Theory of pressure-induced vibrational and rotational absorption of diatomic molecules at high temperatures

A derivation is given for the integrated absorption coefficient of pressure-induced pure rotational and vibrational transitions in binary collisions of homonuclear diatomic molecules of the same chemical species. The previously neglected effects of excited vibrational states, mechanical anharmonicity, and vibration-rotation interaction are taken into account to obtain more accurate absorption coefficients at high temperatures. In the region of the fundamental wave number the excited vibrational states make more of a contribution to the absorption than their relative population would lead one to expect.     

Determination of rotational temperatures of diatomic molecules from absorption spectra measured at moderate resolution

Two methods, one based on non-linear least squares and one based on an approximation, are described for determining the rotational temperature of diatomic molecules from absorption spectra measured with moderate resolution. Experimental tests with CO and CO/air mixtures gave good results. The importance of line widths and instrumental distortions is emphasized.     

Highest rotational and vibrational excitation of swift diatomic molecules scattered by solid surface

It is shown that at nondissociative scattering of swift molecules by solid surface and inverse population of the highest rotational and some vibrational states unattainable at thermal excitation could be achieved. For single crystal surface a specific polarization and orientational effects in rotational and vibrational excitation of the scattered molecules could be observed.     

Estimation of rotational and vibrational constants for diatomic molecules using Mattera's potential function

Summary The potential function suggested by Mattera, Salvo, Terreni and Tommasini is investigated further and the expressions for rotational constant α_e and anharmonicity constantw _e x _e are obtained. The α_e andw _e x _e values of twentyseven diatomic molecules are calculated using those expressions and they are compared with their experimental values.     

Investigation of the 2-0 pressure-induced vibrational absorption spectrum of hydrogen at temperatures below ambient

A theoretical fit has been made to oue laboratory measurements of the 2-0 collisionally induced H₂ absorption band for temperatures of 122 and 273.3 K and at a density of 20 amagats. A Lennard-Jones 6–12 intermolecular potential and a Birnbaum-Cohen line profile have been used. The fit resulted in a chi-square of 0.2%. Line widths have also been derived as a function of temperature. The lifetimes of the states have been calculated.     

Investigation of the 1-0 pressure-induced vibrational absorption spectrum of hydrogen at temperatures below ambient

A theoretical fit has been made to our laboratory measurements of the 1-0 collisionally induced H₂ absorption band over a temperature range of 100–273°K and for densities up to 22 amagats. Both the Birnbaum-Cohen and the MacTaggert-Hunt line shape profiles were used. In addition, an intermolecular potential of either a Lennard-Jones 6–12 or a Morse-spline-van der Waals has been used for each line shape. The best fit resulted in a chi-square of 5%. Line widths have also been derived as a function of temperature. The lifetimes of the states were calculated.     

Theory of the rotational structure of resonant Raman scattering by diatomic molecules

The apparatus of irreducible tensor operators is used to calculate the rotational structure of resonant Raman light scattering by freely rotating diatomic molecules. It is shown that solution of the problem reduces to the calculation of certain special coefficients. Their relation to the Placzek-Teller factors (which are well known in the theory of polarizability) is established. The nonzero coefficients are computed for the case when resonant rotational scattering is due to the¹ terms of the diatomic molecule.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 54–58, October, 1987.The author thanks T. N. Popov for interest in the work.     

Rotational and vibrational excitation of sputtered diatomic molecules

The rotational and vibrational level population distributions of ground and electronically excited states of several homonuclear and heteronuclear molecules are calculated for direct ejection, association, and associative ionization mechanisms of molecule sputtering. The cascade properties, formation mechanism, initial atom separation, and axis orientation to the surface are clearly reflected in the sputtered molecule distributions. In general, extensive non-Boltzmann rotational and vibrational distributions are predicted. The probability that an atom pair survives the ejection, for typical sputtering parameters, is high; approximately 50% for homonuclear molecules to near 100% for hydrides. The predictions are compared with experimental optical emission spectra in the accompanying paper.     

Multiphoton dissociation of diatomic molecules at high intensities

A non-perturbative method is used to obtain an analytic expression for the rate of multiphoton dissociation of diatomic molecules as a function of the incident radiation. The two-photon dissociation process is considered as an example.     

The pressure-induced rotational absorption spectrum of hydrogen: I

The pressure-induced rotational absorption spectrum of hydrogen has been investigated at ?60°c, 25°c and 80°c in pure hydrogen and in mixtures of hydrogen with helium, argon, nitrogen and carbon monoxide. The integrated absorption coefficients have been evaluated. In mixtures of hydrogen and carbon monoxide a simultaneous rotational-vibrational transition could be observed.     

差分收敛法对双原子分子高J值转动谱线的预言

为了更精确地预言转动量子数J ≥ 100时双原子分子R支和Q支的振转跃迁谱线, 本文在考虑了转动能级展开式中高阶小项H_v的前提下重新推导出能更好地预言R支和Q支跃迁谱线的物理解析公式. 另一方面, 通过对差分收敛法计算过程的细致分析, 从物理误差的角度提出了一个在没有实验数据作为参照时仍然能有效收敛的重要物理判据. 应用这些新公式和新判据对TiF和CO分子R支振转跃迁谱线和TiF分子Q支振转跃迁谱线进行了研究. 结果表明: 包含高阶小项H_v的新公式的预言结果精度比原有不含H_v的公式的结果提高了一个数量级; 新判据的使用能更有效地减小预言谱线的可能误差, 提高预言结果精度. 最后通过与最小二乘法计算结果的对比, 进一步说明新公式和新判据在预言R支和Q支振转跃迁谱线数据方面的有效性和准确性.     

Transitions between Rydberg states of diatomic molecules in slow collisions with atoms

A close analytic representation has been found for the Green function of highly excited diatomic molecule in the framework of the multichannel quantum defect method. This expression has been used to describe the potential energy surfaces of the quasi-molecule X ₂ ^* +A. The specific behaviour of the terms of this system has been studied as a function of the angular orientation of the moleculeX ₂ and of the distanceR between the molecule and atomA. The terms have been found to have quasi-crossings responsible for the transitions when particles suffer collision. Some terms located near the continuous spectrum boundary, when the distance varies, cross the spectrum boundary and pass into auto-ionization state. Calculations have been made for the system H ₂ ^* +B, whereB is an inert gas atom. Cross-sections of the vibrational transitions occurring under slow atom-molecule collisions have been evaluated.     

双原子分子振动能谱与离解能的精确研究

代数方法(AM)的建立解决了实验方法和精确量子力学理论方法难以获得双原子分子的包含最高振动能级在内的所有高阶振动能级的精确数值这一问题.基于LeRoy与Bernstein的工作,孙卫国等又建立了精确计算双原子分子离解能的新解析表达式.应用新公式和代数方法(AM),研究了一些双原子分子部分电子态的振动能谱和分子离解能,获得了与实验值符合非常好的理论结果.该方法在理论上提供了获得双原子分子完全振动能谱和精确分子离解能的物理新方法.     

Ratiometric comparison of intense field ionization of atoms and diatomic molecules

Intense-laser ionization rates for rare gas atoms and diatomic molecules have been precisely compared by making simultaneous measurements of ionization yield vs laser intensity for mixed atomic and molecular targets. At a given laser intensity, the N (2) and F (2) ionization yields are slightly greater than that of Ar. Conversely, comparison of O (2) and S (2) with Xe indicates significant ionization suppression in these molecules. Recent molecular ionization models that successfully describe ionization suppression in O (2) and its absence in N (2) fail to explain our observations in F (2) and S (2).     

Quantum mechanical calculation of rotational constants and Franck-Condon factors of diatomic molecules

In this paper, the question of reliability of the Morse potential as a potential curve for a diatomic molecule is investigated on the basis of calculating the rotational constant. It is shown that the Morse potential describes well potential curves of X¹Σ _q ⁺ and B¹Π_u electronic states of a Na₂ molecule. Calculations of Franck-Condon factors for X¹Σ _q ⁺ ? B¹Π_u band of a Na₂ molecule using wave functions of the Morse potential confirm the known correlation between the values of Franck-Condon factors and rotational constants of combined electronic states.     

Atom-pair formulation of the rotational and vibrational motions of molecules

We have expressed the angular momentum and the internal kinetic energy of a molecule (a system of point masses) in terms of atom-pair contributions, paralleling the use of pairwise additive potential energy functions. The partitioning of the internal kinetic energy into rotational and vibrational contributions is then made following the analysis of Jellinek, J., and Li, D. H., 1989, 98, Phys. Rev. Lett., 62, 241. The resulting expressions contain pair position and velocity variables whose redundancy may be removed by transformation to Jacobi vector coordinates. These expressions should prove especially useful for describing the internal motions of clusters of like atoms.     

Studies on dissociation energies of diatomic molecules using vibrational spectroscopic constants

New analytical expression and numerical approach are suggested to calculate dissociation energies De of diatomic molecular states using an extreme value method (EVM). Studies on some electronic states of OH, BH, N2, Br2, ClF and CO molecules show that the accuracy of the EVM dissociation energies depends on the number of correct vibrational constants used in the calculations. The convergence qualities of De are suggested to be an alternative physical criterion to measure the qualities of the various sets of vibrational constants from different literature for the same diatomic state.