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Two- and Three-Photon Partial Photoionization Cross Sections of Li+, Ne8+ and Ar16+ under XUV Radiation
摘要： In this work, we present the photon energy dependence of the two- and three-photon cross sections of the two-electron Li+, Ne8+ and Ar16+ ions, following photoionization from their ground state. The expressions for the cross sections are based on the lowest-order (non-vanishing) perturbation theory for the electric field, while the calculations are made with the use of an ab initio configuration interaction method. The ionization cross section is dominated by pronounced single photon resonances in addition to peaks associated with doubly excited resonances. In the case of two-photon ionization, and in the non-resonant part of the cross section, we find that the 1D ionization channel overwhelms the 1S one. We also observe that, as one moves from the lowest atomic number ion, namely Li+, to the highest atomic number ion, namely Ar16+, the cross sections generally decrease.
关键词： free-electron laser,X-ray radiation,cross sections,lowest-order perturbation theory,multiphoton ionization
更新于2025-09-23 15:23:52
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Application of Karpman-Maslov-Solov’ev soliton perturbation theory to systems with distributed gain or losses
摘要： We analyze the most important ideas of the Karpman-Maslov-Solov’ev soliton perturbation theory, and based on it, we solve analytically the long-standing problem of the Schr?dinger soliton interactions in the systems with distributed losses or gain. Our analytical results do give a quite good qualitative and quantitative check of the numerical results known so far. Unexpected and nontrivial result consists in the fact that the relative soliton separation depends on the accumulated (integrated) losses or gain.
关键词： Karpman-Maslov-Solov’ev soliton perturbation theory,Distributed losses or gain,Soliton interactions
更新于2025-09-23 15:23:52
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Vectorial perturbation theory for axisymmetric whispering gallery resonators
摘要： We propose a vectorial perturbation theory for axially symmetric, generally nonspherical whispering gallery resonators made of isotropic and anisotropic optical materials. It is based on analysis of the leading terms in the coupled equations for independent light-field components, as derived from Maxwell's equations, and true boundary conditions. Strong localization of the whispering gallery modes (WGMs) near the resonator rim, controlled by the azimuth modal number m, is the main prerequisite for our analysis. The theory gives high-precision expressions for the WGM frequencies and modal functions, including the evanescent effects. One of important applications of the theory is analysis of anticrossings of the WGM resonances in anisotropic resonators detected in experiments. Simple relations for the frequency avoidance gaps during the anticrossings are derived and compared with experimental data obtained in lithium-niobate-based WGM resonators. We show also that the vectorial effects substantially restrict the field of applicability of the scalar WGM models.
关键词： frequency avoidance gaps,whispering gallery resonators,anisotropic materials,vectorial perturbation theory,anticrossings
更新于2025-09-23 15:23:52
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Diagrammatic approach to nonlinear optical response with application to Weyl semimetals
摘要： Nonlinear optical responses are a crucial probe of physical systems including periodic solids. In the absence of electron-electron interactions, they are calculable with standard perturbation theory starting from the band structure of Bloch electrons, but the resulting formulas are often large and unwieldy, involving many energy denominators from intermediate states. This work gives a Feynman diagram approach to calculating nonlinear responses. This diagrammatic method is a systematic way to perform perturbation theory, which often offers shorter derivations and also provides a natural interpretation of nonlinear responses in terms of physical processes. Applying this method to second-order responses concisely reproduces formulas for the second-order-harmonic shift current. We then apply this method to third-order responses and derive formulas for third-order-harmonic generation and self-focusing of light, which can be directly applied to tight-binding models. Third-order responses in the semiclassical regime include a Berry curvature quadrupole term, whose importance is discussed including symmetry considerations and when the Berry curvature quadrupole becomes the leading contribution. The method is applied to compute third-order optical responses for a model Weyl semimetal, where we find a new topological contribution that diverges in a clean material, as well as resonances with a peculiar linear character.
关键词： Weyl semimetals,perturbation theory,Berry curvature,nonlinear optical responses,Feynman diagrams
更新于2025-09-23 15:23:52
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Nature of the excited states of layered systems and molecular excimers: Exciplex states and their dependence on structure
摘要： Weakly bound systems, like noble-gas dimers or two-dimensional layered materials (graphite, hexagonal boron nitride, or transition-metal dichalcogenides), exhibit excited electronic states of a particular nature. These so-called exciplex states combine on-site (or intralayer) and charge-transfer (or interlayer) configurations in a well-balanced way. We show by ab initio many-body perturbation theory that the energy and composition of the exciplex states depend sensitively on the bond length or interlayer distance of the material. When the constituents approach each other, the charge-transfer contribution increases and the excitation is redshifted to lower energy. If the system is excited into the exciplex state, then a covalent-like bond results. In consequence, noble-gas dimers form excimer complexes, while layered materials exhibit interlayer contraction.
关键词： charge-transfer excitations,many-body perturbation theory,interlayer contraction,exciplex states,layered systems
更新于2025-09-23 15:22:29
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ISA-Pol: distributed polarizabilities and dispersion models from a basis-space implementation of the iterated stockholder atoms procedure
摘要： Recently, we have developed a robust, basis-space implementation of the iterated stockholder atoms (BS-ISA) approach for defining atoms in a molecule. This approach has been shown to yield rapidly convergent distributed multipole expansions with a well-defined basis set limit. Here we use this method as the basis of a new approach, termed ISA-Pol, for obtaining non-local distributed frequency-dependent polarizabilities. We demonstrate how ISA-Pol can be combined with localization methods to obtain distributed dispersion models that share the many unique properties of the ISA: these models have a well-defined basis set limit, lead to very accurate dispersion energies, and, remarkably, satisfy commonly used combination rules to a good accuracy. As these models are based on the ISA, they can be expected to respond to chemical and physical changes naturally, and thus, they may serve as the basis for the next generation of polarization and dispersion models for ab initio force-field development.
关键词： Intermolecular interactions,Symmetry-adapted perturbation theory,Distributed polarizabilities,Distribution algorithms,Atoms in a molecule,Dispersion models,van der Waals
更新于2025-09-23 15:21:21
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Nonlinear Optics || Molecular Origin of the Nonlinear Optical Response
摘要： In Chapter 3, we presented a general quantum-mechanical theory of the nonlinear optical susceptibility. This calculation was based on time-dependent perturbation theory and led to explicit predictions for the complete frequency dependence of the linear and nonlinear optical susceptibilities. Unfortunately, however, these quantum-mechanical expressions are typically far too complicated to be of use for practical calculations. In this chapter we review some of the simpler approaches that have been implemented to develop an understanding of the nonlinear optical characteristics of various materials. Many of these approaches are based on understanding the optical properties at the molecular level. We also present brief descriptions of the nonlinear optical characteristics of conjugated polymers, chiral molecules, and liquid crystals.
关键词： chiral molecules,nonlinear optical susceptibility,liquid crystals,quantum-mechanical theory,conjugated polymers,time-dependent perturbation theory
更新于2025-09-23 15:21:01
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Plasmonic performance of Au <sub/>x</sub> Ag <sub/>y</sub> Cu <sub/>1a??xa??y</sub> alloys from many-body perturbation theory
摘要： We present a detailed appraisal of the optical and plasmonic properties of ordered alloys of the form AuxAgyCu1-x-y, as predicted by means of first-principles many-body perturbation theory augmented by a semi-empirical Drude–Lorentz model. In benchmark simulations on elemental Au, Ag, and Cu, we find that the random-phase approximation (RPA) fails to accurately describe inter-band transitions when it is built upon semi-local approximate Kohn–Sham density-functional theory band-structures. We show that non-local electronic exchange-correlation interactions sufficient to correct this, particularly for the fully-filled, relatively narrow d-bands which contribute strongly throughout the low-energy spectral range (0–6 eV), may be modeled very expediently using band-stretching operators that imitate the effect of a perturbative G0W0 self-energy correction incorporating quasiparticle (QP) mass renormalization. We thereby establish a convenient work-flow for carrying out approximated G0W0 + RPA spectroscopic calculations on alloys and, in particular here, we have considered alloy concentrations down to 12.5% in AuxAgyCu1-x-y, including all possible crystallographic orderings of face-centred cubic type. We develop a pragmatic procedure for calculating the Drude plasmon frequency from first principles, including self-energy effects, as well as a semi-empirical scheme for interpolating the plasmon inverse lifetimes between stoichiometries. A distinctive M-shaped profile is observed in both quantities for binary alloys, in qualitative agreement with previous experimental findings. A range of optical and plasmonic figures of merit are discussed, and plotted for ordered AuxAgyCu1-x-y at three representative solid-state laser wavelengths. On this basis, we predict that certain compositions may offer improved performance over elemental Au for particular application types. We predict that while the loss functions for both bulk and surface plasmons are typically diminished in strength through binary alloying, certain stoichiometric ratios may exhibit higher-quality (longer-lived) localized surface-plasmons and surface-plasmon polaritons, at technologically-relevant wavelengths, than those in elemental Au.
关键词： alloy design for plasmonics,theoretical spectroscopy,many-body perturbation theory
更新于2025-09-23 15:21:01
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Third-Order Unitary Coupled Cluster (UCC3) for Excited Electronic States: Efficient Implementation and Benchmarking
摘要： The efficient implementation of the third-order unitary coupled-cluster scheme (UCC3) for the calculation of excited electronic states is reported. The UCC3 scheme and its second-order UCC2 variant have been benchmarked and compared to Jacquemin’s recently introduced as well as Thiel’s well-established benchmark sets for excitation energies and oscillator strengths. For the latter, the calculation of 134 excited singlet and 71 excited triplet states of 28 small to medium-sized organic molecules has revealed that UCC2 exhibits a mean error and standard deviation of 0.36 ± 0.41 eV for singlet states and 0.22 ± 0.21 eV for triplet states, whereas UCC3 revealed an accuracy of 0.06 ± 0.27 eV for singlet and ?0.22 ± 0.15 eV for triplet states. Additionally, the oscillator strengths obtained with effective transition moments correct through second order in perturbation theory are in very good agreement with literature data.
关键词： perturbation theory,unitary coupled-cluster,oscillator strengths,excited electronic states,benchmarking
更新于2025-09-23 15:21:01
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Cyclic versus straight chain oligofuran as sensor: A detailed DFT study
摘要： This study is a novel approach for exploring the sensitivity and selectivity of cyclic oligofuran (5/6/7CF) toward gaseous analytes and their comparison with straight chain analogues (5/6/7SF). The work is not only vital to understand the superior sensitivity but also for rational design of new sensors based on cyclic ring structures of oligofuran. Interaction of cyclic and straight chain oligofuran with NH3, CO, CO2, N2H4, HCN, H2O2, H2S, CH4, CH3OH, SO2, SO3 and H2O analytes is studied via DFT calculation at B3LYP-D3/6-31++G (d, p) level of theory. The sensitivity and selectivity are illustrated by the energetic parameters (Ebind, SAPT0 energies, NCI analysis) electronic properties (H-L gap, percentage of average energy gap, CHELPG charge transfer, DOS spectra) and UV-Vis analysis. All these properties are simulated at B3LYP/6-31G (d) level of theory while UV-Vis is calculated at TD-DFT method. Cyclic oligofuran has high binding energy with analytes compared to 5/6/7SF which corresponds the higher sensitivity of 5/6/7CF. Furthermore, the cyclization of oligofuran significantly improve the sensitivity and selectivity of the system. Alteration in electronic properties of 5/6/7CF and 5/6/7SF is remarkably high upon complexation with SO2 and SO3. Further the stability of rings (5, 6 and 7 membered cyclic oligofurans) and their SO3 complexes is also confirmed by molecular dynamics calculations. The finding of the work clearly suggests that the cyclic geometry enhances not only sensitivity but also selectivity of conducting polymers (oligofuran).
关键词： Oligofuran,Noncovalent interaction index (NCI),Density Functional Theory (DFT),CHELPG charge transfer,Symmetry adopted perturbation theory (SAPT)
更新于2025-09-23 15:19:57