Influence of pressure on the relative population of the two lowest vibrational levels of the C <Superscript>3</Superscript> Π<Subscript>u</Subscript> state of nitrogen for electron beam excitation

Continuous and pulsed 12 keV electron beams were used to excite nitrogen within a gas cell at pressures ranging from 10 to 1400 hPa. The pressure dependence of the ratio of photon fluxes for emission from vibrational levels v'=0 and 1 of the C ³Π _u state has been studied. The results confirm the presence of a collisional excitation mechanism populating v'=0, 1 in addition to electron impact excitation. Rate constants of (1.27 ±0.04)×10^-11 cm³s^-1 [ v'=0] and (2.68 ±0.08)×10^-11 cm³s^-1 [ v'=1] were measured for C ³Π _u quenching by ground state nitrogen. For electron beam conditions relative excitation efficiencies of 1:0.59:0.22 for vibrational levels 0, 1 and 2 were calculated. The recorded flux ratios are compared with the predictions given by a vibrational relaxation model.     

Optical Emission of Molecular Hydrogen in a Recombining Hydrogen Plasma

We observed optical emission of molecular hydrogen in a recombining hydrogen plasma with an electron temperature of 0.1 eV and an electron density of 3 × 10¹²cm^–3. The optical emission intensities of molecular hydrogen in the recombining plasma were roughly 10%–45% of those in an ionizing plasma with an electron temperature of 4 eV. The ratio was greater for a transition line originated from an excited state with a larger vibrational quantum number. Because of the low electron temperature of 0.1 eV, the production processes of excited states are not considered electron impact excitation in the recombining plasma. Possible recombination processes are discussed which produce excited states of molecular hydrogen in the recombining plasma (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

态—态振动能量跃迁的时间分辨研究(Ⅰ)——碘分子的自碰撞过程

本文介绍了采用可调脉冲激光技术和时间分辨色散荧光方法研究态-态碰撞动力学的实验过程。在实验中直接观测了处于电子振动激发态B³Π_ou⁺(v＇=19)的碘分子在自碰撞事件中朝相邻振动态跃迁的衰变过程,得到态—态振动跃迁速率常数,k_v(19→18)=(2.21±0.33)×10^-11cm³s^-1mol^-1和k_v(19 关键词：     

约化场强对氮-氧混合气放电等离子体演化特性的影响

采用零维等离子体动力学模型,计算了不同约化场强条件下N₂/O₂放电等离子体的演化特性.结果表明,平均电子能量与约化场强有着近似的线性关系,在约化场强为100 Td时,平均电子能量约为2.6 eV、最大电子能量达35 eV;约化场强是影响电子能量函数分布的主要因素.气体放电过程结束后,振动激发态氮分子的粒子数浓度不再变化,电子激发态的氮分子、原子和氧原子的粒子数浓度达到一峰值后开始降低;放电结束后的氧原子通过复合反应生成臭氧.约化场强升高,由于低能电子减少的影响,振动激发态氮分子的粒子数浓度降低,当约化场强由50 Td增加75 Td,100 Td时,粒子数浓度由3.83×10¹¹ cm^-3降至1.98×10¹¹ cm^-3和1.77×10¹¹ cm^-3,其他粒子浓度则相应增大. 关键词： 等离子体 约化场强 粒子演化 数值模拟     

12C18O2: High-resolution emission spectra in the 4.5-μm region rovibrational transitions 0v′2v3 → 0v′2(v3 − 1), v2 = l

Emission spectra of gaseous mixtures involving isotopic species of CO₂ excited by a dc discharge were recorded under Doppler-limited resolution, using a high-information Fourier Transform Interferometer, in the region 4–5 μm. In this paper are given the results concerning 34 vibrational transitions (Δv₃ = 1), for ¹²C¹⁸O₂. The band centers and the spectroscopic constants for the 39 vibrational levels involved are reported. They reproduce more than 1000 experimental wavenumbers with a RMS of the order of 2 × 10^?5 cm^?1 for the best vibrational transition and less than 3 × 10^?4 cm^?1 for most of the others. From a weighted simultaneous fit of all the experimental wavenumbers belonging to the Σ-Σ transitions, a set of molecular parameters was computed. A good reproduction of the experimental wavenumbers was obtained for all the vibrational transitions except those involving the level v₃ = 9, our conclusion being that a local vibrational perturbation exists for this level.     

A New Candidate Laser Dye Based 1,4-Bis[β-(2-Naphthothiazolyle)Vinyl]Benzene. Spectroscopic Behavior,Laser Parameters and Excitation Energy Transfer

A new candidate laser dye based 1,4-bis[β-(2-naphthothisolyl) vinyl] benzene (BNTVB) were prepared, and characterized in various organic solvents. The center polarity is less sensitive than electronic absorption. A red shift was noticed in the fluorescence spectra (ca. 40 nm) with increment in the solvent’s polarity, this means that BNTVB’s polarity appreciates upon excitation. The dipole moment of ground state (μ_g) and the excited singlet state dipole moment (μ_e) are determined from Kawski – Chamma and Bakshiev–Viallet equations using the disparity of Stokes shift with solvent polarity function of ε (dielectric constant) and n (refractive index) of the solvent. The result was found to be 0.019D and 5.13D for ground and exited state, in succession. DFT/TD-DFT manners were used to understand the electronic structures and geometric of BNTVB in other solvents. The experimental and theoretical results showed a good agreement. The photochemical quantum yield (Ф_c) of BNTVB was calculated in variable organic reagents such as Dioxane, CHCl₃, EtOH and MeOH at room temperature. The values of φ_c were calculated as 2.3?×?10^?4, 3.3?×?10^?3, 9.7?×?10^?5 and 6.2?×?10^?5 in Dioxane, CHCl₃, EtOH and MeOH, respectively. The dye solutions (2?×?10^?4 M) in DMF, MeOH and EtOH give laser emission in the blue-green region. The green zone is excited by nitrogen pulse 337.1 nm. The tuning range, gain coefficient (α) and cross – section emission (σ_e) of laser were also estimated. Excitation energy transfer from BNTVB to rhodamine-6G (R6G) and N,N-bis(2,6-dimethyphenyl)-3,4:9,10-perylenebis-(dicarboximide) (BDP) was also studied in EtOH to increase the laser emission output from R6G and BDP when excited by nitrogen laser. The dye-transfer power laser system (ETDL) obeys the Foster Power Transmission (FERT) mechanism with a critical transmission distance, R_o of 40 and 32 ? and k_ET equals 2.6?×?10¹³ and 1.06?×?10¹³ M^?1 s^?1 for BNTVB / R6G and BNTVB / BDP pair, respectively.     

Luminescence and decay times of CsI:In+

Luminescence spectra of single crystals of CsI:In⁺ excited in the A(304 nm), B(288 nm), C(268 nm) and D(257 nm) absorption bands have been studied in the temperature range 4.2–300 K. Excitation in the A band at 4.2 K gives rise to the principal emission at 2.22 eV accompanied by a partly-overlapping weak band at 2.49 eV. An additional emission band at about 2.96 eV is observed on excitation in the B, C or D bands. Yet another emission band located at 2.67 eV is excited only in the D band. The relative intensities of the bands are very sensitive to excitation wavelength as well as to temperature. The origin of all these bands is assigned in terms of a model for the relaxed excited states (RES). All the luminescence spectra were resolved into an appropriate number of skew-Gaussian components. Moments analysis leads to a value of (1.35 ± 0.02) × 10¹³ rad s^-1 for the effective frequency (ω_eff) of lattice vibrations coupled to the RES. At the lowest temperature, the radiative decay times of each of the intracenter emission bands (2.22, 2.49 and 2.96 eV) show a slow decay ( ～ 10–100 μs) and a fast decay ( ～ 10–100 ns). The 2.96 eV band, which is assigned to an emission process which is the inverse of the D-band absorption, exhibits a single decay mode ( ～ 10 μs). The intrinsic radiative decay rates (k₁, k₂), the one-phonon transition rate (K) and the second-order spin-orbit splitting (D) for the RES responsible for the principal emission are: k₁ = (6.0±-0.3)×10³ s^-1, k₂ = (1.33±-0.06)×10⁵ s^-1, K = (2.4±-0.4)×10⁷ s^-1 and D = (13.8±-0.5) cm^-1.     

On the nature of emissions of polymethyl methacrylate excited by an electron beam of subnanosecond or nanosecond duration

The results of studies of the physical nature of emissions produced in polymethyl methacrylate excited by electron beams of a subnanosecond or a nanosecond duration are presented. The spatial, amplitude, and spectral-kinetic properties of emissions have been examined under an electron beam energy density varying from 10^–4 to 4 × 10^–1 J/cm². It has been found that cathodoluminescence is the primary type of emission under low energy densities of the electron beam. When the energy density of a nanosecond electron beam and/or the number of pulses of excitation by a subnanosecond electron beam were increased, an electrical breakdown of polymethyl methacrylate occurred in the irradiated region. This process was accompanied by a burst of emission of dense, low-temperature plasma.     

Influence of Ar, Ne, Xe, and CCl4 impurities on luminescence kinetics of Cd II ions (5s22D5/2-5p2P3/2 transition, λ = 441.6 nm) in He-Cd mixture

The luminescence kinetics of the Cd II ion at a wavelength of 441.6 nm has been studied experi-mentally in a high-pressure He-Cd mixture in the presence of Ar, Ne, Xe, and CCl₄ impurities. Cadmium ions were excited through the bombardment of a cadmium foil heated up to 240°C by a pulsed electron beam with an electron energy of 150 keV, a pulse duration of 3 ns, and a current of 500 A. The constants of collisional quenching of the Cd II 5s ^{2 2} D _5/2 level by Ar, Ne, and Xe atoms and CCl₄ molecules and the integral luminescence quenching constants of this level in the helium medium by these impurity gases have been determined. The constants of collisional quenching appeared to be 8.1 × 10⁻¹² (Ar), 1.2 × 10⁻¹² (Xe), 1.5 × 10⁻¹³ (Ne), and 1.8 × 10⁻¹⁰ cm³/s (CCl₄, for λ = 325 nm), while the integral constants were found to be, respectively, 4.1 × 10⁻¹¹, 3.4 × 10⁻¹¹, 9.5 × 10⁻¹², 1.4 × 10⁻⁹ cm³/s for Ar, Ne, Xe, and CCl₄ at a buffer gas pressure of 1 atm. Original Russian Text ? A.I. Miskevich, Liu Tao, 2009, published in Optika i Spektroskopiya, 2009, Vol. 107, No. 1, pp. 45–49.     

Low temperature vibrational relaxation of OD in the A2Σ, state

The vibrational relaxation of the A ²Σ state of OD has been studied in the low translational temperature environment of an argon free-jet (T_trans near 5 K). Using laser induced fluorescence (LIF), the absolute vibrational relaxation rate coefficients were measured for OD A²Σ (ν′) to be 7.1 ± 2.6 × 10^?11, 5.9 ± 1.4 × 10^?11, and 2.7 ± 1.1 × 10^?11 cm³ s^?1 for the ν = 3, 2 and 1 states, respectively. State-to-state relaxation rate coefficients were also obtained for the ν= 1, ? = 1 level going to ν= 0, ? levels in the A²Σ manifold. The rotational relaxation rate coefficient for ν= 1, ?= 1 in the A state of OD was found to be 9.6 ± 1.0 × 10^?11cm³s^?1. These values are consistent with values measured for OH A²Σ, and the total loss rates are near the capture rate coefficient value. The vibrational relaxation rate coefficients k_ν appear to be governed by the vibrational energy of the molecule rather then by interaction with nearby dissociative states such as the a⁴Σ state. The relative Einstein A factors for the A²σ (ν = 3) state of OD were determined and compared with the available calculated value.     

N2(B3IIg) Quenching by Ethanol

The reaction rate values for the molecular nitrogen B³II_g state quenching by ethanol for vibrational quantum numbers v′ = 4–12 have been evaluated from the change of N₂ first positive system spectrum at ethanol addition to a high speed, microwave produced, plasma flow. The wall influence is avoided using a 0.9 m large reaction chamber. Computed N₂(B³II_g) quenching rate values are comprised between 0.9 × 10^?10 and 1.4 × 10^?10 cm³ · s^?1, being smaller than the corresponding gaskinetics rate.     

A new study of the ν 2(A 1) infrared band of phosphorus trifluoride

The high-resolution Fourier transform infrared spectrum of phosphorus trifluoride (PF₃) has been reinvestigated in the v_2?=?1 vibrational excited state near 487?cm^?1 (at a resolution of 3?×?10^–3?cm^–1). Thanks to our new accurate rotational ground-state C ₀ value, 0.159970436(69)?cm^–1, and to recent pure rotational measurements, 318 new infrared transitions of the ν ₂ fundamental band have been assigned, extending the rotational quantum number values up to K _max?=?71 and J _max?=?72. A merge, for the first time, of 135 reported microwave data (K _max?=?42 and J _max?=?49) within the v_2?=?1 excited level and 2860 rovibrational transitions yielded improved constants of ν ₂. Parameters of this band have been obtained, up to sextic centrifugal distortion constants, by least-squares fits, σ _IR?=?3.60?×?10^–4?cm^–1 and σ _MW?=?5.53?×?10^–6?cm^–1 (166?kHz). Comparison of these constants with those measured previously by infrared spectroscopy reveals orders of magnitude higher accuracy of these new values.     

Intensification of shock-induced combustion by electric-discharge-excited oxygen molecules: numerical study

Mechanisms of combustion enhancement in a supersonic H₂–O₂ reactive flow behind an oblique shock wave front are investigated when vibrational and electronic states of O₂ molecule are excited by an electric discharge. The analysis is carried out on the base of updated thermally nonequilibrium kinetic model for the H₂–O₂ mixture combustion. The presence of vibrationally and electronically excited O₂ molecules in the discharge-activated oxygen flow allows to intensify the chain mechanism and to shorten significantly the induction zone length at shock-induced combustion. It makes possible, for example, to ignite the atmospheric pressure H₂–O₂ mixture at the distance shorter than 1 m behind the weak oblique shock wave at a small energy E_s = 1.2 × 10^–2 J · cm^–3 input to O₂ molecules. At higher pressure it is needed to put greater specific energy into the gas in order to ignite the mixture at appropriate distances. It is shown that excitation of O₂ molecules by electric discharge is much more effective for accelerating the hydrogen–oxygen mixture combustion than mere heating the gas.     

Adsorption and desorption of ammonia,hydrogen, and nitrogen on ruthenium (0001)

The adsorption of ammonia, hydrogen, and nitrogen on a Ru(0001) surface have been investigated by Auger electron spectroscopy, low-energy electron diffraction, and thermal flash desorption. The adsorption of ammonia on Ru(0001) can be divided into a low temperature mode (100 K) and a higher temperature mode (300–500 K). For a crystal temperature of 100 K the ammonia adsorbs into two weakly bound molecular γ states with s = 0.2. The ammonia desorbs as NH₃ molecules with desorption energies of 0.32 and 0.46 eV. At 300–500 K adsorption occurs via an activated process with a low sticking probability (s ? 2 × 10^?4).This adsorption is accompanied by dissociation and formation of an apparent (2 × 2) LEED pattern. Hydrogen adsorbs readily (s = 0.4) on Ru(0001) at 100 K and desorbs with 2nd order kinetics in the temperature range 350–450 K. Nitrogen does not appreciably adsorb on Ru(0001) even at 100 K; maximum nitrogen coverage obtained was estimated to be <2% of a monolayer. Changes in the ammonia flash desorption spectra after hydrogen preadsorption at 100 K will be discussed.     

Molecular nanocluster fluorescence in microwave infrared-radiation fields

The paper considers a donor-acceptor nanocluster fluorescing in a microwave infrared radiation field. It is assumed that the nanocluster consists of two dipole-dipole interacting organic molecules. It is shown that the fluorescence process of the nanocluster occurs if the donor molecule contains a substructure of identical diatomic pairwise interacting bonds of dipoles (an IR antenna). This antenna is capable of accumulating vibrational energy as a sum of collective vibrational quanta (excimols). The acceptor molecule has no permanent dipole moment and cannot be excited by microwave IR radiation. This molecule is polarized in the dipole moment field of the donor IR antenna and can receive energy accumulated in the IR antenna of the donor molecule. If the acceptor molecule has an electronically excited state in the long-wavelength visible region of its absorption spectrum, then after receiving energy equal to the energy of this state from the donor antenna, the electronic excitation of the acceptor molecule and its fluorescence is possible. As an example, the fluorescence of a nanocluster is considered whose donor molecule has a C _n H_2n IR antenna. The acceptor molecule is aromatic and the external infrared frequency, 1.1 × 10¹⁴ s^?1, is equal to the frequency of the excimol in the donor infrared antenna.     

First high-resolution analysis of the 5ν3 band of nitrogen dioxide near 1.3 μm

The first high-resolution absorption spectrum of the 5ν₃ band of the ¹⁴N¹⁶O₂ molecule at 7766.071 cm^?1 was recorded by high sensitivity CW-Cavity Ring Down Spectroscopy between 7674 and 7795 cm^?1. The noise equivalent absorption of the recordings was α_min≈1×10^?10 cm^?1. The assignments involve energy levels of the (0,0,5) vibrational state with rotational quantum numbers up to K_a=9 and N=47. The set of the spin–rotation energy levels were reproduced within their experimental uncertainty using a theoretical model, which takes explicitly into account the Coriolis interactions between the spin rotational levels of the (0,0,5) vibrational state and those of the (0,2,4) dark state together with the electron spin–rotation resonances within the (0,0,5) and (0,2,4) states. Precise values were determined for the (0,0,5) vibrational energy rotational, spin-rotational constants and for the (0,2,4)?(0,0,5) coupling constants. In addition the (0,2,4) rotational and spin-rotational constants were estimated. Using these parameters and the value of the transition dipole moment operator determined from a fit of a selection of experimental line intensities, the synthetic spectrum of the 5ν₃ band was generated and is provided as Supplementary material.     

High density excitation effects on fluorescence from the crystals of aromatic hydrocarbons and charge-transfer complexes

High density excitation effects on fluorescence were studied for the crystals of fluoranthene, chrysene, benzo[g, h, i]perylene, pyrene and pyrene-d₁₀ and also for the crystal of 1,2,4,5-tetracyanobenzene (TCNB)-hexamethylbenzene (HMB) complex. Relative fluorescence intensity in the shorter wavelength region decreased with increasing excitation density (for chrysene, fluoranthene, and benzo[g, h, i]perylene), and the vibrational structure became diffuse at high density excitation (for fluoranthene and chrysene). The rate constants of the bimolecular quenching and exciton migration were obtained by analysis of the fluorescence decay curves at high density excitation for chrysene, pyrene, pyrene-d₁₀, and TCNB-HMB. The exciton hopping rates at 295 K were 2.4 × 10¹⁰ s^?1 in chrysene and 7.9 × 10⁸s^?1 in TCNB-HMB. The differences in the rate between chrysene and fluoranthene (2.2 × 10⁹s^?1) and between TCNB-HMB and TCNB-durene (4.2 × 10⁹s^?1) are discussed in terms of the coupling intensity between two neighboring oscillators accompanying the transition between ground and the lowest excited singlet state. The difference in the rate and activation energy of exciton migration between pyrene and pyrene-d₁₀ corresponded to a quasilocalized exciton model.     

Study of anharmonic effects in the IR spectrum of a solution of CF<Subscript>3</Subscript>Br in liquid argon

The vibrational spectrum of CF₃Br with the natural abundance ratio of isotopologues is studied in solutions in liquid Ar at T = 90 K in the frequency range 4000–400 cm^?1 with a resolution of 0.1 cm^?1 for the concentration range 3.1 × 10^?7?6.3 × 10^?3 mol %. The parameters of the vibrational spectrum of the molecule are determined: the frequencies are measured accurate to ± 0.1 cm^?1, and the transition probabilities are found up to the fourth order inclusive. One hundred fifty absorption bands of CF₃Br are interpreted, including the bands belonging to all the isotope modifications of this compound; the halfwidths of these bands are determined. For all the fundamental frequencies, the isotope shifts are obtained. Vibrational ?-resonance is studied. Using the experimental data obtained and taking into account this resonance, a complete set of parameters describing the experimental frequencies with the error δ ≈ 0.3 cm^?1 was found. This set consists of 6 harmonic frequencies and 30 anharmonicity constants, including the constants r _ik related to vibrational ?-resonances.     

Spectroscopic and structural proprieties of LiAr and LiAr<Subscript>2</Subscript> molecules

We determined and tried to understand the spectroscopic and structural properties of small LiAr and LiAr₂ molecules within a simple model considering LiAr as a result of interaction between a valence electron and a LiAr⁺ molecular ion. Potential energy curves, spectroscopic constants, and vibrational levels corresponding to the Li(2s, 2p, 3s, and 3p)+Ar dissociation are reported for the LiAr molecule. The depth of the potential well for the X ²Σ⁺ ground state is found to be 50 cm⁻¹ (the corresponding experimental value is (42.5±1.2) cm⁻1 [1]). R _e is determined to be 9.36 a.u. (the experimental value is 9.24 a.u.). For the first excited state A, R _e = 4.97 a.u. and D _e = 993cm ⁻¹ (the corresponding experimental values are 4.68 a.u. and (925−40) cm⁻¹, respectively [1]). The spacing between the vibrational levels for the ground and first excited states is in very good agreement with the experiment. For the ground state, the difference between our results and the data of the most recent experiment is about 1 cm⁻¹. The model has been extended to study the LiAr₂ molecule in two forms (linear and triangular). We have determined the potential energy surfaces of the states dissociating to Li(2s, 2p)+Ar₂ and thus found the triangular form to be more stable as compared to the linear one. We have also calculated the transition energy between the ground state and first excited states of this molecule. The emission spectrum of the Li(2s)+Ar₂→Li(2p)+Ar₂ transition in both forms redshifts as compared to the Li(2s)→Li(2p) atomic transition.     

Determination of the reaction rate constant and activation energy for pressure-induced 2+2 cycloaddition of the C60 fullerene

The kinetics of fullerene solid-phase dimerization proceeding through the 2+2 cycloaddition of C₆₀ at a pressure of 1.5 GPa is investigated by vibrational spectroscopy in the temperature range 373–473 K. Kinetic curves for the formation of (C₆₀)₂ dimers are obtained using the analytical band at 796 cm^?1 in the IR spectra of the (C₆₀)₂ dimer molecule. Under the assumption that the pressure-induced dimerization of C₆₀ is an irreversible second-order reaction, the reaction rate constants are determined at different temperatures. The activation energy and the preexponential factor are found to be equal to 134±6 kJ/mol and (1.74±0.24)×10¹⁴ s^?1, respectively.