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Encyclopedia of Spectroscopy and Spectrometry || Ion Collision, Theory ☆
摘要： Collisions between an ion and neutral species result in a number of possible outcomes depending upon the chemical and physical properties of the two reactants, their relative velocities, and the impact parameter of their trajectories. These include elastic and inelastic scattering of the colliding particles, charge transfer (including dissociative charge transfer), atom abstraction, complex formation and dissociation of the colliding ion. Each of these reactions may be characterized in terms of their energy-dependent rate coefficients, cross sections and reaction kinetics. This article outlines a theoretical framework for discussing these processes that emphasizes simple models and classical mechanics. The discussion of collision processes has been divided into two categories: low-energy and high-energy thermal or quasi-thermal collisions. Experiments under conditions – swarms, drift tubes, chemical ionization and ion cyclotron resonance – are strongly influenced by long-range forces and often involve ‘capture collisions’ in which atom exchange and extensive energy exchange are common characteristics. High-energy collisions are typically impulsive, involve short-range intermolecular forces and are direct, fast processes.
关键词： Low-energy Collisions,Elastic and Inelastic Scattering,Reaction Kinetics,Theory,Complex Formation,Rate Coefficients,Charge Transfer,Atom Abstraction,High-energy Collisions,Ion Collision,Dissociation,Cross Sections
更新于2025-09-04 15:30:14
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Binding of hydrogen to phosphorus dopant in phosphorus-doped diamond surfaces: A density functional theory study
摘要： Although phosphorus is an n-type donor in diamond, H impurities can bind to and passivate P. Here, H binding to a P dopant in both diamond (0 0 1) and (1 1 1) surfaces is investigated by density functional theory. The energy calculations reveal the most stable P–H complex structures for each P-doped position. P–H binding energies are the lowest for the second P doped C layer among those for four investigated P-doped C layers. H migration from on-surface to P in the second C layer is exothermic, with an energy barrier of zero, whereas that from on-surface to P below the second C layer is endothermic, with an energy barrier greater than 0.95–7.09 eV. Thus, both of binding energy and migration calculations imply that P–H complex is more likely to form when P is doped in the second C layer than when P is doped below the second C layer. Moreover, H migration energy barrier from on-surface to P below the second C layer in the (1 1 1) surface is at least 0.85 eV greater than that in the (0 0 1) surface, which indicates that P–H complex is less likely to form in (1 1 1) surface than in (0 0 1) surface.
关键词： P–H complex,Hydrogen,Density functional theory,P-doped diamond
更新于2025-09-04 15:30:14
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Structural stability and electronic properties of XTO2 (X= Cu, Ag; T=Al, Cr): an ab initio study including X vacancies and Mg doping
摘要： Ab initio density functional theory-based calculations are used to study the structural and electronic properties of CuAlO2, AgAlO2, CuCrO2, and AgCrO2 transparent conducting oxides (TCOs). The hexagonal 2H delafossite polymorph is determined here to be one of the most stable polymorphs, by comparing total energies for different structural phases. The simple antiferromagnetic configuration is chosen to model magnetic effects in CuCrO2 and AgCrO2 due to it having one of the lowest ground state total energies and containing the most semiconductor like behavior of the magnetic configurations considered. Electronic structures of 2H CuAlO2 and AgAlO2 obtained from different approximations for the exchange-correlation functional, GGA (PBE), PBE+U, PBE+mBJ, PBE+mBJ+U, and the Hybrid HSE06 are compared. Supercells are employed to model 6.25% Cu and Ag vacancies, 3.13% O vacancies, and 6.25% Mg doping replacing Al and Cr, from which structural and electronic properties are obtained and used to predict on the effectiveness of these native defects and dopant on increasing the conductivity in all TCOs studied in this work. The obtained partial density of states for the pristine systems supports a model of hole conduction in the a – b plane, perpendicular to the O – X – O dumbbells of the delafossite structure. Additionally, the partial density of states of the defective and doped systems suggest a growth environment deficient in X and saturated in O may increase conductivity in these materials.
关键词： Delafossite,Density functional theory,Transparent conducting oxides,Mg doping,Structural stability,Ab initio,Vacancies,Electronic properties
更新于2025-09-04 15:30:14
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Tailoring the Linear and Second-Order Nonlinear Optical Responses of the Titanium-MIL-125 Metal-Organic Framework through Ligand Functionalization: A First Principles Study
摘要： Density functional theory calculations have been performed to investigate the linear and second order nonlinear optical (NLO) properties of titanium-based MIL-125 metal-organic frameworks in crystalline form, in which the 1,4-benzene-dicarboxylate (BDC) linkers are modified by introducing different functional groups or by extending BDC ligand to contain two (MIL-126) and three (MIL-127) benzene rings. Our results reveal that the functionalization of BDC linker tends to increase the dielectric constants and the magnitude of birefringence of MIL-125, especially for the aminated derivatives. Correspondingly, the incorporation of substituent group will improve the phase matching performance of MIL-125. As for the second harmonic generation (SHG) susceptibility, the SHG activity of the pristine MIL-125 is comparable to KDP, which can be attributed mostly to the contributions of TiO5(OH) octahedra. It is noted that after introducing substituent group into BDC linker, the organic part will have a remarkable influence on the SHG intensity. However, the specific effect on the NLO response is dependent on the type of functional group incorporated into BDC ligand, and only the inclusion of amine group that is strongly electron-donating can obviously enhance the SHG activity of MIL-125. In addition, MIL-126 and MIL-127 with longer aromatic linking unit are not suitable to act as NLO materials due to their poor phase matching abilities, but they are the promising candidates for the low dielectric constant materials. The present study can provide theoretical insights to design new second-order NLO materials based on MIL-125.
关键词： Nonlinear Optical Properties,Density Functional Theory,Hybrid Materials,Ligand Functionalization,Metal-Organic Framework,Plasmonics,Optical,Magnetic
更新于2025-09-04 15:30:14
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POLARIZATION TRANSFORMATION BY A HYPERBOLIC METAMATERIAL ON A METAL SUBSTRATE
摘要： In the present paper we focus on the study of polarization properties of biaxial metamaterial, which consist of alternate ferrite and semiconductor layers, located on an ideally conducted metal substrate. The system is placed into an external magnetic field along the boundaries of the layers. The effective medium theory is applied. Effective linear-to-elliptic polarization conversion has been shown, by means of physical and geometrical parameters of the system under consideration.
关键词： biaxial metamaterial,ferrite,linear-to-elliptic polarization conversion,metal substrate,polarization properties,semiconductor layers,external magnetic field,effective medium theory
更新于2025-09-04 15:30:14
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Applicability of Effective Medium Approximations to Modelling of Mesocrystal Optical Properties
摘要： Rigorous superposition T-matrix method is used to compute light interaction with mesocrystalline structures. The results are used to validate the applicability of effective medium theories for computing the effective optical constants of mesocrystal structures composed of optically isotropic materials. It is demonstrated that the Maxwell-Garnett theory can fit the rigorous simulation results with an average accuracy of 2%. The thus obtained refractive indexes can be used with any electromagnetic simulation software to represent the response of mesocrystals composed of optically small primary particles arranged into a cubic type lattice structures.
关键词： Mie scattering,numerical modelling,particles,mesocrystals,T-matrix,Maxwell-Garnett,light scattering,effective medium theory
更新于2025-09-04 15:30:14
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Collisional - radiative model of xenon plasma with calculated electron impact fine-structure excitation cross sections
摘要： Detailed electron impact excitation cross section results for xenon in the wide range of incident energy from threshold to 1000eV are calculated using relativistic distorted wave (RDW) theory. Various transitions from the ground 5p6 state to the excited 5p56s, 5p56p, 5p55d, 5p57s and 5p57p as well as among these excited states are considered. The relativistic Dirac-Fock multi-configuration wave functions for the ground and excited states of the xenon are obtained and used in the calculations. Where available our cross section results are compared with previously reported measurements and calculations. We have also fitted the calculated cross sections through analytical formulae for plasma modeling purposes. As an application, using the obtained cross sections, a collisional Radiative (C-R) model coupled with an optical emission measurement from the inductively coupled Xe plasma is developed and the extracted plasma parameters are reported.
关键词： relativistic distorted wave theory,Electron impact excitation,cross-sections,collisional radiative model
更新于2025-09-04 15:30:14
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Conserving approximations in cavity quantum electrodynamics: Implications for density functional theory of electron-photon systems
摘要： By analyzing the many-body problem for nonrelativistic electrons strongly coupled to photon modes of a microcavity I derive the exact momentum/force balance equation for cavity quantum electrodynamics. Implications of this equation for the electron self-energy and the exchange-correlation potential of the quantum electrodynamic time-dependent density functional (QED-TDDFT) are discussed. In particular I generalize the concept of (cid:2) derivability to construct approximations which ensure the correct momentum balance. It is shown that a recently proposed optimized effective potential approximation for QED-TDDFT is conserving, and its possible improvements are discussed.
关键词： cavity quantum electrodynamics,density functional theory,conserving approximations,momentum balance,electron-photon systems
更新于2025-09-04 15:30:14
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Heterodimer on MgO
摘要： We report on the magnetic properties of HoCo dimers as a model system for the smallest intermetallic compound of a lanthanide and a transition metal atom. The dimers are adsorbed on ultrathin MgO(100) films grown on Ag(100). New for 4f elements, we detect inelastic excitations with scanning tunneling spectroscopy and prove their magnetic origin by applying an external magnetic field. In combination with density functional theory and spin Hamiltonian analysis, we determine the magnetic level distribution, as well as sign and magnitude of the exchange interaction between the two atoms. In contrast to typical 4f ? 3d bulk compounds, we find ferromagnetic coupling in the dimer.
关键词： ferromagnetic coupling,heterodimer,density functional theory,spin excitations,scanning tunneling spectroscopy
更新于2025-09-04 15:30:14
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Effects of Varying the Benzannulation Site and π Conjugation of the Cyclometalating Ligand on the Photophysics and Reverse Saturable Absorption of Monocationic Iridium(III) Complexes
摘要： A series of monocationic iridium(III) complexes, [Ir(C^N)2(pqu)]+PF6? [pqu = 2-(pyridin-2-yl)quinoline, C^N = 2-phenylquinoline (1), 3-phenylisoquinoline (2), 1-phenylisoquinoline (3), benzo[h]quinoline (4), 2-(pyridin-2-yl)naphthalene (5), 1-(pyridin-2-yl)naphthalene (6), 2-(phenanthren-9-yl)pyridine (7), 2-phenylbenzo[g]quinoline (8), 2-(naphthalen-2-yl)quinoline (9), and 2-(naphthalen-2-yl)benzo[g]quinoline (10)], were synthesized in this work. These complexes bear C^N ligands with varied degrees of π conjugation and sites of benzannulation, allowing for elucidation of the effects of the benzannulation site at the C^N ligand on the photophysics of the complexes. Ultraviolet?visible (UV?vis) absorption and emission of the complexes were systematically investigated via spectroscopic techniques and time-dependent density functional theory calculations. Their triplet excited-state absorption and reverse saturable absorption (RSA) were studied by nanosecond transient absorption (TA) spectroscopy and nonlinear transmission techniques. The fusion of phenyl ring(s) to the phenyl ring or the 4 and 5 positions of the pyridyl ring of the C^N ligand resulted in red-shifted UV?vis absorption and emission spectra in complexes 2, 5?7, 9, and 10 compared to those of the parent complex 0, while their triplet lifetimes and emission quantum yields were significantly reduced. In contrast, the fusion of one phenyl ring to the other sites of the pyridyl group of the C^N ligand showed an insignificant impact on the energies of the lowest singlet (S1) and triplet (T1) excited states in complexes 1, 3, and 4 but noticeably affected their TA spectral features. The fusion of the naphthyl group to the 5 and 6 and positions at the pyridyl ring did not influence the S1 energy of complex 8 but altered the nature of the T1 states in 8 and 10 by switching them to the benzo[g]quinoline-localized 3π,π* state, which resulted in completely different emission and TA spectra in these two complexes. The site-dependent variations of the ground- and excited-state absorption induced strong but varied RSA from these complexes for 4.1-ns laser pulses at 532 nm, with the RSA strength decreasing in the trend of 3 > 7 ≈ 4 ≈ 9 ≈ 6 > 8 ≈ 1 ≈ 2 ≈ 5 > 10.
关键词： iridium(III) complexes,time-dependent density functional theory,spectroscopic techniques,photophysics,reverse saturable absorption,benzannulation
更新于2025-09-04 15:30:14