C2H221分子转动角动量定向分布(Orientation)及其碰撞弛豫和转移

利用圆偏振激光受激Raman抽运,以 C₂H₂分子为样品选择性地制备了它的电子基态单一转动态(X¹Σ⁺_g,ν″₂＝1,J″的角动量定向布居(orientation)．并从圆偏振紫外激光诱导的A¹A_u(ν′₃＝1)←X¹Σ⁺_g(ν″₂＝1)的荧光（谱）,直接测定了 C₂H₂(X¹Σ^＋_g,ν″₂＝1,J″＝4,7,8,…,13）的角动量定向布居值．从时间分辨的荧光信号谱测定了角动量定向布居的碰撞弛豫速率常数,同时还研究了由各初始激励的转动态向其他邻近转动态碰撞诱导的角动量定向布居转移． 关键词：     

UV laser desorption of nitric oxide from semiconducting C<Subscript>60</Subscript>/Cu(111)

The desorption of NO from a well-characterized, epitaxially grown semiconducting C₆₀ surface is reported. Two different channels are identified in the laser desorption. Both channels yield a comparably high desorption cross section of σ₁=7.0×10^-17 cm² and σ₂=5.5×10^-17 cm² for the first and second channel, respectively. The laser desorbed NO molecules are detected with rovibrational state selectivity by (1+1) REMPI in the -bands. In the first channel the desorbing molecules are highly excited with an average kinetic energy of 〈E_kin〉=174 meV. The rotational population distribution can be fitted by a rotational temperature of T_rot=800 K. A rotational–translational coupling is observed, with velocities ranging from 1000 m/s for low to 1300 m/s for high rotational states. The vibrationally excited population is estimated to be less than 1% of the ground state. The second channel yields less excited molecules and an almost Boltzmann distributed rotational population with a temperature of T_rot=280 K. The apparent velocity distribution derived from the pump-probe delay yields molecules much too slow to be explained by even a thermal desorption. This desorption is probably caused by a long-lived electronic excitation in the substrate for which a lifetime of τ≈160 μs is estimated. PACS 42.62.Fi; 34.50.Dy; 68.49.Df; 68.43.Tj; 79.20.La     

Laser-induced Alignment and Coulomb Explosion of CO2

实验研究了CO₂分子在飞秒强激光脉冲作用下的动力学过程,包括分子取向,隧穿电离和库仑爆炸,激光强度从1×10¹³W/cm²变化到6×10¹⁴W/cm². 当激光强度小于分子的电离阈值时,CO₂分子的非绝热转动激发形成一个相干转动波包,波包演化导致分子沿激光电场方向取向. 激光脉冲结束后,分子取向可以周期性地再现,利用另一束激光可以对取向结构进一步进行修饰. 当激光强度大于分子     

光学泵浦的锂分子激光

以可见染料激光泵浦锂分子,在高于900℃的蒸气温度下,获得了由理分子A¹∑_u⁺态跃迁到基态X¹∑_g⁺的位于874—912nm区的许多光泵激光输出。谐振腔使输出信号增强约9倍。对部分激光跃迁的振转量子数作了标识。 关键词：     

Diode laser study of IR multiphoton-induced depletion of rotational sublevels of the ground vibrational state of SF6 molecules cooled in a pulsed free jet

A pulsed frequency tunable diode laser was used to investigate the IR multiphoton-induced depletion of rotational sublevels of the ground vibrational state of SF₆ molecules cooled in a pulsed free jet at exciting energy densities between ≈10^-2 and 2.3 J cm^-2. The depletion of all rotational sublevels was effective at considerable (≈5–11 cm^-1) pumping frequency detunings from the linear absorption spectrum (LAS) of the molecule the width of which under the conditions of experiment (T_rot ≈ 18 K) was ≈2–3 cm^-1. The fraction of molecules excited by a pumping pulse from individual rotational sublevels was measured and its dependence on the exciting pulse frequency and energy density investigated. The effect of collisions on the depletion of the rotational sublevels was studied.     

Infrared-microwave double-resonance probing of the population-depopulaton of rotational states in the NO2 molecule

A 10.6-μm CO₂ laser operating over a power range 5 ≤ p ≤ 135 watts was used to pump some select vibrational transitions in the NO₂ molecule while monitoring the rotational transitions (9_1,9 → 10_0,10), (23_2,22 → 24_2,23), and (40_2,38 → 39_3,37) in the (0, 0, 0) vibrational level and the (8_0,8 → 7_1,7) rotational transition in the (0, 1, 0) vibrational level. These rotational transitions were monitored by microwave probing to determine how the population of states in the rotational manifolds was being altered by the laser. Coincidences between some components of the ν₃-ν₂ band of NO₂ and the CO₂ infrared laser lines in the 10-μm region appeared to be responsible for the strong interaction between the continuous laser beams and the molecular states. Characteristic rate curves for population-depopulation changes in the chosen rotational levels listed above were found for various power levels from the laser pump. Rate coefficients for intensity decay for various laser powers were calculated from experimental data and are presented.     

Upconversion-pumped population kinetics for4I13/2 and4I11/2 laser states of Er3+ ion in several host crystals

Population kinetics of the upper⁴I_11/2 and lower⁴I_13/2 laser states of the Er³⁺ ion were studied experimentally and theoretically in (Er)BaY₂F₈, (Er)YLF, (Er)YSGG, (Er)CaF₂ and (Er)YALO. Fluorescence from these states to the⁴I_15/2 ground state was excited through upconversion simultaneously with the⁴I_11/2 →⁴I_13/2 lasing using 1.53 µm radiation from an erbium : glass laser for optical pumping. Lifetimes of both states are altered during lasing by co-operative energy transfer processes: the lifetime of the lower state τ₁ is shortened and that of the upper state τ₂ increased with the resultant ratio τ₂/τ₁>1. After lasing the lifetime ratio returns to the ‘normal’ value τ₂/τ₁ <1; that is, one obtained under weak ultraviolet excitation. Kinetic rate equations for the population density functions for both laser states were set up and solved by approximation in three time domains. It was assumed that only one co-operative energy transfer process operates in the laser crystals and determines the population inversion kinetics. Consistency relationships for comparison of the theoretical results with the experiment were developed. Only (Er)BaY₂F₈ spectral features showed close agreement with theory, resulting in a high score of 94% for the overall correlation in the consistency test, whereas all other crystals scored <50%. As a result of this high correlation, a close match between theoretical and experimental population decay curves was shown for (Er)BaY₂F₈. Most probably, more than one energy transfer process shapes the decay curves and determines the population inversion kinetics for the other laser crystals. (Er)YALO showed little lifetime change for the laser states, apparently due to inefficient co-operative energy transfer processes. As a result it probably lased in a self-terminating short-pulse mode.     

The H2S Spectrum around 0.7 μm

The overtone spectrum of H₂S has been recorded by intracavity laser spectroscopy in the 14100–14400 cm⁻¹spectral region. The rovibrational analysis was performed allowing one to assign not only lines involving the pair of interacting states {(402), (303)} ({(60⁺, 0), (60⁻, 0)} in local mode notation), but also lines involving the interacting states {(322), (223)} ({50⁺, 2), (50⁻, 2)} in local mode notation). Indeed, apart from the strong H₂₂interactions that link the rotational levels of the states (60^±, 0) on the one hand, and the rotational levels of the states (50⁺, 2) on the other hand, we observe that the rotational levels of the two pairs of states interact strongly through anharmonic and Coriolis-type resonances. These resonances transfer intensity to lines involving the (50⁺, 2) pair of states. Altogether 80 rotational upper-state levels have been observed and reproduced satisfactorily using an Hamiltonian matrix that takes explicitly into account the various interactions and assumes the same vibrational energy and rotational constants for the two components of the local mode pairs. The following band centers have been obtained: ν₀(60⁺, 0) = 14291.122 cm⁻¹and ν₀(50^±, 2) = 14284.705 cm⁻¹. Finally a local mode-type behavior is evidenced by the values of the Hamiltonian constants, and refined vibrational local mode parameters are obtained.     

Two Dimensional Rotational Temperature Measurement by Multiline Laser Induced Fluorescence of Nitric Oxide in Combustion Flame

Two-dimensional rotational temperature measurement was performed in a stable combustion flame of premixed butane and oxygen using multiline laser induced fluorescence (LIF) of nitric oxide molecules. Multiple rotational absorption lines of A²∑⁺Π;X²II(0,0) Q₁ and Q₂ lines were excited by laser light around 226 nm, and the LIF signal was observed by an image-intensified digital camera. Temperature was determined through least squares fitting correlation between LIF intensity and excitation rotational quantum number for the Boltzmann distribution function. The measured LIF intensity was approximated by the Boltzmann distribution with good accuracy, and the temperature obtained was between 500 K and 1800 K for the test flame. The measuring error of the temperature was evaluated and found to be 80 K, which corresponded to 8% of the measured fluorescence intensity. The two-line LIF scheme was evaluated by different pairs of excitation lines (Q₁(31.5)/Q₁(16.5) and Q₁(18.5)/Q₁(16.5)) for comparison with the multiline LIF approach. Temperature which was obtained by two-line LIF scheme corresponded well with multiline LIF results for Q₁(31.5)/Q₁(16.5) excitation. However, for Q₁(18.5)/Q₁(16.5) excitation, the obtained temperature did not agree with the multiline LIF result because the population of rotational states J=18.5 and J=16.5 is similar at high temperatures. We found that two-line LIF temperature measurement was reliable when excitation lines were suitably selected.     

Raman紫外双共振研究C2H2分子的碰撞转动弛豫

本文利用受激Raman抽运,选择性地制备了C₂H₂分子电子基态的红外非激活振动能级的单一转动态(X¹∑_g⁺,v″₂=1,J″=9,11,13),并从紫外激光诱导的A¹Au(v′₃=1)←X¹∑_g⁺(v″₂=1)荧光谱,直接测定上述三个转动态的C< 关键词：     

HF-laser performance of CO2-laser-ignited mixtures of SF6 :H2 and of S2F10 :H2

We have used a CO₂ laser to ignite mixtures of SF₆ :H₂ and S₂F₁₀ :H₂. We observed HF lasing from these mixtures when an optical resonator was constructed around the reaction cell. The HF-lasing performance of the two mixtures was compared as a function of mixture ratio, fluorine-donor pressure, and CO₂-laser frequency. Under comparable conditions, the HF-laser output for S₂F₁₀ :H₂ mixtures was typically 5–6 times greater than that for SF₆ :H₂ mixtures. Spectral output of the HF laser was coarsely resolved to provide data about the vibrational and rotational states of the HF molecule.     

Laser induced collisional energy transfer processes in a rubidium-potassium mixture

Two laser induced collisional energy transfer processes in alkali vapours are investigated. For process K(4²S_1/2)+ Rb(5²P_3/2)+?ω_T→K(6²S_1/2)+Rb(5²S_1/2), a population inversion between the final state K(6²S_1/2) and lower states, leading to a superradiant emission has been observed. Comparison between experiment and theory shows a qualitative agreement in the limit of low atomic densities and laser power. However the transfer profile width is about two times larger than the calculated one for both processes.     

Quantitative laser-induced fluorescence of CH in atmospheric pressure flames

Absolute number densities of the CH radical were determined in a partially premixed methane/air flame (equivalence ratio was 1.36) at atmospheric pressure by exciting a predissociating level via the CH B–X(1,0) transition using a quasi-linear laser-induced fluorescence scheme. The peak number density was (1.0±0.4)×10¹³ cm^-3 or 2.4±1 ppm at 1900 K, with a flame-front width of 250 μm (FWHM). Rotational energy transfer must be considered for correct laser-induced fluorescence signal interpretation. Competition between optical pumping and rotational relaxation in both excited and ground states produces a signal that varies almost linearly with laser pulse energy even for large pumping rates. For these conditions, the population of the initial ground-state rotational level is depleted by optical pumping, and rotational energy transfer collisions rapidly repopulate the level during the laser pulse. Deviations from linear behavior are less than 20%. The effects of spatial resolution and polarization of the fluorescence on the absolute measurements are also discussed. Received: 27 March 2002 / Revised version: 22 August 2002 / Published online: 15 November 2002 RID="*" ID="*"Present address: Lam Research Corporation, Fremont, CA 94538, USA RID="**" ID="**"Present address: Mechanical Engineering, Eindhoven University of Technology, 5600 MB Eindhoven, The Netherlands RID="***" ID="***"Present address: Mechanical Engineering Dept., Stanford University, Stanford CA 94305, USA RID="****" ID="****"Corresponding author. Fax: +1-650/859-6196, E-mail: smith@mplvax.sri.com     

Resonance excitation of C2H4-molecule luminescence by pulsed high-pressure continously tunable CO2 laser

The visible luminescence of ethylene in a focused 10⁹W/cm² continously frequency-tuned field of a high-pressure CO₂ laser was investigated. Q-branch excitation resonance was observed width of 10 cm^-1. No direct correlation between detailed rotational structure and intensity of luminescence was revealed.     

Measurement of rotational temperature in CO2 waveguide laser medium

A small-signal gain in CO₂ waveguide laser medium has been measured on rotational-vibrational transitions in the P-branch of the (0, 0, 1)-(0, 2⁰, 0) band. It has been found that the rotational temperature is well defined in the waveguide laser system where high excitation power is injected and a large amount of energy is flowing through vibrational, rotational, and translational degrees of freedom. The rotational temperature is slightly higher than the translational temperature.     

Effective nonchain HF laser excited by a self-sustained discharge

Lasing and discharge in mixtures of SF₆ with hydrogen and hydrocarbons are investigated. If the chemical reaction is initiated by a self-sustained discharge (a generator with both an inductive and capacitive energy storage can be used), the maximum lasing efficiency is attained at high values of the ratio E/p (where E is the electric field intensity and p is the pressure in the mixture) if shaped electrodes and preionization of the discharge gap are employed. For the first time, the lasing efficiency obtained in a nonchain HF laser is as high as 10% of the energy deposit and 4.5% of the stored energy for a specific radiation energy of ≈140 J/(l atm). At high efficiencies, the emission spectrum of the nonchain HF laser significantly broadens and cascade lasing at P(3-2) → P(2-1) → P(1-0) vibrational transitions for several rotational lines is realized.     

Effect of helium/argon gas ratio in a He-Ar-Cu<Superscript>+</Superscript> IR hollow-cathode discharge laser: modeling study and comparison with experiments

The He-Ar-Cu⁺ IR laser operates in a hollow-cathode discharge, typically in a mixture of helium with a few-% Ar. The population inversion of the Cu⁺ ion levels, responsible for laser action, is attributed to asymmetric charge transfer between He⁺ ions and sputtered Cu atoms. The Ar gas is added to promote sputtering of the Cu cathode. In this paper, a hybrid modeling network consisting of several different models for the various plasma species present in a He-Ar-Cu hollow-cathode discharge is applied to investigate the effect of Ar concentration in the gas mixture on the discharge behavior, and to find the optimum He/Ar gas ratio for laser operation. It is found that the densities of electrons, Ar⁺ ions, Ar_m ^* metastable atoms, sputtered Cu atoms and Cu⁺ ions increase upon the addition of more Ar gas, whereas the densities of He⁺ ions, He₂ ⁺ ions and He_m ^* metastable atoms drop considerably. The product of the calculated Cu atom and He⁺ ion densities, which determines the production rate of the upper laser levels, and hence probably also the laser output power, is found to reach a maximum around 1–5 % Ar addition. This calculation result is compared to experimental measurements, and reasonable agreement has been reached. Received: 14 October 2002 / Revised version: 28 November 2002 / Published online: 19 March 2003 RID="*" ID="*"Corresponding author. Fax: +32-3/820-23-76, E-mail: annemie.bogaerts@ua.ac.be     

Rotational relaxation of the 0001 level of CO2 including radiative transfer in the 4.3-μm band of planetary atmospheres

Accurate numerical solutions have been obtained for a model problem of rotational relaxation within the 00⁰1 vibrational level of C¹²O₂¹⁶ accounting for the transfer of radiation in the lines of the fundamental transition 00⁰1-00⁰0 of the 4.3-μm band. Intramolecular exchange of vibrational energy with the reservoir of v₂ quanta and absorption of solar radiation in the 00⁰1- 00⁰0 band are accounted for. A plane-parallel isothermal atmosphere of pure CO₂ with the barometric pressure distribution and solar illumination is assumed. The line opacity is represented by nonoverlapping Voigt profiles depending on temperature and pressure. The transfer problem, which is equivalent to that of a multiplet with a large number of lines with a common lower level, was solved by a generalization of the Rybicki method. We find significant deviations from ratational LTE (local thermodynamic equilibrium) in regions in which the harmonic average of the optical depth over the band is of order 10³-10⁴. Absorption of solar radiation can affect significantly the source functions of lines at the centers of the P and R branches. Deviations from rotational LTE are shown to influence the intensity and shape of the 4.3-μm band of CO₂ in the spectra of Mars and Venus, and should be taken into account in the interpretation of the observations in which the rotational structure is resolved, especially in limb measurements, where these effects are particularly apparent.     

Tunable infrared diode laser measurements of line strengths and collision widths of 12C16O at room temperature

A tunable diode laser was used to scan 33 vibration-rotation lines in the fundamental band of CO in room-temperature CO-N₂ and CO-Ar mixtures. Each absorption record was fitted with a Voigt profile from which the line strength and collision width were determined. The fundamental band strength of ¹²C¹⁶O at 273.2°K was determined to be 283±4 cm^-2 atm^-1. Results are also presented for the rotational quantum number dependence of the collision width for broadening by N₂ and Ar.     

Excitation,inversion, and relaxation mechanisms of the HCN FIR discharge laser

Millimeter/submillimeter rotational absorption spectroscopy has been used as a diagnostic probe of a cw HCN discharge laser. This sensitive technique allowed in situ absolute population measurements of a number of vibrational states of HCN (including the upper lasing state) and other pertinent molecules. This unique set of data, which was obtained under a variety of discharge and laser conditions, is directly related to excitation, inversion, and relaxation processes. Along with elucidating several fundamental aspects of inversion and relaxation these results also strongly indicate that the primary laser excitation mechanism is near-resonant energy transfer from vibrationally excited nitrogen, N₂ (v=1), to the fundamental symmetric stretching mode of hydrogen cyanide, HCN(100), and subsequent thermal population exchange between HCN (100) and the upper laser state, HCN (110).Work supported by ARO Contract DAAG-29-83-K-0078