Formation of transient pairs of F and H centers at next nearest neighbor sites in alkali chloride crystals studied by the time delayed double excitation spectroscopy in picosecond range

Abstract

By making use of the time delayed double excitation spectroscopy, transient absorption spectra just after the excitation of self-trapped excitons (STE) from the lowest triplet state to higher excited states have been observed to find the transient F-H center pair [F-H]. Absorption bands due to transient [F-H] appeared as a doublet peaking at 2.70eV and 2.86eV (NaCl), at 2.25eV and 2.38eV (KCl) and at 1.97eV and 2.09eV (RbCl) at 108ps after the excitation. The ratio of peak heights between bands at low and high energy sides was 2:1 in all crystals. The results were tentatively understood by a recent theory for the STE by Song et al. (1987).     

Optical properties and stable,broadly tunable cw laser operation of new FA-type centers in Tl+-doped alkali halides

A new group of complex color centers with F_A-type properties, involving simple center production and high thermal and optical stabilities, has been found in six Tl⁺-doped alkali halides: NaCl, KCl, RbCl, KBr, RbBr and RbI. In its first tested examples, KCl and KBr, broadly tunable cw laser operation over the 1.4 to 1.7 μm range has been obtained, with output powers in the 100 mW range. In contrast to already existing F⁺₂ and F⁺₂-like centers, operating in the same wavelength range, the new F_A(Tl⁺) lasers are optically stable and do not show any bleaching effects under laser operation.     

The lifetime of the 2pπu → 1sσg transition of the F2+ center in KCl

The lifetime of the 2pπ_u → 1sσ_g transition for the F₂⁺ center in KCl has been measured (15.8 ± 0.7 ns at 8 K) and found to be constant over the temperature range (8–90 K) investigated. No contradiction is found with the Aegerter and Lüty quantum yield data. A forecast for the lifetime of the 2pσ_u → 1sσ_g transition is also made, within the framework of the H₂⁺ model for the F₂⁺ center in alkali halides.     

RAMAN STUDY ON (Pb) CENTERS IN SINGLE CRYSTALS OF ALKALI HALIDES DOPED WITH LEAD

Low frequency modes were observed in a series of alkali halides doped with lead after X-irradiation at 77K. The peak positions of the Raman signals are at 34cm^-1 for NaCl:Pb²⁺, 30cm^-1 for KCl:Pb²⁺,28cm^-1 for RbCl:Pb²⁺ and 22cm^-1 for KBr:Pb²⁺. They are assigned to the inelastic light scattering caused by the local vibration of X^-_i (Pb⁺) center, which consists of an interstitial halogen ion stabilized by a substitutional ion Pb⁺ . Polarized Raman measurements and Behavior Typer(BT) analysis show that the symmetry of the X^-_i (Pb⁺) center belongs to the point group C_3v A structure model of the X^-_i (Pb⁺) center is proposed based on the Raman data and the result of BT analysis.     

Spectroscopy of the a3Σu + state and the coupling to the X1Σg + state of K2

We report on high resolution Fourier-transform spectroscopy of fluorescence to the a³Σ_u ⁺ state induced by two-photon or two-step excitation from the X¹Σ_g ⁺ state to the 2³Π_g state in the molecule K₂. These spectroscopic data are combined with recent results of Feshbach resonances and two-color photoassociation spectra for deriving the potential curves of X¹Σ_g ⁺ and a³Σ_u ⁺ up to the asymptote. The precise relative position of the triplet levels with respect to the singlet levels was achieved by including the excitation energies from the X¹Σ_g ⁺ state to the 2³Π_g state and the frequencies of the fluorescence down to the a³Σ_u ⁺ state in the simultaneous fit of both potentials. The derived precise potential curves allow for reliable modeling of cold collisions of pairs of potassium atoms in their ²S ground state. Electronic supplementary material Supplementary Online Material     

Selective non-radiative transitions at excited states of the self-trapped exciton in alkali halides

Generation of F-H pairs and σ-luminescence induced by excitation of the self-trapped excitons with polarized light causing the 1s→ 2p transitions has been measured. The results were analyzed based on the assumption that the non-radiative transitions that follow photoexcitation depend only on the state reached by the excitation, irrespective of the photon energy of the excitation. The absence of the dependence on exciting photon energy of the effective yield of removal from the triplet manifold after excitation to each substate obtained from the analysis proves that the above assumption is valid. The relative non-radiative transition probabilities between the 2p substates and from the 2p-substates to the lowest triplet state, the F-H pair, the σ-luminescent state and the ground state were obtained. It is shown that the de-excitation channels from each substate are substantially different from each other. The following transitions are found to have high probabilities: from the B_1g state to the F-H pairs in KCl and KBr, from theA_g state to the σ-luminescent state and the lowest triplet state in KBr and to the lowest triplet state in KCl and from the B_2g state to the B_1g state in KCl and KBr, where A_g, B_1g and B_2g denote the states with the electron excited to the σ_u orbital, the π_u orbital lying in the (100) plane in which the (halogen)₂^?-molecular ion is situated and the other π_u orbital, respectively. The mechanisms of these non-radiative transitions were discussed.     

Dipole moment functions for electronic transitions from ion-pair states of the second tier of molecular iodine

The emission spectra caused by the transitions from the ion-pair states and f0 _g ⁺ and G1_g of the I₂ molecule are obtained by excitation of individual rovibronic levels of the molecule by the method of optical-optical double resonance. The emission spectra from the state F0 _u ⁺ populated due to collisions I₂(f) + I₂(X) are also measured. By modeling the experimental emission spectra, the dipole moment functions for the electronic transitions f _g ⁺ -B0 _u ⁺ , A0 _u ⁺ , and B″0 _u ⁺ ; G1_g-A0 _u ⁺ and B″0 _u ⁺ ; and F0 _u ⁺ -X0 _g ⁺ and a′0 _g ⁺ of the iodine molecule are reconstructed.     

X形色心激光谐振腔参数的确定及类F2+型色心激光运转

文中,针对X形谐振腔的特点及结合纵向泵浦理论,分析了X形谐振腔几何参数的确定条件和模式匹配条件;根据有关NaCl(OH^-):(F₂⁺)_H和KCl(Na⁺,OH^-):(F₂⁺)AH色心激光的主要研究结果,分析了提高色心激光输出效率的可能途径.     

Ab initio MRD-CI investigation of the electronic spectrum of glyoxal (CHO)2

Multireference configuration interaction (MRD-CI) calculations are used to compute the electronic spectrum of glyoxal (CHO)₂, a key species in atmospheric chemistry. The calculations place the first dipole-allowed transition 1¹A_u←X¹A_g at 2.80?eV (442.8?nm) with an oscillator strength of 0.0002 and the dipole forbidden 1¹B_g?←?X¹A_g transition at 4.22?eV (293.8?nm), in accordance with prior experiments. In addition, a much stronger transition (3¹B_u?←?X¹A_g) at 8.51?eV (145.7?nm) is predicted, which has not yet been reported in the literature. This transition corresponds to 1b_g?→?2a_u excitation and can be characterized as π(CO)?→?π?(CO) type in accordance with the computed relatively large oscillator strength f?=?0.38. The corresponding triplet states are also computed.     

Threshold energy electron impact excitation of carbon dioxide and carbon disulphide

The threshold energy electron impact excitation spectra of CO₂ and CS₂ have been studied using the sulfur hexafluoride scavenger technique. The main results are triplet state excitation and autoionisation of negative ions associated with resonant excited states of the molecules. This confirms previous data concerning diatomic molecules. Furthermore, transitions such as ¹Π_g?X¹Σ_g⁺ and ¹Π_u?X ¹Σ_g⁺ are only weakly induced by low energy electrons, while the corresponding triplet excitations are probably more easily produced. Structures at 5.6, 6.1 and 6.6 eV observed in CS₂ are due to negative ions and/or to ³Π_u, ³Π_g excitation.The autoionisation of CO₂^?(X²Π_u) proceeds also by ejection of a thermal energy electron and leads to highly excited vibrational levels (3–5 eV) of the ground electronic state of CO₂.     

Fluorescence spectra of matrix-isolated Se2

Laser induced fluorescence spectra are reported for samples of natural selenium and of the separated ⁷⁸Se and ⁸⁰Se isotopes in Ar and Kr matrices. The B(0_u⁺) → X(0_g⁺) and B(1_u) → X(1_g) systems of Se₂, already known in the gas, are observed by both single photon and biphotonic excitation considerably red-shifted in the matrices. The A(0_u⁺) → X(0_g⁺) emission of Se₂, not observed in the vapor, appears in the matrices with its origin near 15 100 cm^?1. Another system with ν₀₀ = 24 429 cm^?1 and ω″_e = 538 cm^?1 is thought to belong most probably to some polyatomic Se_n molecule.     

Absorption of Ni-centres in alkali chlorides

Absorption spectra of Ni²⁺ doped NaCl, KCl, and RbCl were measured in the spectral range from 55,000 to 5,000 cm^?1. The bands in the UV region are ascribed to the transition 3t _1u(σ, π)→3e _g(σ) of NiCl₆ complex ion. The connection of the intensity of charge transfer andd-d transitions has been discussed.     

Fine and hyperfine structure in 14N2+

The fine and hyperfine structure of ¹⁴N₂⁺ has been observed in 31 rotational lines of the (0, 1) band of the B²Σ_u⁺-X²Σ_g⁺ system using the method of Doppler-tuned laser-induced fluorescence on a molecular ion beam. The spin-rotation constants (γ′, γ″, γ′_J) are in good agreement with other experiments in which the hyperfine structure was not resolved. The Fermi-contact (b′_F, b″_F) and dipolar (t′, t″) hyperfine coupling constants are in reasonably good agreement with values calculated from ab initio wavefunctions. The least-squares experimental values in MHz are γ″ = 279.1(6), γ′ = 726.4(6), γ′_J = ?0.0460(2), b″_F = 105(4), b′_F = 708(3), t″ = 49(6), and t′ = 26(5).     

Surface‐enhanced Raman spectroscopy of indanthrone and flavanthrone

The normal Raman and surface‐enhanced Raman scattering (SERS) spectra of flavanthrone and indanthrone were obtained at several excitation wavelengths. The spectral assignments were aided by density functional calculations. Since both molecules have very high symmetry (C_2h) including a center of inversion, we expect that the modes of u symmetry will be forbidden in the normal Raman spectrum. However, proximity to the surface causes special SERS enhancement of several of the b_u modes, along with somewhat weaker enhancement of the a_u and b_g modes. Copyright © 2009 John Wiley & Sons, Ltd.     

Li2分子自旋一致激发态a3Σ+u和b3Πu的分析势能函数的从头算

使用对称性匹配簇-组态相互作用方法首次计算了Li₂分子自旋一致激发态a³Σ⁺_u和b³Π_u的离解能、平衡几何及其谐振频率。使用最小二乘法、利用Murrell-Sorbie函数形式拟合出了Li₂分子三重态的第一激发态a³Σ⁺_u 和第二激发态b³Π_u的完整势能函数，并计算了这两个态的光谱常数 (B_e, α_e, ω_e 和 ω_eχ_e) 和力常数 (f₂, f₃和f₄)。得到了Murrell-Sorbie函数形式既适用于基态、又适用于激发态的结论。将计算得到的激发态（a³Σ⁺_u和b³Π_u）的离解能、平衡几何及其谐振频率与实验结果及其它理论计算结果进行了比较。从比较的结果中可以清楚地看出，本文的计算结果在计算精度方面有很大的改进。     

Effect of M+2 ions on the luminescence of Pb+2 in NaCl

The effect of additional doping with M⁺² ions on the luminescence of NaCl:Pb⁺² has been systematically investigated. The data show that the same two emissions at 310 and 380 nm are observed for mixed Pb⁺²-M⁺² clusters as for Pb⁺² aggregates. Moreover, the presence of a M⁺² ion associated to a Pb⁺² ion in a mixed cluster shifts the 310 nm emission (predominantly observed for free Pb⁺²-vacancy dipoles) to 380 nm. The results are consistent with the Fukuda's model, involving an emission at 310 nm from tetragonal (T) minima in the adiabatic potential energy surface (APES) and another one from less symmetry (X) minima at 380 nm. The data for NaCl:Pb⁺²:Mn⁺², show that an excitation transfer is taking place from the X minima of the ³T_1u state of Pb⁺² to Mn⁺².     

Accurate theoretical spectroscopic investigations of the 20 Λ-S and 58 Ω states of O2+ cation including the spin–orbit coupling effect

The potential energy curves (PECs) are calculated for the 20 Λ-S states (X²Π_g, A²Π_u, B²Σ^?_g, a⁴Π_u, b⁴Σ^?_g, b′⁴Π_g, c⁴Σ^?_u, 1²Σ⁺_g, 1²Σ⁺_u, 1²Σ^?_u, 1⁴Σ⁺_g, 1⁴Σ⁺_u, 1⁴Δ_g, 1⁴Δ_u, 1⁶Σ⁺_g, 1⁶Σ⁺_u, 1⁶Π_g, 1⁶Π_u, 2⁴Π_g and 2⁴Π_u) of O₂⁺ cation and their corresponding 58 Ω states. Of these 20 Λ-S states, the 1⁶Π_u state is found to be repulsive. The 1²Σ⁺_g, 1⁴Σ⁺_u, c⁴Σ^?_u and 1⁴Δ_u states are found to possess the double well. The b⁴Σ^?_g, 1⁶Σ⁺_g, 1⁴Σ⁺_u, a⁴Π_u, A²Π_u, 1⁶Π_g and 2⁴Π_g states are found to be inverted with the spin–orbit coupling effect included. The b′⁴Π_g, 1⁶Π_g, 1⁶Σ⁺_g, 1⁴Σ⁺_u and 1⁴Δ_u states, and the second well of the 1²Σ⁺_g state are found to be the weakly bound states. The b′⁴Π_g state is found to possess one well with one barrier. The PECs are calculated by the complete active space self-consistent field method, which is followed by the internally contracted multireference configuration interaction approach with the Davidson correction in combination with the aug-cc-pV6Z basis set. The core–valence correlation and scalar relativistic corrections are included. The convergent behaviour of present calculations is discussed with respect to the basis set and theoretical level. The spin–orbit coupling effect is accounted for. The PECs are extrapolated to the complete basis set limit. The spectroscopic parameters are evaluated, and compared with available measurements. It demonstrates that the spectroscopic parameters reported here can be expected to be reliably predicted ones.     

Kinetic ion-acoustic solitary waves in collisional plasmas

In this study, a bipolar high-voltage pulse with 20 ns rising time is employed to generate diffuse dielectric barrier discharge plasma using wire-plate electrode configuration in nitrogen at atmospheric pressure. The gas temperature of the plasma is determined by comparing the experimental and the best fitted optical emission spectra of the second positive bands of N₂(C³Π_u → B³ Π_g, 0-2) and the first negative bands of N₂ ⁺ (B² Σ_u ⁺ → X² Σ_g ⁺, 0-0). The effects of the concentration of argon and oxygen on the emission intensities of N₂ (C³Π_u → B³Π_g, 0-0, 337.1 nm), OH?(A ²Σ → X²Π, 0-0) and N₂ ⁺ (B² Σ_u ⁺ → X² Σ_g ⁺, 0-0, 391.4 nm) are investigated. It is shown that the plasma gas temperature keeps almost constant with the pulse repetition rate and pulse peak voltage increasing. The emission intensities of N₂ (C³Π_u → B³Π_g, 0-0, 337.1 nm), OH(A²Σ → X²Π, 0-0) and N₂ ⁺ (B² Σ_u ⁺ → X² Σ_g ⁺, 0-0, 391.4 nm) rise with increasing the concentration of argon, but decrease with increasing the concentration of oxygen, and the influences of oxygen concentration on the emission intensities of N₂(C³Π_u → B³Π_g, 0-0, 337.1 nm) and OH (A²Σ → X²Π, 0-0) are more greater than that on the emission intensity of N₂ ⁺ (B² Σ_u ⁺ → X² Σ_g ⁺, 0-0, 391.4 nm).     

Dislocation spectroscopy of crystals

A new method of studying the energy characteristics of dislocations is proposed, which is based on the investigation of the interaction of moving dislocations with purposefully introduced electronic and hole centers. A study has been made of KCl, NaCl, KBr, LiF, and KI alkali halide crystals containing electronic F and hole V _K and Me ⁺⁺ (Cu⁺⁺, Ag⁺⁺, Tl⁺⁺, In⁺⁺) centers. Investigation of the temperature dependence of the dislocation interaction with the F centers permitted determination of the position of the dislocation-induced electronic band (DEB) in the band diagram of the crystal. In KCl, the DEB is separated by ≈2.2 eV from the conduction-band minimum. It is shown that dislocations transport holes from the centers lying below the dislocation-induced hole band (DHB) (X ⁺, In⁺⁺, Tl⁺⁺, V _K) to those above the DHB (the Cu⁺ and Ag⁺ centers). Such a process is temperature independent. The DHB position in the crystal band diagram has been determined; in KCl it is separated by ≈1.6 eV from the valence-band top. The effective radii of the dislocation interaction with the electronic F and hole X ⁺, V _K, and Tl⁺⁺ centers have been found. Fiz. Tverd. Tela (St. Petersburg) 41, 2139–2146 (December 1999)     

Comparative study of the semiempirical three-parameter potential energy functions for diatomic molecules

A comparative study is made of four three-parameter semiempirical potential energy functions for 32 electronic states of diatomic molecules and their ions:n ₂:X¹gS _g ⁺ ,B ³π_g,A ³ gS_u,C ³ _u,B′ ³ gS_u.a ¹ π_g, a′gS _u ^? ,Ω ¹δ_u N ₂ ⁺ :X ² gS _g ^gS +A ² π,C ² gS _u ⁺ ,B ² gS _u ⁺ CO:X¹gS⁺,a ³ π, a′³ gS_u,e ³ gS^?,d ³gD₁,A ¹π CO⁺:X²gS⁺,A ² π,B ²gS⁺ O₂:X³gS _g ^? ,B ³ gS_u,c ¹ gS _u ^? ,b ¹gS _g ^s ,a ¹ δ_g,c ³ δ_u O ₂ ⁺ :X ²π_g,A ² π_g, a¹ π_g,b ⁴ gS _g ^? A program for numerically integrating the radial Schrödinger equation by the Cooley method is worked out. Certain additional units are introduced to conserve computer time. The resulting vibrational levels are compared with the experimental levels for all the electronic states studied. It is concluded on the basis of this analysis that it is not possible to describe equally well all the electronic states of various molecules on the basis of any single three-parameter potential function. A method for choosing a potential function for describing some particular electronic state of a diatomic molecule is proposed.