狭缝微放电等离子体参数的光谱测量

利用平行管水电极介质阻挡放电装置,在氩气和空气混合气体中,得到了狭缝微放电等离子体。利用发射光谱法,研究了此放电中分子振动温度、分子转动温度和电子的平均能量随气体压强的变化。通过氮分子第二正带系(C3Πu→B3Πg)的发射谱线计算了氮分子的振动温度;利用氮分子离子(N2+)的第一负带系(B2Σu+→X2Σg+)的发射谱线计算了氮分子的转动温度;测量了氮分子离子391.4 nm和激发态的氮分子337.1 nm两条发射谱线的相对强度之比,研究了电子能量的变化。结果表明,当压强从60 kPa增大到100kPa,分子振动温度及分子转动温度均减小,氮分子离子谱线与激发态的氮分子谱线的强度之比亦减小。     

团簇六边形斑图等离子体参数的光谱测量

在氩气和空气混合气体介质阻挡放电中,首次发现了团簇六边形斑图。运用发射光谱法,研究了此斑图中单个团簇的三种等离子体参数：分子振动温度、分子转动温度以及电子的平均能量随空气含量的变化。实验通过测量氮分子光谱并采用氮分子第二正带系(C3Π_u→B 3Π_g)计算了振动温度;同时采集氮分子离子(N+₂)的第一负带系(B 2Σ+_u→X 2Σ+_g)计算转动温度。利用氮分子离子391.4 nm和激发态的氮分子337.1 nm两条发射谱线的相对强度之比,作为研究电子平均能量的变化的依据。结果显示,当混合气体中空气含量从16%逐渐增大到24%时,三种等离子体参数均逐渐增大。     

Evidence for subthermal rotational populations in stored molecular ions through state-dependent dissociative recombination

We demonstrate that the dissociative recombination of D2H+ with low-energy electrons depends on the rotational energy of the molecular ion such that highly excited ions have a larger rate coefficient than colder ones. Observations on an ion beam continuously interacting with electrons at low relative velocity indicate that excited rotational levels are preferentially depleted which, in competition with radiative heating due to blackbody radiation, provides an opportunity for controlling the rotational temperature of stored molecules.     

Rotational effects in low energy dissociative recombination of diatomic ions

The effect of rotational interaction in the low energy dissociative recombination process of diatomic molecules has been explored for typical molecular ions () which sample a large range of molecular masses. We show that rotation plays a role mainly for the indirect recombination process through bound Rydberg states, and for light molecules. When the direct process based on a strong electronic interaction is fast and dominating, rotational couplings can be safely neglected especially for heavier molecules like NO. Received: 18 September 1997 / Revised in final form: 17 October 1997 / Accepted: 20 October 1997     

Non-adiabatic interactions in charge transfer collisions

An analysis of the charge transfer mechanism in the collision of multiply charged ions with molecular and biomolecular targets is performed, considering the non-adiabatic interactions between the molecular states involved. Collisions of doubly charged C ²⁺ ions on small molecular targets, CO and OH, have been investigated, together with the analysis of charge transfer between C ⁴⁺ ions on uracil and halouracil biomolecular targets. The process is studied theoretically by means of ab-initio molecular calculations followed by a semi-classical treatment of the collision dynamics. The influence of rotational couplings is discussed with regard to the collision energy. Strong anisotropic and vibration effects are pointed out.     

High-resolution rotational spectroscopy in a cold ion trap: H2D+ and D2H+

The lowest-lying 1(01) <-- 0(00) transition of para-H(2)D(+) and 1(11) <-- 0(00) of ortho-D(2)H(+) has been detected by the enhancement of the D/H isotope exchange reaction in collisions with p-H2 upon rotational excitation. These are the first pure rotational spectra of molecular ions by action spectroscopy. For this purpose, a cryogenic multipole ion trap has been combined with narrow-band tunable radiation sources operating in the 1.25 to 1.53 THz range. The low temperature of the ions allows us to determine the astronomically important transitions with a relative precision of Delta nu/nu=10(-8). While the 1 476 605.708(15) MHz line center frequency for the o-D(2)H(+) transition agrees very well with previous unpublished work, the 1 370 084.880(20) MHz line center frequency for the p-H(2)D(+) transition deviates by 61 MHz. Potential future applications of this new approach to rotational spectroscopy are discussed.     

Spectroscopy of molecular ions: Laser induced predissociation of O 2 +

The technique of laser induced predissociation and laser induced fluorescence is applied to study spectra of gas-phase molecular ions. The main feature of the experiment is a beam of mass selected molecular ions illuminated by a pulsed dye laser. Over an extended range of excitation energies spectroscopic information can be obtained about positive and negative ions including transient species. As a first result we present predissociation spectra of O ₂ ⁺ ,b ⁴ bE _g ^? ?a ⁴ π _u Δv=3 andgDv=2 which can well be simulated by calculated spectra assuming a rotational ion temperature of 300δK.     

Electric/Magnetic Cross-Field Investigations of Aqueous Electrolytes in the Dielectric Region 0.3 MHz-3GHz

We are not aware of any techniques that have been developed to utilize the rotational magnetic properties of either ions or molecular dipoles in solution for analytical applications. Nor have any recent fundamental studies attempted to detect specific permeability dispersion of solutions in the upper-UHF region. The electromagnetic spectral regions which extend from high frequencies (MHz) to microwaves (THz) are presently used for liquid/solid nmr studies, esr studies, microwave spectroscopy of gases, and dielectric spectroscopy of electrolytes and solids. However, the effects of a magnetic field on the rotational behaviour of certain molecules, functional groups, and ions in solution also could be investigated using methodologies based on inductive coupled measurements from cross-field excitation. Some preliminary data are presented which indicate that a 1T magnetic field can cause what appears to be inductive peaks in concentrated aqueous lithium nitrate at approximately 0.84 and 2.14 GHz. Further studies are necessary to ascertain the origin of such phenomena, which are perhaps atomic nuclei relaxation and/or molecular effects.     

Role of highest occupied molecular orbitals in molecular field-free alignment by a femtosecond pulse

This paper studies the molecular rotational excitation and field-free spatial alignment in a nonresonant intense laser field numerically and analytically by using the time-dependent Schr?dinger equation. The broad rotational wave packets excited by the femtosecond pulse are defined in conjugate angle space, and their coefficients are obtained by solving a set of coupled linear equations. Both single molecule orientation angles and an ensemble of O₂ and CO molecule angular distributions are calculated in detail. The numerical results show that, for single molecule highest occupied molecular orbital (HOMO) symmetry σ tends to have a molecular orientation along the laser polarization direction and the permanent dipole moment diminishes the mean of the orientation angles; for an ensemble of molecules, angular distributions provide more complex and additional information at times where there are no revivals in the single molecule plot. In particular, at the revival peak instant, with the increase of temperature of the molecular ensemble, the anisotropic angular distributions with respect to the laser polarization direction of the π _g orbital gradually transform to the symmetrical distributions regarding the laser polarization vector and for two HOMO configurations angular distributions of all directions are confined within a smaller angle when the temperature of the molecular ensemble is higher.     

Topological chern indices in molecular spectra

Topological Chern indices are related to the number of rotational states in each molecular vibrational band. Modification of the indices is associated to the appearance of "band degeneracies," and exchange of rotational states between two consecutive bands. The topological dynamical origin of these indices is demonstrated through a semiclassical approach, and their values are computed in two examples. The relation with the integer quantum Hall effect is briefly discussed.     

Lability of the Configuration of Free Complex Molecules and Polarized Luminescence

We compare the sensitivity of the degree of polarization of integral fluorescence for excitation by light with a spectral width larger than the width of the rotating loop or only in the Qbranch of the rotating loop to a change in the principal moment of inertia (rotational constants) of complex molecules in vapors. It is shown that the sensitivity depends on the degree of asymmetry of the molecular top and the intramolecular orientation of the dipole transition moments. Improvement of the symmetry of the asymmetric top leads to an increase in the sensitivity to at least one of the rotational constants. Such effects are also noted for the sensitivity of the period of the rotational quantum echo to a change in the rotational constants.     

Design and analysis of MEMS MWCNT/epoxy strain sensor using COMSOL

Wiesenfeld and Faure investigated rotational quenching of H ₂CO by molecular hydrogen where they considered 40 rotational levels of o-H ₂CO and 41 rotational levels of p-H ₂CO. Data on energies of rotational levels of the molecule are fundamental in the investigation. We have found that the sequence of levels reported by Wiesenfeld and Faure is not as per convention of molecular physics. Their results are also available on the website: http://www.home.strw.leidenuniv.nl/~moldata/datafiles/ph2co-h2.dat, where the collisional transitions are shown even between the levels having equal energies. Data for such transitions should not be there.     

Role of electric field polarisation in rotational transitions

The molecular dynamics of polar diatomic molecule, interacting with linearly and circularly polarised laser field is studied. Non-perturbative quasi-energy technique is used to determine the rotational field surfaces. Degeneracy in different M-levels is found to be removed in the presence of circularly polarised electromagnetic radiation. In this paper, we present the calculations exhibiting the dynamics of rotational excitation of a linear molecule and characteristic features of spectra which become observable in considered fields. Received 22 March 2002 / Received in final form 15 July 2002 Published online 6 November 2002 RID="a" ID="a"e-mail: nsinghal@physics.du.ac.in RID="b" ID="b"e-mail: vnautiyal@himalaya.du.ac.in RID="c" ID="c"e-mail: manmohan@physics.du.ac.in     

离子分子束源的浓度调制光谱研究

建立了一套交流放电产生离子分子束源的装置,以N₂为例,束流中N＋₂的发射谱强度远大于N₂的发射谱强度,N+₂(B)/N₂(C)高达6∶1。根据其发射谱,对交流放电过程和浓度调制光谱进行了测量研究,并计算了离子分子激发态振动温度和转动温度,分别为3 310和282 K。     

Monomer counterrotations and tunneling splitting in CO dimer by data of millimeter wave spectroscopy

Analysis of the rotational spectrum of the molecular dimer (CO)₂ measured in the millimeter wave range has been performed and four new rotational states are revealed. Three of these states are characterized by almost free rotations of both monomers in the dimer. These states have approximately the same first term σ in the expansion of the rotational energy in powers of the rotational angular momentum J for various values of the momentum projections on the dimer axis (K=0, 1, 2) and various rotational constants B. The intrinsic rotational angular momenta of CO dimers, j₁=j₂=1, are determined from the σ value. In addition, a state with K=2 is found which corresponds to one of the known shape isomers of (CO)₂. The values of the tunneling splitting for each of the new states are determined. The results indicate that previous data on the suppressed tunneling are determined by the asymmetry of internal rotations in the CO monomers rather than by the _K value.     

On the dynamics of the orientationally disordered ionic crytals in two dimensions

The translational and rotational generalized susceptibilities have been calculated in a two-dimensional model crystal with orientational disorder. The Michel and Naudts' method has been employed to account for the rotation-translation coupling. The elastic and displacive character of the phase transition in the system has been shown to be independent of the mass and of the size of the disordered molecular ions. The plausibility of the third order continuous fraction expansion of the dynamic susceptibilities has been evidenced. The influence of the rotation-translation coupling on the dispersion relations are shown to be of the character observed experimentally.     

Structure and dynamics of water at liquid–vapour interfaces covered by surfactant monolayers of neutral stearic acid and charged stearate ions

The behaviour of water molecules at liquid–vapour interfaces with a surfactant monolayer of either stearic acid molecules or anionic stearate ions is investigated by means of molecular dynamics simulations. The density and dipolar orientational profiles and also the dynamics of translational and rotational motion of interfacial water molecules are calculated in the present work and the results are compared with the bulk liquid water and also of liquid–vapour interface of surfactant-free water. The present simulation results are also compared with available experimental results of similar interfacial systems with a monolayer of either neutral or ionic surfactants.     

Effect of tunneling ionization on dynamic alignment and post-ionization alignment of nitrogen molecules irradiated by different laser intensities

The dynamic alignment and post-ionization alignment of nitrogen molecules are investigated while considering the effect of tunneling ionization. The effects of tunneling ionization on the angular distribution are calculated when the molecules are irradiated by different laser intensities. The results show that laser intensity directly affects the time and extent of dynamic alignment. Furthermore, the extent of post-ionization alignment is not only determined by laser intensity but also affected by the final extent of dynamic alignment. The post-ionization alignment will dominate during the process of molecular (or molecular ion) rotational alignment for femtosecond laser pulse. The time of tunneling ionization is a significant factor to the final ensemble angular distribution of molecular ions when laser intensity is low.     

Laser Raman Investigation of Solid State Reactions

Abstract

Traditionally, molecular ions have been studied by mass spectrometers or ion-counting techniques. The great sensitivity and versatility of these techniques are clearly attested to by the vast amount of mass spectrometric literature. However, it is equally true that mass spectroscopy has its limitations; basically, it provides one only with a charge-to-mass ratio for an ion. Obviously, all quantum state information is lost, particularly the vibrational and rotational, and usually even the electronic distributions of the ions. Similarly, no structural information such as bond lengths and angles is obtained. Indeed, in some cases the information obtained is so slight that one cannot even write a structural formula for the ion or distinguish between different chemical isomers.     

Spectroscopy of Molecular Ions

Abstract

Traditionally, molecular ions have been studied by mass spectrometers or ion-counting techniques. The great sensitivity and versatility of these techniques are clearly attested to by the vast amount of mass spectrometric literature. However, it is equally true that mass spectroscopy has its limitations; basically, it provides one only with a charge-to-mass ratio for an ion. Obviously, all quantum state information is lost, particularly the vibrational and rotational, and usually even the electronic distributions of the ions. Similarly, no structural information such as bond lengths and angles is obtained. Indeed, in some cases the information obtained is so slight that one cannot even write a structural formula for the ion or distinguish between different chemical isomers.