链间耦合对聚乙炔多链体系中电子极化子再激发态的影响

采用拓展紧束缚Su-Schrieffer-Heeger(SSH)模型,研究了链间耦合对反式聚乙炔多链体系中电子极化子再激发态的晶格位形、净电荷密度、局域能级波函数和态密度的影响.结果发现:对于两条链体系,当链间耦合很小(t⊥≤0.01 e V)时,注入到系统中的电子只会在第一条链上诱发产生一个晶格缺陷,形成电子极化子再激发态,这和单链体系是一致,而第二条链仍是二聚化基态.随着链间耦合的增大,第一条链上缺陷的局域度减少而第二条链上的缺陷局域度相应增加,直至两条链上的位形相同;对于多条链(5条链和6条链)体系,当耦合很小(t⊥≤0.05 e V)时,电子极化子再激发态也只会存在于一条链上,当链间耦合较强时,极化子再激发态会在链间层次性地扩展开来,并不会出现多条链位形相同;从两条链的能级图上可以看到随着链间耦合t⊥的增大,体系的带隙不断的增大和电子态密度显示的是完全吻合的,体系的导电性减弱.通过分析两条链体系在t⊥=0 e V和t⊥=0.1 e V的能级态密度,发现链间耦合越强,则中间局域能级的态密度越小,最后没有中间局域态.     

链间耦合对聚乙炔多链体系中电子极化子再激发态的影响

从拓展紧束缚模型出发,研究了链间耦合对反式聚乙炔多链体系中电子极化子再激发态的晶格位形、净电荷密度、局域能级波函数和态密度的影响。结果发现：对于两条链体系,当链间耦合很小（eV）时,注入到系统中的电子只会在第一条链上诱发产生一个晶格缺陷,形成电子极化子再激发态,这和单链体系是一致,而第二条链仍是二聚化基态。随着链间耦合的增大,第一条链上缺陷的局域度减少而第二条链上的缺陷局域度相应增加,直至两条链上的位形相同。对于多条链（5条链和6条链）体系,当耦合很小（0.05eV）时,电子极化子再激发态也只会存在于一条链上,当链间耦合较强时,极化子再激发态会在链间层次性地扩展开来,并不会出现多条链位形相同。从两条链的能级图上可以看到随着链间耦合的增大,体系的带隙不断的增大和电子态密度显示的是完全吻合的,体系的导电性减弱。通过分析两条链体系在eV和eV的能级态密度,发现链间耦合越强,则中间局域能级的态密度越小,最后没有中间局域态。     

Static Rouse modes and related quantities: Corrections to chain ideality in polymer melts

Following the Flory ideality hypothesis intrachain and interchain excluded-volume interactions are supposed to compensate each other in dense polymer systems. Multichain effects should thus be neglected and polymer conformations may be understood from simple phantom chain models. Here we provide evidence against this phantom chain, mean-field picture. We analyze numerically and theoretically the static correlation function of the Rouse modes. Our numerical results are obtained from computer simulations of two coarse-grained polymer models for which the strength of the monomer repulsion can be varied, from full excluded volume ("hard monomers") to no excluded volume ("phantom chains"). For nonvanishing excluded volume we find the simulated correlation function of the Rouse modes to deviate markedly from the predictions of phantom chain models. This demonstrates that there are nonnegligible correlations along the chains in a melt. These correlations can be taken into account by perturbation theory. Our simulation results are in good agreement with these new theoretical predictions.     

Chain "melting" in the composite Rb-IV structure

The Bragg peaks from the structure formed by the guest chains in the incommensurate composite structure of Rb-IV are all found to broaden strongly at pressures below 16.7(1) GPa. This signals a loss of the interchain correlation. At the lowest reachable pressure before the transition to Rb-III, 16.2 GPa, the correlation length is only approximately 30 A, or 4 times the interchain distance. There is also evidence of a loss of long-range order within each chain. The chains thus exhibit the onset of the characteristics of an ordered 1D liquid.     

Chain conformations and bound-layer correlations in polymer nanocomposites

Small angle neutron scattering studies on polystyrene loaded with spherical silica nanoparticles under contrast-matched conditions unequivocally show that chain conformations follow unperturbed Gaussian statistics independent of chain molecular weight and filler composition. Liquid state theory calculations are consistent with this conclusion and also predict filler-induced modification of interchain polymer correlations which have a distinctive scattering signature that is in nearly quantitative agreement with our observations.     

The competition between CDW and SDW in quasi-one-dimensional organic magnetic polymer with interchain coupling interaction

Based on a theoretical model proposed for interchain-coupled quasi-one-dimensional organic magnetic polymer, the effects of the interchain couplings and electron–electron interactions on the charge density wave (CDW) and spin density wave (SDW) that exist in the system are studied. It is found that the amplitude of the SDW along the main chain will decrease with increasing of the oscillatory term of the interchain couplings in the system, which is unfavorable to the ferromagnetic ground state of the system. Moreover, with different interchain couplings, there will all exist a critical value of the inter-site electron–electron Coulomb repulsion, and at this value, the system will experience a transformation from strong SDW state to strong CDW one, which will weaken the mediating function of the antiferromagnetic SDW along the main chain. As a result, the ferromagnetic correlation intensity between the spins of the side radicals will be affected and consequently the stability of the ferromagnetic state in the system will be weakened.     

Effect of single ion anisotropy on the critical temperature of classical quasi-one-dimensional magnets

The effect of single ion anisotropy energy on the three-dimensional ordering temperature of a classical quasi-one-dimensional magnetic chain is estimated using a mean field approximation for the interchain coupling and a classical spin field model for a chain. Numerical results are presented for T_c as a function of the interchain and interchain exchange interactions and the single ion anisotropy.     

On Perpendicular and Tilted Chains in Lamellar Crystals

Chain tilt and surface disorder were investigated in end-deuterated long n-alkane C₁₂D₂₅C₁₉₂H₃₈₄C₁₂HD₂₄ crystallized from solution and in n-alkane C₁₆₂H₃₂₆ crystallized from melt. Small-angle X-ray scattering and infrared spectroscopy were employed. Extended-chain crystals of C₁₂D₂₅C₁₉₂H₃₈₄C₁₂HD₂₄ as-grown from solution have the molecular axis perpendicular to the lamellar surface, but when heated, around 90°C, they start tilting relative to the layer normal. The tilt increases gradually to reach 35° just below the melting point. C₁₆₂H₃₂₆ crystallized from the melt at small supercoolings has chains tilted at 35° at the outset, as found previously for all melt-crystallized long alkanes and polyethylene. However, for the first time in long alkanes, it is found that when molten C₁₆₂H₃₂₆ is supercooled to ΔT≥10 K, crystals with perpendicular chains form. At still larger ΔT, the chains are once-folded, with a mixed population of tilted and perpendicular chain crystals. The use of Davydov splitting of the CH₂ and CD₂ bending vibration of the end-labelled alkane C₁₂D₂₅C₁₉₂H₃₈₄C₁₂HD₂₄ allows independent IR probing of molecular disorder at the deuterated surface and in the hydrogenous crystal interior. The initially small CD₂ splitting and the presence of an additional singlet component indicate a rough surface in as-grown crystals, with considerable longitudinal interchain disorder. It is estimated that about 10% of chains are displaced by up to a dozen C-atoms. The increase in splitting and decrease in absorbance of the singlet, which occur on annealing at progressively higher temperatures, are evidence of steady improvement in translational surface order, occurring simultaneously with increasing chain tilt angle. From the above evidence, it is concluded that the absence of tilt in as-grown crystals is not the result of high surface order, as in the case of shorter odd n-alkanes, but rather of a high frozen-in longitudinal disorder with chain ends or folds protruding out of or sunken beneath the crystal surface. It is also concluded that chain tilt only becomes necessary as the crystal surface becomes translationally more ordered and the crystal–amorphous interface sharpens. The effect of chain tilt on the Davydov splitting is addressed briefly.     

一维导电聚合物中激发态的链间弛豫

本文系统地研究了顺式高强聚乙炔的Raman和发光光谱,根据其Raman和发光光谱随激发能量的变化规律,以及分子链之间距离的改变对这种变化规律的影响,证明了聚乙炔中存在着激发态的链间弛豫,井且,这种弛豫过程随着分子链之间距离的减小而被加快.     

链间耦合对聚合物中双激子态反向极化的影响

从紧束缚模型出发，研究了链间相互作用对双激子态反向极化的影响.结果发现：加链间耦合后，双激子态仍主要局域在一条链中.当简并破缺较小时，反向极化程度随耦合强度的增加大幅提高；当简并破缺较大时，反向极化程度随耦合强度的增加基本不变. 关键词： 反向极化 双激子态 链间耦合     

Influence of the interatomic potential on thermotransport in binary liquid alloys: case study on NiAl

Equilibrium molecular dynamics simulation in conjunction with the Green-Kubo formalism is employed to study the transport properties of a model Ni₅₀Al₅₀ melt with the embedded-atom method potential developed in [G.P. Purja Pun, Y. Mishin, Phil. Mag., 2009, 89, 3245]. The principal objective of the work is to quantitatively characterise and analyse thermotransport in the system, i.e. diffusion driven by a temperature gradient. In addition, direct phenomenological coefficients for mass and thermal transport are also evaluated and analysed in the process. Furthermore, the results obtained are compared with previously published data for a different model of Ni₅₀Al₅₀ melt with an alternative embedded-atom method potential for the alloy as well as with experiment where possible. It is found that both potentials are able to consistently predict both direct transport coefficients over a wide temperature range. However, these two potentials are found to be inconsistent in characterising the cross-coupled heat and mass transport, predicting even different directions (sign) of the heat of thermotransport. The origin of this difference is discussed in the paper in detail.     

Interchain Coupling in Polydiacelene

Interchain coupling in polydiacetylene is investigated by considering two parallel chains and taking into account a hopping of π electrorls from one chain to the other. The correction in energy and the change of polaronic bioding energy resulting from interchain coupling are calculated by using Green's function, and the results are compared with experimental data.     

A theoretical insight into the solid-state optical properties of luminescent materials: the supermolecular approach

The way interchain interactions affect the absorption and luminescence properties of organic conjugated materials is addressed by means of correlated quantum-chemical calculations on molecular aggregates. Special emphasis is given to the influence of chain length and relative positions of the interacting units. The consideration of α -oligothiophenes in their crystalline structure allows us to shed light into the chain-length evolution of the optical splitting of the lowest optically-allowed excited state and to validate the theoretical approach by confronting the theoretical predictions to experimental results. Various strategies are proposed to prevent luminescence quenching when going from solutions to films or crystals.     

有机共轭高聚物的分子链间耦合局域态

有机共轭高分子中,孤子、极化子及激子都是基本的元激发,对解释有机聚合材料的导电发光特性起着主导作用.孤子、极化子以及激子等在晶格位形上都是各具特征的空间局域状态.本文将讨论在有机共轭高分子中存在着另一种局域态——链间耦合局域态,这种局域态是由于分子链间的相互作用所导致,在相互作用分子链端附近形成势阱,可有效束缚电子和空穴等带电粒子.     

Intermolecular interaction effects on the ultrafast depolarization of the optical emission from conjugated polymers

We have investigated the effect of interchain interactions on the ultrafast depolarization of the photoluminescence from solid films of a conjugated polymer. Accurate control was exercised over the interchain separation by threading of the conjugated chains with insulating macrocycles or complexation with an inert host polymer. Our measurements indicate that excitation into the higher electronic states of a chain aggregate is followed by a fast (<100 fs) relaxation into lower excited states with an associated rotation of the transition dipole moment. These findings emphasize the need for consideration of initial excitonic delocalization across more than one polymeric chain.     

Polymers near metal surfaces: selective adsorption and global conformations

We study the properties of a polycarbonate melt near a nickel surface as a model system for the interaction of polymers with metal surfaces by employing a multiscale modeling approach. For bulk properties, a suitably coarse-grained bead-spring model is simulated by molecular dynamics methods with model parameters directly derived from quantum chemical calculations. The surface interactions are parametrized and incorporated by extensive quantum mechanical density functional calculations using the Car-Parrinello method. We find strong chemisorption of chain ends, resulting in significant modifications of the melt composition when compared to an inert wall.     

Self-assembly of adenine-dimer chains on Cu(1 1 0): Driving forces from first-principles calculations

The formation of self-assembled adenine-dimer chains on the Cu(1 1 0) surface is studied theoretically by means of ab initio calculations. The main driving forces for the appearance of the long-range order within the molecular overlayer are identified. The stable and metastable adenine overlayers are the result of the interplay between dimer bonding, intra- and interchain interactions and geometry effects imprinted by the metal surface. An adsorption pathway is proposed to explain the characteristic directionality of the dimer chains. Scanning tunneling microscopy images are computed for the optimized chain structures and compared with the available experimental data.     

On the dynamics of polymers in dense systems – Results of neutron spin echo spectroscopy

One of the basic problems in the dynamics of polymers concerns the importance of geometrical or topological interactions which are directly related to the large scale molecular structures. In the famous reptation model these constraints are pictured in terms of a tube of localization following the average chain profile and confining the chain motion to the curve‐linear tube. Recently studying the dynamic structure factor of a single labeled chain in a polymer melt by means of neutron spin echo spectroscopy (NSE) led to a direct observation of these tube constraints. Here I shall summarize these neutron spin echo experiments. I shall address the NSE technique, present results on the entropy driven segmental chain dynamics, discuss the dynamics of single chains in the melt where the chain length is increased through the transition to “reptation” dynamics and display NSE measurements on long chain systems which revealed the molecular existence of the entanglement distance. Their magnitudes agree very well with tube diameters derived from dynamical mechanical measurements on the basis of the reptation model proving thereby the basic assumption of this Nobel Price winning concept. This revised version was published online in August 2006 with corrections to the Cover Date.     

Molecular fields in chainlike metamagnets

A two-sublattice metamagnet is formed of ferromagnetic Ising chains which interact ferromagnetically and antiferromagnetically. The intrachain coupling is strong compared to the interchain ones, as is observed in CoTAC. We treat the chains exactly and describe interchain interactions with molecular fields. The Neel temperature and tricritical point differ qualitatively from conventional molecular field results.