well as with available other theoretical results than experimental data.In the present work,a new correlated wave function is presented to express analytically the total energies for the 2s21S ground state and each doubly 2p^(2)^(1)D,3d^(2)^(1)D,4f^(2)^(1)I excited states in the He-like systems.The present accurate data may be a useful guideline for future experimental and theoretical studies in the(nI^(2))systems.

Full-Dimensional Potential Energy Surfaces of Ground(X^(2)A′)and Excited(A^(2)A″)Electronic States of HCO and Absorption Spectrum

In this work,high-fidelity full-dimensional potential energy surfaces(PESs)of the ground(X^(2)A′)and first doublet excited(A^(2)A″)electronic states of HCO were constructed using neural network method.In total,4624 high-level ab initio points have been used which were calculated at Davidson corrected internally contracted MRCI-F12 level of theory with a quite large basis set(ACV5Z)without any scaling scheme.Compared with the results obtained from the scaled PESs of Ndenguéet al.,the absorption spectrum based on our PESs has slightly larger intensity,and the peak positions are shifted to smaller energy for dozens of wavenumbers.It is indicated that the scaling of potential energy may make some unpredictable difference on the dynamical results.However,the resonance energies based on those scaled PESs are slightly closer to the current available experimental values than ours.Nevertheless,the unscaled high-level PESs developed in this work might provide a platform for further experimental and theoretical photodissociation and collisional dynamic studies for HCO system.

Calculations Energy of the (<i>nl</i>²) ¹<i>L^π</i>Doubly Excited States of Two-Electron Systems via the Screening Constant by Unit Nuclear Charge Formalism

In this work, the total energies of doubly excited states (ns2) 1Se, (np2) 1De, (nd2) 1Ge, (nf2) 1Ie, (ng2) 1Ke, and (nh2) 1Me of the helium isoelectronic sequence with Z ≤ 10 are calculated in the framework of the variational method of the Screening Constant by Unit Nuclear Charge (SCUNC). These calculations are performed using a new wavefunction correlated to Hylleraas-type. The possibility of using the SCUNC method in the investigation of high-lying Doubly Excited States(DES) in two-electron systems is demonstrated in the present work in the case of the (nl2) 1Lπ doubly excited states, where accurate total energies are tabulated up to n = 20. All the results obtained in this paper are in agreement with the values of the available literature and may be useful for future experimental and theoretical studies on the doubly excited (nl2) 1Lπ states of two-electron systems.

Ab initio calculation on accurate analytic potential energy functions and harmonic frequencies of c^3∑g^＋ and B^1-Пu states of dimer 7Li2

The comparison between single-point energy scanning （SPES） and geometry optimization （OPT） in determining the equilibrium geometries of c^3∑g^＋ and B^1-Пu states of dimer 7Li2 is made at numerous basis sets by using a symmetryadapted-cluster configuration-interaztion （SAC-CI） method in the Gaussian 03 program package. In this paper the difference of the equilibrium geometries obtained by SPES and by OPT is reported. The results obtained by SPES are found to be more reasonable than those obtained by OPT in full active space at the present SAC-CI level of theory. And the conclusion is attained that the cc-PVTZ is a most suitable basis set for these states. The calculated dissociation energies and equilibrium geometries are 0.8818 eV and 0.3090 nm for c^3∑g^＋ state, and 0.3668 eV and 0.2932 nm for B^1-Пu state respectively. The potential energy curves are calculated over a wide internuclear distance range from about 2.5α0 to 37α0 and have a least-squares fit into the Murrell-Sorbie function. According to the calculated analytic potential energy functions, the harmonic frequencies （We） and other spectroscopic data （ωeXe, Be and αe） are calculated. Comparison of the theoretical determinations at present work with the experiments and other theories clearly shows that the present work is the most complete effort and thus represents an improvement over previous theoretical results.

Study of the excitation properties of the Si_3 O_2 cluster under an external electric field

The structure of the Si3Ox （x =2, 3） cluster is investigated; we find that the geometry of Si3O2 is similar to that of Si3O3 except for the oxygen-deficient defect structure （Si-Si band） which exists only in the Si3O2 cluster. It is known that oxygen-deficient defects are used to explain visible luminescence （especially blue, purple and ultraviolet light） from silicon-based materials, which are directly bound up with the excited states of the molecules. Therefore the excitation properties of the two clusters are also studied. Our results show that the absorption spectrum of Si3O2 is concentrated in the visible light region. In contrast, the absorption spectrum of Si3O3 is mainly located in the ultraviolet light region. The calculations are perfectly consistent with experimental data and also support the theory of oxygen-deficient defects.

Green, orange, and red upconversion luminescence in Nd^(3+)/Yb^(3+): Cs_2NaGdCl_6 powders under 785 nm laser excitation

Nd^3＋：Cs2NaGdCl6 and Nd^3＋, Yb^3＋：Cs2NaGdCl6 polycrystalline powder samples were prepared by Morss method E. Under 785 nm semiconductor laser pumping, the upconversion luminescence of Nd^3＋ ions in Cs2NaGdCl6 was investigated at room temperature, and three upconversion emissions near 538 nm （Green）, 603 nm （Orange）, and 675 nm （Red） were observed and assigned to ^4G7/2→^4I9/2, （^4G7/2→^4I11/2; ^4G5/2→^4I9/2）, and （^4G7/2→^4I13/2; ^4G5/2→^4I11/2 ）, respectively. The dependences of these upconverted emissions on laser power and Nd^3＋ ion concentration were investigated, to explore the upconversion mechanism. The effect of doping Yb^3＋ ions on the upconversion luminescence of Nd^3＋ in Cs2NaGdCl6 was also studied under 785 nm laser excitation. The energy transfer processes were discussed as the possible mechanism for the above upconversion emissions.

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.

Four-Level Decay Model of^6P_(7/2) Excited State of Eu^(2+) Ion in KMgF_3

A four-level decay model of ~6P_(7/2) excited state of Eu^(2+_ ion in KMgF_3: Eu^(2+) has been proposed. The decay profiles of the ~6P_(7/2) excited state of Eu^(2+) are two exponential and the physical implication of each term in the fit equation responsible for the model is interpreted. The data obtained spectroscopically are in good agreement with the fit results.

Six-Dimensional ab initio Potential Energy Surface and Bound States for He-H2S Complex

We present a new six-dimensional potential energy surface for He-H2S including the intramolecular Q1,Q2,and Q3 normal modes for theν1 symmetric stretching,ν2 bending andν3 asymmetric stretching of H2S.The potential was calculated at the coupled-cluster singles and doubles with noniterative inclusion of connected triples[CCSD(T)]-F12a level with augmented correlation-consistent polarized-valence triple-zeta(aug-cc-p VTZ)basis set plus the midpoint bond function(3s3p2d1f1g).Three vibrationally averaged potentials with H2S at the vibrational ground stateν1 as well as the excited statesν2 andν3 were generated from the integration of the six-dimensional potential over the Q1,Q2 and Q3 coordinates.Each potential has a planar T-shaped global minimum,a planar local minimum,two inplane saddle points as well as an out-plane saddle point.The global minimum is located at R=3.46A,θ=109.9° andφ=0.0° with a well depth of 35.301 cm^-1.The radial discrete variable representation/angular finite basis representation method and the Lanczos algorithm were employed to calculate the rovibrational energy levels.The calculated band origins are blue-shifted(0.025 cm^-1 and 0.031 cm^-1)and(0.041 cm^-1 and 0.060 cm^-1)for He-(paraH2S)and He-(ortho-H2S)in theν2 andν3 region of the H2S molecule,respectively.

A POST-SCF STUDY ON THE EXCITED STATES OF MgH_2

The calculations on the ground state and two excited states3B2,BIB2 of MgH2 system are carried out by using (Second Order Configuration Interaction)method.For each state,the electronic structure and related properties are investigated,The vibration and localization analyses are also performed.The reasonable explanations of bending geometries for the excited states are given.

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.

Critical Behavior of the Energy Gap and Its Relation with the Berry Phase Close to the Excited State Quantum Phase Transition in the Lipkin Model

In our previous work [Phys. Rev. A 85 （2012） 044102], we studied the Berry phase of the ground state and exited states in the Lipkin model. In this work, using the Hellmann-Feynman theorem, we derive the relation between the energy gap and the Berry phase closed to the excited state quantum phase transition （ESQPT） in the Lipkin model. It is found that the energy gap is approximately linearly dependent on the Berry phase being closed to the ESQPT for large N. As a result, the critical behavior of the energy gap is similar to that of the Berry phase. In addition, we also perform a semiclassical qualitative analysis about the critical behavior of the energy gap.

Studies on heteronuclear diatomic molecular dissociation energies using algebraic energy method

The algebraic energy method （AEM） is applied to the study of molecular dissociation energy De for 11 heteronuclear diatomic electronic states： a^3∑＋ state of NaK, X^2∑＋ state of XeBr, X^2∑＋ state of HgI, X^1∑＋ state of LiH, A3∏（1） state of IC1, X^1∑＋ state of CsH, A（3∏1） and B0＋（3∏） states of CIF, 21∏ state of KRb, X^1∑＋ state of CO, and c^3∑＋ state of NaK molecule. The results show that the values of De computed by using the AEM are satisfactorily accurate compared with experimental ones. The AEM can serve as an economic and useful tool to generate a reliable De within an allowed experimental error for the electronic states whose molecular dissociation energies are unavailable from the existing literature

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.

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.

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.

Ab initio investigation of excited state dual hydrogen bonding interactions and proton transfer mechanism for novel oxazoline compound

Owing to the importance of excited state dynamical relaxation, the excited state intramolecular proton transfer(ESIPT) mechanism for a novel compound containing dual hydrogen bond(abbreviated as "1-enol") is studied in this work.Using density functional theory(DFT) and time-dependent density functional theory(TDDFT) method, the experimental electronic spectra can be reproduced for 1-enol compound. We first verify the formation of dual intramolecular hydrogen bonds, and then confirm that the dual hydrogen bond should be strengthened in the first excited state. The photo-excitation process is analyzed by using frontier molecular orbital(HOMO and LUMO) for 1-enol compound. The obvious intramolecular charge transfer(ICT) provides the driving force to effectively facilitate the ESIPT process in the S1 state. Exploration of the constructed S0-state and S1-state potential energy surface(PES) reveals that only the excited state intramolecular single proton transfer occurs for 1-enol system, which makes up for the deficiencies in previous experiment.