State-to-state dissociation–recombination and chemical exchange rate coefficients in excited diatomic gas flows

In this paper, simple analytical state-to-state rate coefficients for the dissociation–recombination and chemical exchange reactions are presented on the basis of kinetic theory in nonequilibrium excited diatomic gases. They take into account the excited vibrational and electronic states of the chemical species and are expressed according to the preferential character of the chemical reactions. Evolution of these rate coefficients varying according to the translational temperature, bringing into play molecules CO and C₂, are discussed.     

Efficient non-resonant intermolecular vibrational energy transfer

Molecular excited vibrational states are metastable states and we incorporate their finite lifetimes into the theory of vibrational energy transfer between weakly interacting molecules, i.e., at internuclear distances at which they do not have a chemical bond. Expressions for the effective lifetime of an initially vibrationally excited molecule in the presence of a neighbouring molecule are derived in closed form. These expressions allow one to analyse the physics behind the energy transfer. It is shown that due to different finite lifetimes of the isolated excited molecules, a very efficient vibrational energy transfer can take place between them even if their energies are rather off-resonance. Examples are discussed.     

Na2分子部分电子态的完全振动能谱和离解能的精确研究

对于大多数双原子分子的电子态，用现代实验方法或精确的量子理论方法往往可以获得含m个振动能级的能谱子集合［Ev］，而不易得到包含最高振动能级在内的所有高振动量子态能级的完全振动能谱{Ev}.鉴于Na2分子电子态的振动能谱和分子离解能De在实际研究和应用中的重要性，使用基于微扰理论的代数方法（AM），获得了Na2分子一些电子态的振动光谱常数和完全振动能谱；使用基于AM的代数能量方法（AEM）获得了这些电子态的正确离解能.研究结果表明：AM方法能从少数精确的实验能级获得精确的分子振动光谱常数集合和正确的完全振动能谱{Ev}，AEM方法获得的分子离解能比由文献发表的振动光谱常数计算得到的近似离解能值更准确，对于难以获得分子离解能的那些电子激发态，AEM方法能给出合理的离解能数据. 关键词： Na2分子 代数方法 振动能级 离解能 电子激发态     

强红外场作用下BCl3振动态传能动力学研究

基于文献[1],本工作在较高泵浦激光能通量范围,测量并研究了BCl₃分子振动激发v_3吸收谱及时间演变,观察了v₃激发弛豫的几种能量转移过程,以及对泵浦激光能量BCl₃气压等参数的依赖关系。表明泵浦光脉冲产生一个振动态非热分布的系综,转动能量转移对引起这种非热分布有重要作用。用简化碰撞动力学模型讨论了BCl₃振动激发吸收谱的演变过程,得到振动态再分布的简单关系;Pτ_v-v≌c/K′(T_v,T₀,q)和等效振动温度、平均吸收光子数的分析表达式,与实验结果定性地符合。 关键词：     

Impact of the Vibrationally Excited States on the Macroscopic Behaviour of the Band-like Electron Beam Discharge Plasma in H/H2-Mixture

The investigation of the impact of the vibrationally excited molecules in the electronic ground state was performed by simultaneously solving a balance equation system for the main charge carriers, the H atoms, the metastable H atoms, the H₂ molecules in the different vibrational states and for the power transfer of the electrons in the beam discharge mixture plasma. The balance equations for the vibrational states include in particular one-quantum step excitation and deexcitation, electronic excitation, dissociation and ionization from each vibrational level in electron collisions as well as the finite life time of these states because of the gas transfer through the band-like plasma. A main finding is that due to the additional impact of vibrationally excited molecules there is a marked enhancement of the resulting dissociation and ionization degree in the beam discharge plasma at medium power input from the turbulent electric field. For discharge parameters of practical interest the ionization and dissociation budget, the population of the vibrational states, the different energy dissipation processes and the energy pumping into the ladder of the vibrational states were calculated and discussed in detail.     

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.     

Improvement of the parametric method of the theory of vibronic spectra of polyatomic molecules: Absorption spectra and the structure of butadiene, hexatriene, and octatetraene in the excited state

The structure of the excited states and absorption spectra of butadiene, hexatriene, and octatetraene are calculated by the parametric method of the theory of vibronic spectra using models of the first-and second-order approximations. It is shown that these molecular models adequately reflect the molecular structure and allow one to predict quantitatively the shape and fine vibrational structure of the absorption spectra. When passing to the second-order approximation, only two additional (angular) parameters are used. These parameters are transferable in the series of polyenes. Compared to the first-order approximation model, the second-order approximation model more accurately takes into account the angular deformations of polyenes upon their excitation and describes the intensity distribution in the vibrational spectrum, including weak lines. In addition, the calculations also quantitatively predict spectral variations in the molecular series. The parametric method is more efficient for modeling polyatomic molecules in the excited states and their vibrational spectra compared to other semiempirical and ab initio methods.     

A comprehensive model to predict the microwave spectrum of propyne in the region 17–70 GHz for the ground and v10 = 1, 2, 3, 4, 5 vibrational states

A comprehensive model for predicting rotational frequency components in various v₁₀ vibrational levels of propyne was developed. A number of components of the rotational spectra in the ground and v₁₀ = 1, 2, 3, 4 excited vibrational states of propyne in the frequency range 17–70 GHz have been obtained. Molecular constants for these vibrationally excited states have been determined from more than 100 observed rotational transitions. From these experimentally observed components and a model based upon first principals for C_3v molecules, rotational constants have been expressed in a form which enables one to predict rotational components for vibrational levels for propyne up to v₁₀ = 5. The model also appears to be useful in predicting rotational components in more highly excited vibrational levels but data were not available for comparison with the theory. Experimentally measured frequencies are presented and compared with those calculated using the results of basic perturbation theory.     

Theory of pressure-induced vibrational and rotational absorption of diatomic molecules colliding with atoms 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 with neutral atoms. The previously neglected effects of excited vibrational states, mechanical anharmonicity, vibration-rotation interaction, transverse components of the dipole moment, and a higher order term in the expansion of the z component of the dipole moment are taken into account to obtain more accurate absorption coefficients at temperatures above 423 K. In the region of the fundamental wave number the excited vibrational states make more of a contribution to the absorption than their relative populations would indicate.     

Optoacoustic laser spectroscopy of excited vibrational molecular states

A new detection method for absorption from excited vibrational states is suggested, based on optoacoustic detection of weak absorption in a heated gas. Using this method CO₂ laser radiation (λ=9.6 μm) absorption was investigated from excited vibrational states of CO₂, BCl₃, and BF₃ molecules.     

Distribution of Vibrational Energy Levels of Protein Molecular Chains

The distributions of the quantum vibrational energy levels of the protein molecular chain are found by the discretely nonlinear Schoedinger equation appropriate to protein obtained from the Davydov theory.The results calculated by this method are basically consistent with the experimental values.Furthermore,the energy spectra at high excited states have also been obtained for the molecular chain which is helpful in researching the properties of infrared absoption and Raman Scattering of the protein molecules.     

Modeling vibronic spectra and excited states of polyenes with a parametric method

The structural-dynamic models of excited states and vibronic structure of absorption spectra of linear polyenes (R-(CH=CH)_n-R, R=H, CH₃, n=4, 5, 7) are calculated using the parametric method of the theory of vibronic spectra of such molecules. Good agreement is obtained between the calculated and experimental spectra. It is shown that the system of parameters of the method for the polyenes has a high degree of transferability in the series of related polyenes. The constructed models adequately reflect the real structure of the molecules in excited states and allow one to predict quantitatively the fine vibrational structure of the spectra, including relatively weak effects related to the methyl substitution. The dynamic of structural changes of the molecules upon their excitation is studied in the series of polyenes.     

Quantum ergodicity and energy flow in molecules

We review a theory for coupled many-nonlinear oscillator systems that describes quantum ergodicity and energy flow in molecules. The theory exploits the isomorphism between quantum energy flow in Fock space, that is, vibrational state space, and single-particle quantum transport in disordered solid-state systems. The quantum ergodicity transition in molecules is thereby analogous to the Anderson transition in disordered solids. The theory reviewed here, local random matrix theory (LRMT), describes the nature of the quantum ergodicity transition, statistical properties of vibrational eigenstates, and quantum energy flow through the vibrational states of molecules. Predictions of LRMT have been observed in computational studies of coupled nonlinear oscillator systems, which are summarized here. We also review applications of LRMT to molecular spectroscopy and chemical reaction rate theory, including adoption of LRMT in theories that predict rates of conformational change of molecules taking place at energies corresponding to those below and above the quantum ergodicity transition. A number of specific examples are reviewed, including the application of LRMT to predict (1) dilution factors of IR spectra of organic molecules, (2) rates of conformational change in chemical and photochemical reactions, (3) conformational dynamics of biological molecules in molecular beams, (4) rates of hydrogen bond breaking and rearrangement in clusters of biological molecules and water, and (5) excited state proton transfer reactions in proteins.     

Role of binding energy in Feshbach-resonant positron-molecule annihilation

Measurements of positron-on-molecule annihilation have established that positrons bind to a variety of molecules via vibrational Feshbach resonances. Data for deeply bound states in benzene and 1-chlorohexane and for positronically excited (i.e., second) bound states in alkanes are used to establish the dependence of annihilation rates on the binding energy and incident positron energy. With this dependence removed, annihilation rates for a broad class of molecules lie on a universal curve as a function of the number of molecular vibrational degrees of freedom. The implications of these results for theoretical models are discussed.     

Analysis of vibrational spectra of nano-bio molecules： Application to metalloporphrins

In this paper, we have applied the Lie algebraic model to nano-bio molecules to determine the vibrational spectra of different stretching and bending vibrational modes. The determined vibrational energy levels by the Lie algebraic model are compared with the experimental data. The results from the theoretical mode[ are consistent with the experimental data. The vibrational energy levels are clustering in the excited states.     

飞秒时间分辨质谱和光电子影像对分子激发态动力学的研究

分子量子态的研究,特别是分子激发态演化过程的研究不仅可以了解分子量子态的基本特性和量子态之间的相互作用,而且可以了解化学反应过程和反应通道间的相互作用.飞秒时间分辨质谱和光电子影像是将飞秒抽运-探测分别与飞行时间质谱和光电子影像相结合的超快谱学方法,为实现分子内部量子态探测,研究分子量子态相互作用及超快动力学过程提供了强有力的工具,可以在飞秒时间尺度下研究单分子反应过程中的光物理或光化学机理.本文详细介绍了飞秒时间分辨质谱和光电子影像的技术原理,并结合本课题组的工作,展示了这两种方法在量子态探测及相互作用研究领域,特别是激发态电子退相、波包演化、能量转移、分子光解动力学以及分子激发态结构动力学研究中的广泛应用.最后,对该技术的发展前景以及进一步的研究工作和方向进行了展望.     

Vibrational spectroscopy of bio-molecules: an algebraic approach

Porphyrins have received numerous considerable attentions during recent years because of their great biological importance. The most interesting areas of current research in molecular spectroscopy are the study of the vibrational ground and excited states of polyatomic molecules especially for the Metalloporphyrins. In this paper, we have calculated the fundamental and extrapolated vibrational energy levels of Magnesium, Nickel, Copper, Zinc, Metalloporphyrin molecules using U (2) algebraic model Hamiltonian. The results obtained by this method are in good agreement with the experimental data. This study gives a general approach for solving the vibrational spectra of Metalloporphyrin molecules.     

Experimental investigation of ultracold atom-molecule collisions

Ultracold collisions between Cs atoms and Cs2 dimers in the electronic ground state are observed in an optically trapped gas of atoms and molecules. The Cs2 molecules are formed in the triplet ground state by cw photoassociation through the outer well of the 0-(g) (P3/2) excited electronic state. Inelastic atom-molecule collisions converting internal excitation into kinetic energy lead to a loss of Cs2 molecules from the dipole trap. Rate coefficients are determined for collisions involving Cs atoms in either the F=3 or F=4 hyperfine ground state, and Cs2 molecules in either highly vibrationally excited states (nu'=32-47) or in low vibrational states (nu'=4-6) of the a3 summation(u)+ triplet ground state. The rate coefficients beta approximately 10(-10) cm3/s are found to be largely independent of the vibrational and rotational excitation indicating unitary limited cross sections.     

Ab initio study of ground and low-lying excited states of MgLi and MgLi+ molecules with valence full configuration interaction and MRCI method

The ground and low-lying excited states of MgLi and MgLi⁺ molecules have been investigated. The potential energy curves and the permanent and transition dipole moments of the MgLi and MgLi⁺ molecules are determined making use of the multi-reference configuration interaction and valence full configuration interaction with large basis sets. The core–valence correlation and scalar relativistic correction are also taken into account with aug-cc-pCVQZ basis set and the third-order Douglas–Kroll Hamiltonian approximation, respectively. The transition dipole moments are used to evaluate the radiative lifetimes of the vibrational levels for the low-lying excited states of the MgLi and MgLi⁺ molecules. The derived spectroscopic constants of the ground and low-lying excited states are in good agreement with available experimental and theoretical works.