小分子在真空紫外波段从量子态到量子态的光解离动力学

本文主要描述小分子在真空紫外波段(VUV,6-20 eV)光解离动力学的最新实验和理论研究进展.得益于基于商业化激光器的真空紫外光源技术,以及离子速度成像、高分辨氢原子-里德堡态标记-飞行时间测量和VUV-VUV泵浦-探测等方法的发展,研究人员现在可以对很多小分子在真空紫外波段的光解离动力学进行量子态到量子态层面的测量和研究,本文重点综述H_2(D_2,HD),CO,N_2,NO,O_2,H_2O(D_2O,HOD),CO_2,N_2O以及一些多原子分子在真空紫外波段光解离动力学的最新研究进展.这些小分子在真空紫外波段的光解离在天体化学以及大气化学中有着非常重要的应用.分子吸收一个VUV光子以后,通常会被直接激发到比较高的电子激发态,解离过程会涉及到多个电子态势能面之间的复杂非绝热相互作用.在实验上对解离截面等参数进行从量子态到量子态层面的精细测量对于深入了解这些复杂的势能面之间的相互作用有非常重要的意义.最近建成的大连相干光源是目前世界上唯一一台在真空紫外波段工作的自由电子激光,具有脉冲能量高、扫描范围宽(50～150 nm)等优越的性能,它的建成必将会大大促进小分子真空紫外光解离研究的发展.     

Accurate depolarization ratio measurements for all diatomic hydrogen isotopologues

The Raman depolarization ratios for individual Q₁(J”) branch lines of all diatomic hydrogen isotopologues – H₂, HD, D₂, HT, DT, and T₂ – were measured, for all rotational levels with population larger than 1/100 relative to the Boltzmann maximum at room temperature. For these measurements, the experimental setup normally used for the monitoring of the tritiated hydrogen molecules at KArlsruhe TRItium Neutrino experiment was adapted to optimally control the excitation laser power and polarization, and to precisely define the Raman light collection geometry. The measured Raman depolarization values were compared to theoretical values, which are linked to polarizability tensor quantities. For this, the ‘raw data’ were corrected taking into account distinct aspects affecting Raman depolarization data, including (1) excitation polarization impurities; (2) extended Raman excitation volumes; and (3) Raman light collection over finite solid angles. Our corrected depolarization ratios of the hydrogen isotopologues agree with the theoretical values (based on ab initio quantum calculations by R.J. LeRoy, University of Waterloo, Canada) to better than 5% for nearly all of the measured Q₁(J”) lines, with 1σ confidence level. The results demonstrate that reliable, accurate Raman depolarization ratios can be extracted from experimental measurements, which may be substantially distorted by excitation polarization impurities and by geometrical effects. Copyright © 2013 John Wiley & Sons, Ltd.     

Probing the paramagnetic interactions between the unpaired electronic spins of carbon atoms and the nuclear spins of hydrogen molecules with Raman spectroscopy

Carbon materials typically have a high density of unpaired electronic spins but the exact nature of the defect sites that give rise to their magnetic properties are not yet well understood. In this work, the paramagnetic interactions between the unpaired electronic spins of carbon atoms and the nuclear spins of hydrogen molecules were probed with Raman spectroscopy by monitoring the relative population of H₂ rotational states. For H₂, the symmetries of nuclear spin and rotational wave functions are correlated. Because of the weak interactions between H₂ nuclear spins, the transitions between odd and even rotational states are normally hindered. The magnetic field generated by unpaired electronic spins relaxes the selection rules and promotes transitions between H₂ rotational levels of different symmetry. This affects the rotational levels' relaxation kinetics toward equilibrium and makes H₂ molecules useful to study unpaired electrons in paramagnetic materials. It is suggested that simultaneous electron paramagnetic resonance and Raman measurements on carbon materials interacting with hydrogen molecules could result in a better understanding of the nature of paramagnetic defects in carbon materials, which could have a substantial impact on Li‐ion batteries or for understanding the graphene electronic properties. Copyright © 2011 John Wiley & Sons, Ltd.     

On effective molecular electronic charge densities and vibrational potential energy functions

Empirical relationships connecting equilibrium internuclear distances, harmonic force constants and atomic numbers for diatomic molecules which were presented in a recent communication by Anderson and Parr (Chem. Phys. Lett.10, 293 (1971)) are discussed in detail for 4b-6b and 1a-7b molecules as sample cases. It is shown how to estimate cubic and quartic force constants for these diatomic molecules using these relationships. Methods for estimating stretching force constants in polyatomic and excited state diatomic molecules are presented; sample cases CO₂, CS₂, OCS and the states of CO are treated.     

High resolution pulsed cars spectroscopy of the Q-branches of some simple gases

Coherent anti-Stokes Raman spectra of the Q-branches of N₂, O₂ and of v₁ of C₂H₂ have been measured with fairly high resolution (≈ 0.30 cm^-1) by means of a pulsed dye laser system. Calculated CARS spectra show very good agreement with the observed rotational Q-branch structure.     

Coherent antistokes raman scattering instrument for diagnostics of laser-induced processes

Summary A nonintrusive diagnostic system is described which permits simultaneous measurement of number density and temperature of small molecules in hostile environments such as photo-chemical reactors where laser induced processes occur. This system is formed by a frequency-doubled Nd:YAG laser which is partially used to excite a broad-band dye laser. The system utilizes a collinear beam arrangement, the signals are detected with an intensified photodiode array after proper filtering and wavelength separation through a 60° prism and a monochromator. Calibration measurements have been performed on small molecules (SiH₄, NH₃, C₂H₂, C₂H₄, C₂H₆) involved in the IR laser-induced photosynthesis of ceramic powders (Si₃N₄ and SiC). The effect of nonresonant background in number density measurements due to carrier gases used in flow reactors has been carefully investigated in cell experiments. The strong temperature dependence of the envelope of the vibrorotational Raman active band detected under rather low resolution is demonstrated in band contour calculations performed on hydrocarbons (C₂H₂ and C₂H₂). To speed up publication, the authors of this paper have agreed to not receive the proofs for correction.     

Fiber laser intracavity absorption spectroscopy for in situ multicomponent gas analysis in the atmosphere and combustion environments

Intracavity absorption spectroscopy with a broadband Er³⁺-doped fiber laser is applied for the measurements of several molecular species revealing quantitative information about the gas concentration, temperature and chemical reactions in flames. The spectral range of measurements extends from 6200 cm⁻¹ to 6550 cm⁻¹ with the proper choice of the fiber length and by moving an intracavity lens. With a pulsed laser applied in this experiment, the sensitivity to absorption corresponds to an effective absorption path length of 3 km assuming the cavity is completely filled with the sample. For a cw laser, the effective absorption path length is estimated to be 50 km. Absorption spectra of various molecules such as CO₂, CO, H₂O, H₂S, C₂H₂ and OH were recorded separately in the cell and/or in low-pressure methane and propane flames. The presented measurements demonstrate simultaneous in situ detection of three molecular products of chemical reactions at different flame locations. Variation of the relative strengths of OH absorption lines with the temperature enables the estimation of the local flame temperature. The sensitivity of this laser does not depend on the broadband cavity losses and it can be used for in situ measurements of absorption spectra in hostile environments such as contaminated samples, flames or combustion engines. The presented technique can be applied for various diagnostic purposes, such as in environmental, combustion and plasma research, in medicine and in the determination of stable isotope ratios.     

分子里德伯态的电子能级结构——一些小分子及分子离子的里德伯能级结构

本文在独立电子近似的基础上,利用多重散射自洽场理论方法,计算了He₂,H₂等分子和He₂⁺分子离子的里德伯能级结构。根据分子的电子组态极限,确定了各里德伯系列初始态的主量子数,阐明了这些分子和分子离子里德伯能级结构的变化规律。理论计算的结果同已有的实验数据符合良好,从而为超越独立电子近似的计算打下了基础。     

Generation of intense pulsed low-kinetic-energy molecular beams

A method for the generation of intense pulsed low-kinetic-energy molecular beams is described. The method is based on the formation of a cold (≈77 K) pressure shock as a result of interaction between an intense pulsed gas-dynamically cooled molecular beam with a solid surface. The pressure shock is used as a source of a secondary beam for generating low-energy molecules. The suggested method was used to obtain intense molecular beams of H₂, He, CH₄, N₂, and Kr with kinetic energies lower than or equal to 10 meV and H₂/Kr and He/Kr molecular beams with kinetic energies of H₂ and He molecules lower than 1 meV. The energy (velocity) of molecules in low-energy beams can be controlled by varying the intensity of the initial beam or temperature in the pressure shock.     

Investigation of the spatial profile of stimulated Raman scattering beams in D<Subscript>2</Subscript> and H<Subscript>2</Subscript> gases using a pulsed Nd:YAG laser at 266 nm

The stimulated Raman scattering (SRS) beam spatial mode structure is studied in H₂ and D₂ gases, in a 60 cm-long high-pressure Raman cell, using a pulsed Nd:YAG laser at 266 nm. The conversion efficiencies of the first and second Stokes in H₂, D₂ and H₂/D₂ mixtures have been measured precisely in the 1–14 atm range. The SRS beam profiles were recorded for different gas pressures in the high-pressure Raman cell and interesting behaviour is revealed. Homogeneous SRS spatial profiles were obtained only for pressures higher than 7 atm. For lower pressures the profiles are either in the form of a ring or of a more complicated shape. The results are explained in terms of nonlinear self-focusing processes during the pump beam propagation in the Raman cell. Also, from our measurements, a more precise value of the nonlinear index of refraction for the H₂ and D₂ at 266 nm is proposed. PACS 42.65.Dr; 42.60.Jf; 42.60.Lh; 42.65.Jx     

Pressure dependence of vibrational Raman scattering of narrow-band, 248-nm, laser light by H2, N2, O2, CO2, CH4, C2H6, and C3H8 as high as 97 bar

We have previously investigated methods that image high-pressure processes such as combustion inside automobile cylinders and aircraft engines, or chemical phenomena in supercritical fluids. Here we show that vibrational Raman scattering can simply obtain, quantitatively, densities of some combustion-relevant molecules. We use narrow-band KrF excimer-laser light. Measurements for H₂, N₂, O₂, CO₂, and CH₄ are in the pressure range from 1 to 60 bar, whereas those for C₂H₆ and C₃H₈ are up to their respective vapor pressures. All these species are at ambient temperature. Additional measurements are described for CO₂ up to 96.8 bar and 318 K, where CO₂ is a supercritical fluid. The O₂ measurements are complicated by a photochemical formation of O₃; those in supercritical CO₂ by drastic bending of the laser beam within this medium. We show that, for each gas, the Raman signal is directly proportional to gas density, thereby making quantitative analysis particularly convenient. For each species, we present an estimate of its Raman cross-section relative to that of N₂. However we recommend that future diagnostics users calibrate their own systems for relative species sensitivity. Received: 23 December 1999 / Revised version: 6 June 2000 / Published online: 20 September 2000     

Influence of the internuclear vector on ionization of molecules in intense laser field

We theoretically study the influence of the internuclear vector on molecular ionization in linear polarization laser fields through taking O₂, CO₂ as model molecules. We find that the ionization rates of O₂ and CO₂ depend on the molecular orientations. For O₂, the molecular orientation corresponding to the maximum ionization rate is about φ_m = 45^°, which is independent of the laser intensity; while for CO₂, this kind of molecular orientation varies with laser intensity. We also find the ionization suppression of molecule depends on the molecular orientations and the internuclear distance. The ionization suppression easily disappears for molecules with larger internuclear distance.     

Raman scattering from tuneable hot phonons and polaritons

We report the observation of Stokes and anti-Stokes Raman scattering from angular tuneable hot phonons and polaritons which have been pumped in uniaxial RbClO₃ crystals by a Q-switched CO₂ laser and probed with a c.w. argon ion laser.     

Softening of phonon modes in C60 crystals induced by laser irradiation: Thermal effects

Reversible softening of the intramolecular A _g(2) pentagonal pinch (PP) mode of a C₆₀ single crystal in the face centered cubic phase has been studied as a function of laser power density by means of Raman scattering. The average temperature rise in the laser excitation spot has been determined using the Stokes to anti-Stokes integrated peak intensity ratio for the H _g(1) phonon mode. Softening of the PP-mode was found to be due to heating of the sample resulting from laser irradiation, in good quantitative agreement with experimental results obtained for uniformly heated samples. These findings are in excellent agreement with results obtained by numerical calculations of the local temperature distribution and average temperature in the laser spot based on calculated integrated intensities of the Stokes and anti-Stokes bands of the PP-mode. These calculations were based on experimental data for the temperature dependence of phonon frequency and width, absorbance, and thermal conductivity in solid C₆₀. Zh. éksp. Teor. Fiz. 114, 1785–1794 (November 1998) Published in English in the original Russian journal. Reproduced here with stylistic changes by the Translation Editor     

Generating intense beams of low-energy molecules

A method for obtaining intense pulsed beams of molecules possessing low kinetic energies is proposed. The method is based on the formation of a cold pressure shock (shock wave) in an intense pulsed molecular beam interacting with a solid surface, which serves as a source of the secondary beam of low-energy molecules. The proposed method was successfully used to obtain intense beams of H₂, He, CH₄, and Kr molecules with kinetic energies not exceeding 10 meV, and H₂/Kr and He/Kr beams with kinetic energies of H₂ and He molecules below 1 meV.     

Semiempirical calculation of the absolute solvation shift of electronic and vibrational spectra of molecules in the gas-solution phase transition

Calculations of the main components of the absolute solvation shift of Δυ _∑ ^{a, f, R} optical absorption, emission, and Raman spectra of molecules in the gas-solution phase transition for solutions of several diatomic (HCl, DCl, H₂, D₂) and polyatomic (anthracene, 3-and 4-aminophthalimide) substances in some polar and nonpolar solvents are presented. The calculations are made by a new method of the semiempirical theory, which was proposed by the author earlier and makes such calculations possible for the first time. It is shown that the given theory adequately describes the photophysical effect under study and provides a correct prediction of the values of Δυ _∑ ^{a, f, R} , which differ for different systems by more than three orders of magnitude (from several inverse centimeters for vibrational spectra of H₂ and D₂ to many thousands of inverse centimeters for electronic fluorescence spectra of solutions of aminosubstituted derivatives of phthalimide).     

Optical study of a pulsed molecular beam

By using absorption spectra in a pulsed molecular beam, the rotational temperature and the flow density of the jet are deduced. By using this technique, a comparison between a pulsed and a continuous beam is also reported for NH₃, CF₂Cl₂, and C₂H₃Cl molecular beams. Moreover, the behaviour of the temperature and density inside the pulsed beam is analyzed as a function of time for pure Ammonia. From these measurements, we deduce that a small improvement is obtained for absorption spectroscopy in the jet by using a pulsed molecular beam.     

Optoacoustic detection of multiple photon molecular absorption in a strong IR field

A new method based on the optoacoustic effect has been proposed to measure multiple photon absorption at vibrational molecular transitions in a strong IR laser field. Comparison measurements of the average absorbed energy have been done by this method for molecules with different dissociation limits in a strong CO₂-laser field, the field intensity changed therewith by four orders. For the poly-atomic molecules C₂H₄ and SF₆ having a comparatively low dissociation limit, the absorption increases monotonously as the power density of laser radiation P increases up to the dissociation limit. For three-atom molecules, such as D₂O and OCS, absorption saturation takes place with P ? 10 MW/cm².     

Generation of UV and VIS laser light by stimulated Raman scattering in H2, D2, and H2/He using a pulsed Nd:YAG laser at 355 nm

2 ), deuterium (D₂), and mixtures of hydrogen and helium (H₂/He), versus Raman gas pressure and input pump energy of the pulsed Nd:YAG laser at 355 nm, are reported. Photon conversion efficiencies of 50% and 27% are achieved at the first Stokes lines (S₁) in H₂ and D₂, respectively. As a result, ultraviolet and visible laser light (274–503 nm) was generated with energies ranging from a few mJ up to several tens of mJ. Received: 5 January 1998/Revised version: 3 June 1998