硝基甲烷振动能量弛豫的集体模型

用分子动力学方法结合Dlott等人提出的"门槛模"理论研究集体相互作用下硝基甲烷振动能量弛豫过程.其中振动冷却过程与实验符合的很好.在振动激发过程的分子动力学模拟中观测到与实验一致的基频频移现象.用分子动力学方法从微观上详细地描述出分子"门槛模"振动激发过程.研究表明,在高温高压作用下,集体作用效应对多原子振动激发具有不可忽视的作用,能量传递过程中除了基频的作用外,强烈的非线性相互作用引起的振动模泛频也携带有大量的振动能,这些泛频也对分子振动能量传递产生重要影响.     

黑索金的非弹性中子散射及第一性原理计算

黑索金(环三亚甲基三硝胺, RDX, C₃H₆O₆N₆)是一种非常重要的次级炸药, 因其高能量密度及对外界刺激的低感度而具有广泛的军事和工业应用. 为了能在生产、运输、存储以及使用中对其行为进行有效控制, 人们对它的化学性质、力学性质, 尤其是起爆进行了大量的研究. 炸药的起爆是一个非常复杂的过程, 其中最主要的问题之一就是能量是如何从连续介质尺度的刺激转移到原子尺度引起吸热分解的. 根据冲击波致爆的非平衡态Zel'dovich-von Neumann-Doering模型, 声子作为最初的热载体在整个过程中起着非常重要的作用. 实验上, 非弹性中子散射技术是研究晶体中原子和分子运动动力学的有力手段, 尤其是对于包含了大部分声子晶格模式的低频区域来说极具优势. 利用非弹性中子散射技术测得了RDX 在10–104 cm^-1 范围内的振动谱, 结合固态量子化学计算, 对所测的12个振动模式进行指认. 研究结果有助于人们对起爆详细机理的认识.     

Vibrational energy transfer in a protein molecule

Mode coupling in a protein molecule was studied by a molecular dynamics simulation of the intramolecular vibrational energy transfer in myoglobin at near zero temperature. It was found that the vibrational energy is transferred from a given normal mode to a very few number of selective normal modes. These modes are selected by the relation between their frequencies, like Fermi resonance, governed by the third order mode coupling term. It was also confirmed that the coupling coefficients had high correlation with how much the coupled modes geometrically overlapped with each other.     

表面增强的分子间能量转移效应

研究了粗糙金属银表面对分子间能量转移效应的影响，实验观察到吸附分子增强的敏化荧光，结合表面局域电磁理论分析表明，吸附于银表面的分子间非辐射能量转移率被增强１０＾２倍，证实了表面增强的分子间能量转移效应的存在。     

几种硝基苯类炸药在外电场作用下的分子特性

采用密度泛函理论中的B3LYP方法,在6-31G*水平上研究了外电场对一些硝基苯类炸药分子的总能量、偶极矩、分子轨道能级和前线轨道能量差等分子特性的影响;考察了在外电场作用下分子前线轨道能量差与炸药的电火花感度之间的关系.结果表明,在外电场作用下分子总能量降低,偶极矩增大、前线轨道能量差减小;分子前线轨道能量差与炸药的电火花感度之间几乎线性相关,且外电场对这种线性相关性无明显影响.     

Zur Theorie der strahlungslosen Energierelaxation vieler miteinander wechselwirkender Molekülnormalschwingungen

Theory of Radiationless Energy Relaxation of a Large Number of Coupled Molecular Normal Vibrations On the base of a general relaxation theory recently developed by the authors the dissipation and transfer of energy in a system of a large number of coupled molecular vibrations are studied. Especially, vibrations of the same kind belonging to molecules localized at different space points of a dense medium are considered. For a short-range and a long-range interaction potential time-dependent generalized damping parameters are calculated, which give rise to non-exponential decay laws for the vibrational energy of the molecules.     

CO2 laser photoacoustic spectra and vibrational modes of heroin, morphine and narcotine

Heroin, morphine and narcotine are very large molecules having 50, 40 and 53 atoms respectively. Moderately high resolution photoacoustic (PA) spectra have been recorded in 9.6 μm and 10.6 μm regions of CO₂ laser. It is very difficult to assign the modes of vibrations for PA bands by comparison with conventional low resolution IR spectra. The ab initio quantum chemical calculations were used for determining the molecular geometries and normal mode frequencies of vibrations of these molecules for assignments of PA spectra.     

用对称的三聚物分子研究三组分纠缠和分子内能量动力学

为了建立纠缠与能量的联系, 研究了对称三聚物分子的不同初始态的量子纠缠动力学, 用共生度描述三组分纠缠,计算了三个振动模之间的相互作用能. 结果表明非简谐振动局域态的共生度与相互作用能是正关联占优,而简谐振动局域态的共生度与相互作用能是反关联占优.     

Nonlinear capillary vibration of a charged bubble in an ideal dielectric liquid

The problem of nonlinear radial pulsations and surface vibrations of a charged bubble placed in an ideal incompressible dielectric liquid is asymptotically solved up to the second order of smallness by the method of many scales. It is shown that, in the case of nonlinear vibrations, resonance energy exchange may take place not only between surface modes but also between the radial mode and a surface mode. A new type of instability (other than Rayleigh instability against the self-charge), instability against the excess vapor pressure in the bubble, is discovered. The new type of instability shows up as energy transfer from the centrosymmetric pulsation mode to all initially excited surface vibration modes simultaneously.     

用CS2分子研究振动局域态的纠缠和能量

研究CS₂费米共振耦合振动局域态的Neumann纠缠熵动力学, 并研究伸缩与弯曲振动的相互作用能量, 目的是建立纠缠与能量的联系. 结果表明伸缩振动局域态的纠缠与能量是反关联更明显, 而弯曲振动局域态的纠缠与能量是正关联更明显. 还讨论了非局域态的纠缠与能量的关系.     

Normal modes of CO adsorbed on metal surfaces

A normal mode analysis of experimental data from helium atom scattering (HAS) and electron energy loss spectroscopy (EELS) for vibrations of CO molecules adsorbed in on-top and bridge sites on Ni(100) is presented, using a refined force-constant analysis. The similar case of CO adsorbed on Pt(111) is reinvestigated, revealing a misassignment of normal modes in previous work. Finally, available experimental data for CO on Pt(111) is used to construct a trial potential energy surface.     

Spectroscopy of vibrational modes in metal nanoshells

In this work we study the spectrum of vibrational modes in metal nanoparticles with a dielectric core. Vibrational modes are excited by the rapid heating of the particle lattice that takes place after laser excitation, and can be monitored by means of pump-probe spectroscopy as coherent oscillations of transient optical spectra. In nanoshells, the presence of two metal surfaces results in a substantially different energy spectrum of acoustic vibrations than for solid particles. We calculated the energy spectrum as well as the damping of nanoshell vibrational modes. The oscillator strength of the fundamental breathing mode is larger than that in solid nanoparticles. At the same time, in very thin nanoshells, the fundamental mode is overdamped due to instantaneous energy transfer to the surrounding medium. PACS 78.67.-n; 78.67.Bf; 63.22.+m     

芴二聚体三重激发态能量转移的理论研究

利用电子结构计算和电子转移速率理论,研究了芴二聚体的三重激发态能量转移过程. 应用限制性密度泛函理论构造得到非绝热态后,计算了控制能量转移的两个重要参数{电子耦合强度和重组能. 电子耦合强度的波动利用电子动力学模拟计算. 通过对上述参数相关函数的计算,成功得到了体系哈密顿量的对角元和非对角元波动,并应用微扰理论和波包扩散方法得到了能量转移速率. 结果表明,静态和动态的波动都明显地增加了能量转移速率,但是动态波动导致的速度增加却小于静态波动.     

Intramolecular vibrational modes of polychlorodibenzo-p-dioxines of the D 2h symmetry

The infrared and Raman spectra of the octachlorodibenzo-p-dioxine molecule are measured and all normal vibrational modes of the molecule are calculated. Each vibrational mode was assigned to the vibrations of certain functional groups of atoms in the molecule, taking into account the local symmetry characteristics of the vibration mode. A correlation of vibrational modes by their shape was established in a series of molecules: dibenzo-p-dioxine, 2,3,7,8-tetrachlorodibenzo-p-dioxine, and OCDX. The influence of substituents on vibrational frequencies was also examined.     

UF6振动激发态分子的振动-振动驰豫

将振动态能量碰撞转移较成熟的长程力理论应用到大质量分子体系,采用准经典计算方法建立²³⁵UF₆和²³⁸UF₆同位素分子的碰撞理论;对²³⁵UF₆和²³⁸UF₆同位素间分子间v₃振动能量近共振碰撞转移过程进行研究;得到共振函数随能量差、共振转移概率和共振转移速率随温度的变化,发现它们随温度的增大而减小,说明碰撞分子的平动会降低其共振转移概率和速率,为控制²³⁵UF₆和²³⁸UF₆同位素分子间振动-振动转移引起的选择性损失这个激光光化学法分离铀同位素的关键问题提供理论依据,为实际分离铀同位素提供参考.     

Fast and accurate modeling of molecular atomization energies with machine learning

We introduce a machine learning model to predict atomization energies of a diverse set of organic molecules, based on nuclear charges and atomic positions only. The problem of solving the molecular Schr?dinger equation is mapped onto a nonlinear statistical regression problem of reduced complexity. Regression models are trained on and compared to atomization energies computed with hybrid density-functional theory. Cross validation over more than seven thousand organic molecules yields a mean absolute error of ～10 kcal/mol. Applicability is demonstrated for the prediction of molecular atomization potential energy curves.     

Saturable Absorption Enchantment of Au Nanorods Based on Energy Transfer between Longitudinal and Transverse Energy Levels

Four kinds of Au nanorods(NRs)with different aspect ratios are designed to adjust the relationship between resonance energy level of longitudinal(L)and transverse(T)modes.During the femto-second Z-scan experiments,huge saturable absorption phenomena are observed while the energy level T is located between one to two times of the energylevel L.This means that the energy may transfer between longitudinal and transverse energylevels in the same and/or different Au NRs.It effectively depresses the production of revised saturated absorption and increases the saturable absorption efficiency.This method is significant for the preparation of high-efficiency saturable absorption devices.