Interaction of translational and rotational modes of a molecular impurity in two-dimensional atomic crystals

The interaction between the translational and rotational degrees of freedom of a diatomic homonu-clear molecule that executes a motion at the site of a two-dimensional close-packed atomic matrix located on a close-packed atomic substrate (a molecular substitutional impurity in the crystal field of the two-dimensional lattice of a solidified rare gas) is investigated theoretically. The relationships describing the effective dynamic properties of an impurity rotator in the presence of translational excitations of its center of inertia are derived in the framework of consistent procedures on the basis of the Lagrangian (the functional-integral method) and Hamiltonian (the canonical-transformation method) formalisms. The inclusion of the translational-rotational interaction leads to a radical change in the inertial properties of the molecule. This manifests itself in a change in the form of the operator for the rotational kinetic energy as compared to the corresponding expression for a free rotator. The inertia tensor components for the molecule become functions of molecular orientation, and the molecule, in terms of rotational motion, transforms into a “parametric rotator” whose effective kinetic energy is represented as a generalized quadratic form of the angular momentum (or the angular velocity) components with a symmetry corresponding to the symmetry of the external crystal field. The translational-rotational interaction also results in the renormalization of the parameters of the crystal potential without a change in its initial form.     

Index of refraction for cold lithium- and diatomic sodium waves traveling through cold noble gases

In the present paper we propose to measure the index of refraction for diatomic sodium molecules traveling through a cold helium gas. Theoretical calculations of the index of refraction for this system are presented as a function of the molecule velocity and atom gas temperature. Whereas previous theoretical efforts to compute the refractive index have been concerned with atomic systems and atomic matter waves, we extend the investigation to diatomic molecules in the present work. To enable such calculations the potential energy surface for the atom-molecule interaction is calculated ab initio, along with the long range dispersion coefficients for the atom-molecule system. The full close-coupled equations, describing the atom-molecule collisions, are solved numerically to work out the influence of the collisions on the matter waves. We investigate the sensitivity of the results upon changes and inaccuracies in the potential energy surface. Several molecular rotational levels are included in the present study, and the index of refraction is found to depend on the rotational state. In addition, the index of refraction for atomic lithium matter waves traveling through the cold noble gases helium and argon are computed, motivated by a recent experiment with atomic lithium matter waves. Different resonances (glory- and scattering resonances) are identified from the results. Such resonances offer an important opportunity for the comparison of experiment and theory.     

Rotational structures of long-range diatomic molecules

We present a systematic understanding of the rotational structure of a long-range (vibrationally highly-excited) diatomic molecule. For example, we show that depending on a quantum defect, the least-bound vibrational state of a diatomic molecule with -C _n /r ⁿ (n > 2) asymptotic interaction can have only 1, 2, and up to a maximum of n-2 rotational levels. A classification scheme of diatomic molecules is proposed, in which each class has a distinctive rotational structure and corresponds to different atom-atom scattering properties above the dissociation limit.Received: 15 June 2004, Published online: 28 September 2004PACS: 33.15.Mt Rotation, vibration, and vibration-rotation constants - 34.10. + x General theories and models of atomic and molecular collisions and interactions (including statistical theories, transition state, stochastic and trajectory models, etc.) - 03.75.Nt Other Bose-Einstein condensation phenomena - 03.75.Ss Degenerate Fermi gases     

Rovibrational excitation within the infinite conical well: Desorption of diatomic molecules

An analytic model for the hindered rotational states of a diatomic molecule adsorbed upright on a solid surface is discussed. Various model dynamics situations, within the sudden approximation, designed to simulate desorption are presented and rotational state distributions are calculated including both rotational and translational degrees of freedom. Criteria are established for observing rotationally cool desorbed molecules.     

Fullerene quantum gyroscope

We report the observation of quantized rotational states of a diatomic C2 unit in solid endohedral fullerene C(2)Sc(2)@C(84). The rotational transitions induce a periodic line pattern in the low energy Raman spectrum. The rotational constant B and the C-C distance were found to be 1.73 cm(-1) and 0.127 nm, respectively. Density functional calculations revealed an intrinsic rotational barrier of the order of only a few meV for the C2 unit. The Schr?dinger equation involving the potential barrier was solved and the Raman tensor matrix elements were calculated, yielding good quantitative agreement with the experiment. To our best knowledge this is the first intrinsic rotational spectrum of a diatomic plane molecular rotor.     

Rigid rotators and diatomic molecules via Tsallis statistics

We obtain an analytic expression for the specific heat of a system of N rigid rotators exactly in the high temperature limit, and via a perturbative approach in the low temperature limit. We then evaluate the specific heat of a diatomic gas with both translational and rotational degrees of freedom, and conclude that there is a mixing between the translational and rotational degrees of freedom in nonextensive statistics.     

Blackbody-radiation-assisted laser cooling of molecular ions

The translational motion of molecular ions can be effectively cooled sympathetically to temperatures below 100 mK in ion traps through Coulomb interactions with laser-cooled atomic ions. The distribution of internal rovibrational states, however, gets in thermal equilibrium with the typically much higher temperature of the environment within tens of seconds. We consider a concept for rotational cooling of such internally hot, but translationally cold, heteronuclear diatomic molecular ions. The scheme relies on a combination of optical pumping from a few specific rotational levels into a "dark state" with redistribution of rotational populations mediated by blackbody radiation.     

Predicting absorption and dispersion in acoustics by direct simulation Monte Carlo: Quantum and classical models for molecular relaxation

In the current study, real gas effects in the propagation of sound waves are simulated using the direct simulation Monte Carlo method for a wide range of frequencies. This particle method allows for treatment of acoustic phenomena at high Knudsen numbers, corresponding to low densities and a high ratio of the molecular mean free path to wavelength. Different methods to model the internal degrees of freedom of diatomic molecules and the exchange of translational, rotational and vibrational energies in collisions are employed in the current simulations of a diatomic gas. One of these methods is the fully classical rigid-rotor/harmonic-oscillator model for rotation and vibration. A second method takes into account the discrete quantum energy levels for vibration with the closely spaced rotational levels classically treated. This method gives a more realistic representation of the internal structure of diatomic and polyatomic molecules. Applications of these methods are investigated in diatomic nitrogen gas in order to study the propagation of sound and its attenuation and dispersion along with their dependence on temperature. With the direct simulation method, significant deviations from continuum predictions are also observed for high Knudsen number flows.     

The LEDO expansion for diatomic overlap densities: application to the density functional theory of molecules

The limited expansion of differential overlap (LEDO) approach for the expansion of diatomic overlap densities in terms of mono-centre densities is discussed in the context of density functional theory (DFT). It is shown that it leads to a particularly simple construction scheme for major parts of the secular matrix, i.e. the electron-electron interaction and the exchange-correlation potential: using the LEDO expansion coefficients, matrix elements between atomic orbitals located on different centres can be expressed in terms of the corresponding mono-centre elements, thus allowing the reduction of three-centre and four-centre integrals to two-centre integrals. This results in the first DFT method with formal N ² scaling for the construction of the secular matrix, with N being the dimension of the atomic orbital (AO) basis set. Test calculations show that numerical agreement with the results of conventional DFT calculations is excellent.     

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     

Semiempirical study of perturbations of the Landé g factors of the electronic-vibrational-rotational levels of hydrogen: I. Theory

Theoretical analysis of perturbations of the Landé g factors of the electronic-vibrational-rotational levels of a diatomic molecule is performed for the case of interactions between electronic states whose number is arbitrary finite and that are not limited by the smallness of the parameter describing these interactions, with regard for the interaction of rovibrational states with an arbitrary finite number of vibrational-rotational levels of individual perturbing electronic states. The spin-multiplet interaction between rovibrational states was disregarded. As a result of general consideration, formulas are obtained for the g factors of rovibrational levels for the following cases: (i) mutual perturbation of a pair of levels; (ii) an nl complex of terms; and (iii) the interaction between an arbitrary number of vibrational-rotational levels of electronic states (whose number is also not limited) considered in the first order of the perturbation theory. The formulas obtained are given in the form of dependences on differences in observed (perturbed) values of rovibrational terms and matrix elements of vibrational wave functions dependent on the internuclear distance, which, in turn, are matrix elements of the electron wave functions of different operators that take into account the interaction between the electrons and nuclei of a molecule. The possibilities of using the obtained expressions in semiempirical study of perturbations and of determining the absolute dependences of the g factors of rovibrational levels of the electronic states of diatomic molecules (in particular, the hydrogen molecule) on the vibrational and rotational quantum numbers are analyzed.     

Theory of non-adiabatic vibrational relaxation in atom-molecular collisions

The transition complex method is used for calculating the rate constant of non-adiabatic vibrational deactivation of diatomic molecules in the ²II electronic state upon collisions with inert gas atoms. The main contribution to the rate constant comes from vibronic transition caused by spin-orbital and orbital-rotational couplings. The two-dimensional Landau-Zener approximation is considered in connection with calculation of the nonadiabatic transition near the crossing line of two potential surfaces, and the limitations of ideas concerning the activated complex are discussed. The general expression for the rate constant derived from the diatomic molecule-atom collision is correlated with that for the atomic collision.     

E.S.R. spectrum of the radical produced by ultra-violet irradiation in solid azobisisobutyronitrile

The coupled τ operator formalism is applied to derive exact and approximate selection rules that govern the rotational state distribution of products following an interaction between a diatomic molecule and a free atom. The analysis is performed for a two-channel system in which one of the atoms is infinitely heavy.     

考虑转动能的一维/二维Boltzmann-Rykov模型方程数值算法

研究考虑转动能的Boltzmann-Rykov模型方程,基于转动自由度对气体分子速度分布函数矩积分,引入约化速度分布函数,应用离散速度坐标法与数值积分技术,将气体运动论模型方程化为在离散速度坐标点处关于三个约化速度分布函数的联立方程组.应用拓展计算流体力学有限差分方法,数值计算考虑转动自由度的双原子气体一维、二维Boltzmann模型方程,得到高、低Knudsen数一维激波管内流动和二维竖直平板绕流问题的流场,分析验证考虑转动能的Boltzmann-Rykov模型方程全流域统一算法求解一维/二维气体流动问题的可靠性.结果表明,气体稀薄程度与分子内自由度对流场具有较大影响,且Knudsen数较高的稀薄气体流动呈现严重的非平衡流动特点.     

Using molecules to measure nuclear spin-dependent parity violation

Nuclear spin-dependent parity violation arises from weak interactions between electrons and nucleons and from nuclear anapole moments. We outline a method to measure such effects, using a Stark-interference technique to determine the mixing between opposite-parity rotational/hyperfine levels of ground-state molecules. The technique is applicable to nuclei over a wide range of atomic number, in diatomic species that are theoretically tractable for interpretation. This should provide data on anapole moments of many nuclei and on previously unmeasured neutral weak couplings.     

石墨烯等二维原子晶体薄片样品的光学衬度计算及其层数表征

本文以鉴别机械剥离法制备的高质量石墨烯样品的层数为例, 阐明了如何利用传输矩阵来计算二维原子晶体薄片样品的光学衬度, 并进一步精确地鉴别其层数. 计算结果表明测试时所选用的显微物镜数值孔径对精确确定薄片样品的层数非常重要, 并为实验所证实. 同时提出了使用两个激光波长可以快速地表征样品尺寸接近物镜衍射极限的薄片样品层数的方法. 本文所采用的传输矩阵形式非常适合于计算二维原子晶体薄片样品的光学衬度, 并可以方便地推广到更复杂的多层衬底结构, 以便快速和准确地鉴别各种衬底上二维原子晶体薄片样品的厚度. 关键词： 二维原子晶体材料 层数 传输矩阵 光学衬度     

转动喇曼散射截面的群论计算

本文利用群链U(4)U(3)O(3)描述双原子分子N_2和O_2振转谱的对称性质,并利用群论方法计算了N_2和O_2分子转动喇曼散射的跃迁矩阵元,给出了它们的转动喇曼散射的截面。结果与实验较好地符合。     

Mechanism of angular momentum exchange between molecules and Laguerre-Gaussian beams

We derive the interaction Hamiltonian between a diatomic molecule and a Laguerre-Gaussian beam under the assumption of a small spread of the center of mass wave function of the molecule in comparison with the beam waist. Considering the dynamical variables of the center of mass, vibrational, rotational, and electronic motion, we show that, within the electronic dipole approximation, the orbital angular momentum of the field couples with the rotational and electronic motion. The changes in the transition probabilities and selection rules induced by the field orbital angular momentum and the applicability of the derived interaction mechanisms for polyatomic molecules are discussed.