氢键分子系统的非线性激发和质子传递的理论

基于对氢键分子系统中质子激发和移动的特点的仔细分析，提出一个新的哈密顿函数和理论，用以研究由质子位移所导致的质子的局域性涨落和重离子子晶格的构象畸变而引起的质子的集体激发和质子传递的特性，给出了运动方程和相应的孤立子解，讨论了这些解的特征 关键词：     

Properties of Proton Transfer in Hydrogen-Bonded Systems at Finite Temperature

The properties of proton transfer along hydrogen-bonded molecular systems are studied at finite temperature. The dynamic equations of the proton transport along the systems are obtained by using a completely quantum mechanics method. From the dynamic equations and its soliton solutions we find out specific heat arising from the motion of solitons in the systems with finite temperature and the critical temperature of the soliton in the protein molecules, which is about 318 K. This shows that we can continuously study some biological phenomena in the living systems by this model.     

“Symmetrical” phase and collective excitations in the proton system of ice

A model of the ice proton system taking into account quantum-mechanical tunneling of protons along hydrogen bonds has been formulated and investigated. When the tunneling amplitude is small the quantum ground state of the proton system is degenerate, like the classical ground state. At higher tunneling amplitudes, however, a transition to a nondegenerate state with a symmetrical distribution of protons on hydrogen bonds (a symmetrical phase of ice) is possible. Collective excitations of protons in the nonsymmetrical phase have been considered, and an equation that determines their spectrum has been derived. Zh. éksp. Teor. Fiz. 115, 2207–2213 (June 1999)     

Spectral Diagnostics of the Dynamics of the Formation of a Homoconjugated Complex [HCN.H.NCH]+

Optics and Spectroscopy - A quantum-mechanical analysis of the manifestations of the NHN hydrogen bond in the vibrational spectra of the [HCN.H.NCH]+ linear complex along the profile of the proton...     

苯乙烯基吡啶类液晶化合物的分子结构及相变过程的光谱研究

通过本乙烯基吡啶和不同脂肪羧酸间的氢键作用构成液晶的方法具有合成路线灵活、简便、易于变化的特点,本文通过变温红外光谱对做为质子受体的苯乙烯基吡啶粉液晶化合物的分子结构和相变过程中分子排列的变化进行了研究,结果表明在液晶分子中象羰基这样的偶极矩较大的极性基团,对分子所处的相态分子间的相互排列比较敏感。在红外光谱中羰基伸缩振动的变化可以看作是液晶分子相态转变的标志。     

Properties of Proton Transfer in Hydrogen-Bonded Systems at Finite Temperature

The properties of proton transfer along hydrogen-bonded molecular systems are studied at finite temperature. The dynamic equations of the proton transport along the systems are obtained by using a completely quantummechanics method. From the dynamic equations and its soliton solutions we find out specific heat arising from the motionof solitons in the systems with finite temperature and the critical temperature of the soliton in the protein molecules,which is about 318 K. This shows that we can continuously study some biological phenomena in the living systems bythis model.     

Hydration and translocation of an excess proton in water clusters: Anab initio molecular dynamics study

The hydration structure and translocation of an excess proton in hydrogen bonded water clusters of two different sizes are investigated by means of finite temperature quantum simulations. The simulations are performed by employing the method of Car-Parrinello molecular dynamics where the forces on the nuclei are obtained directly from ‘on the fly’ quantum electronic structure calculations. Since no predefined interaction potentials are used in this scheme, it is ideally suited to study proton translocation processes which proceed through breaking and formation of chemical bonds. The coordination number of the hydrated proton and the index of oxygen to which the excess proton is attached are calculated along the simulation trajectories for both the clusters.     

Quantum and classical relaxation in the proton glass

The hydrogen-bond network formed from a crystalline solution of ferroelectric RbH2PO4 and antiferroelectric NH4H2PO4 demonstrates glassy behavior, with proton tunneling the dominant mechanism for relaxation at low temperature. We characterize the dielectric response over seven decades of frequency and quantitatively fit the long-time relaxation by directly measuring the local potential energy landscape via neutron Compton scattering. The collective motion of protons rearranges the hydrogen bonds in the network. By analogy with vortex tunneling in superconductors, we relate the logarithmic decay of the polarization to the quantum-mechanical action.     

Recursion operators, higher-order symmetries and superintegrability in quantum mechanics

A connection between the theory of superintegrable quantum-mechanical systems, which admit a maximal number of integrals of motion, and the standard Lie group theory is established. It is shown that the flows generated by first- and second-order Lie symmetries of the bidimensional Schrödinger equation can be classified and interpreted as quantum-mechanical operators which commute with integrable or superintegrable Hamiltonians. In this way, all known superintegrable potentials in the plane are naturally obtained and slightly more general integrals of motion are found.     

MODELLING AND CONTROL WITH PIEZOACTUATORS FOR A SIMPLY SUPPORTED BEAM UNDER A MOVING MASS

In the paper, the dynamic modelling and control are presented for a simply supported beam under a moving mass. The equations of motion are obtained based on the Euler-Bernoulli beam theory by including the dynamic effect of a moving mass travelling along a vibrating path. The equations of motion are discretized by using the assumed modes method with the static deflection of the beam. In order to reduce the deflection of the beam under a moving mass, a controller with full state feedback is designed based on linearized equations of motion. Two piezoelectric actuators are bonded along the bottom of the beam at different locations determined by the minimization of an optimal cost functional. Numerical simulations are performed with respect to different constant velocities and different moving masses. The controller with two piezoelectric actuators shows excellent performance under unknown disturbances to the system.     

Primary photophysical processes in IR multiphoton excitation: Wavepacket motion and state selectivity

The wavepacket motion and state-selective excitation of harmonic and anharmonic oscillators by intense, monochromatic IR laser radiation are studied by a solution of the relevant quantum-mechanical equations of motion. The results are discussed in the framework of their importance as models for the primary photophysical processes in IR photochemistry.     

Spectroscopic Studies of Proton Transfer Equilibria In Hydrogen Bonded Complexes

Abstract

Recent studies on proton transfer equilibria for many hydrogen bonded complexes are discussed. These studies employ various spectroscopic techniques as infrared, ultraviolet, ¹H NMR, ¹³C NMR, ¹⁵N NMR and nuclear quadrupole resonance (NQR) spectroscopy. Special attention has been paid to Fourier transform infrared (FTIR), and it forms the main focus of this review, in particular for the study of proton transfer equilibria in proton sponges hydrogen bonded complexes. The influence of proton transfer equilibria on the physical, chemical and biological properties of hydrogen bonded complexes is shown. Some applications of proton transfer equilibria are also discussed.

     

Hydrogen bond dynamics in dodecanoic acid studied by QNS and NMR

The dynamics of hydrogen atoms in the hydrogen bonds of molecular dimers in dodecanoic acid (c phase) have been studied by quasi-elastic neutron scattering and pulsed nuclear magnetic resonance. Q-dependence measurements of the intensity of the quasi-elastic peak have established that the hydrogen atoms move along a line connecting the two oxygen atoms in the hydrogen bond. The correlation time for this motion has been studied by temperature dependence measurements of the width of the quasi-elastic line and of the proton spin-lattice relaxation time,T ₁. These studies reveal the quantum mechanical nature of the dynamics in the low temperature region. The dynamical parameters which characterise the motion have been determined by fitting the data to a model which invokes phonon assisted tunnelling. The frequency dependence ofT ₁ at low temperature is anomalous because the gradient of the ln(T ₁) vs 1/T curve is dependent on the applied magnetic field.     

Infrared Study of the Interaction of Tetramethylthiourea and Dimethylthioformamide with Phenol Derivatives

Abstract

The hydrogen bonded complexes between hydroxylic bonds and oxygen or nitrogen bases have been extensively studied by infrared spectrometry. However, meager experimental results are available for sulfur participation in hydrogen bond formation. There seems little doubt that in thioamides - hydroxylic complexes, the donor site for hydrogen bonding is sulfur, particularly in view of the blue shift of the n → π? transition of the thiocarbonyl group in proton donor solvents ¹. This paper reports on a study of the equilibrium constants (K) and on the frequency shifts of the 1 v _OH stretching vibration of hydrogen bonded complexes between tetramethylthiourea (TMTU) or dimethyltnioformamide (DMTF) and some phenol derivatives.     

Magnetic trapping of strongly-magnetized Rydberg atoms

Effective magnetic moments of drift Rydberg atoms in strong magnetic fields are obtained for different energy and angular-momentum states. Classical two-body trajectory calculations and quantum-mechanical one-body calculations are employed. For heavy atoms such as rubidium, the trapping dynamics can largely be explained by the net magnetic moment due to the cyclotron and the magnetron motion of the Rydberg electron. In light Rydberg atoms such as hydrogen, the intrinsic two-body nature of the dynamics becomes manifest in that the ionic motion significantly contributes to the effective magnetic moment. Also, light drift Rydberg atoms exhibit an anisotropic response to field-inhomogeneities parallel and transverse to the magnetic-field lines. The results are relevant to magnetic trapping of Rydberg atoms in strong-magnetic-field atom traps.     

Newtonian trajectories: A powerful tool for solving quantum dynamics

Since Ehrenfest’s theorem, the role and importance of classical paths in quantum dynamics have been examined by several means. Along this line, we show that the classical equations of motion provide a solution to quantum dynamics, if appropriately incorporated into the Wigner distribution function, exactly reformulated in a type of Boltzmann equation. Also the quantum-mechanical features of the canonical ensemble can be studied in this framework of Newtonian dynamics, if the initial distribution function is appropriately constructed from the statistical operator.     

Conductivity properties of proton transfer and influence of temperature on it in hydrogen-bonded systems

We study and calculate the mobility and conductivity of proton transfer and influence of temperature on it by pang's dynamic model in hydrogen bonded systems, which coincide with experiments. We further study the mechanism of magnetization of ciguid water in the basis of this model.     

Relativistic kinetic theory of quantum systems: III. Transport equation for a neutrino system

On the basis of the quantum-mechanical equations of motion and the statistical assumption that dynamical correlations present in the initial state may be ignored, a kinetic equation for a dilute neutrino system is derived. If the system is sufficiently uniform in space this equation reduces to the relativistic Boltzmann equation for massless particles with a quantum-mechanical transition probability.     

Comparative study of resonance-inhibited hydrogen bonded (RIHB) systems with different atoms involved: the leading role of σ-planarity

O, S, Se, and P atoms are considered as different proton donor/acceptor moieties in the resonance-inhibited hydrogen bonded (RIHB) interactions to conduct a comparative investigation. In order to study the effects of resonance and σ-skeleton planarity, the corresponding saturated and planar molecules are also computed. Moreover, to provide a broader perspective, all the given systems are compared to their resonance-assisted hydrogen bonded (RAHB) analogues. The natural bond orbital (NBO), the quantum theory of atoms in molecule (QTAIM), and the gauge-independent atomic orbital (GIAO) analyses, are performed to estimate the strength and nature of the intramolecular hydrogen bonds (IMHBs). The strength of IMHBs is also estimated using energy differences between closed and open conformers. According to the results, all the given RIHB systems suggest that resonance can obviously decrease the strength of the IMHBs. However, in the RIHB systems and also in some RAHB ones, the role of π-conjugation in the IMHB formation is less important than that of σ-planarity. In other words, the constraints imposed by σ-skeleton cause both the H-bond acceptor and donor groups to be situated close to each other; these effects outweigh the undesirable results of resonance, which totally lead to the formation of the RIHB.