基于含时密度泛函理论的表面等离激元研究进展

纳米粒子的局域表面等离激元(LSP)由于其新颖的光学特性成为目前国内外研究的热点之一. 本文利用含时密度泛函理论(TDDFT)对金属团簇及石墨烯纳米结构中的等离激元激发及调制的物理本质进行了研究. 和宏观大小的材料相比, 由于纳米结构的尺寸和量子受限效应, 纳米结构的等离激元具有一些不同的特征. 在低能共振区, 光谱线发生展宽, 并且发生劈裂. 由于纳米单体间的电磁耦合作用, 使聚合的纳米结构表现出了与单体不同的光学性质. 这些结果为等离激元的调控提供了坚实的理论指导.     

一维原子链局域等离激元的非线性激发

本文基于含时密度泛函理论, 研究了不同频率光脉冲场作用下一维钠原子链中电子的输运与等离激元共振之间的耦合规律. 在等离激元共振点附近约0.8 eV频率范围内的光脉冲场, 都可以激发体系的等离激元共振. 这些不同频率外场激发的等离激元共振强度大小在一个数量级. 外场频率越接近等离激元共振频率, 外场激起的等离激元振动的振幅越大. 对于线性原子链等离激元的非线性激发现象, 本文用经典谐振子模型给出了定性解释.     

Tunable localized surface plasmon resonances in one-dimensional h-BN/graphene/h-BN quantum-well structure

The graphene/hexagonal boron-nitride(h-BN) hybrid structure has emerged to extend the performance of graphenebased devices. Here, we investigate the tunable plasmon in one-dimensional h-BN/graphene/h-BN quantum-well structures.The analysis of optical response and field enhancement demonstrates that these systems exhibit a distinct quantum confinement effect for the collective oscillations. The intensity and frequency of the plasmon can be controlled by the barrier width and electrical doping. Moreover, the electron doping and the hole doping lead to very different results due to the asymmetric energy band. This graphene/h-BN hybrid structure may pave the way for future optoelectronic devices.     

碳分子线C5在激光场中的含时密度泛函理论研究

运用含时密度泛函理论和分子动力学相结合的方法, 研究了C₅分子线在强激光场中的电离激发.研究发现, 当考虑激光强度对C₅分子线激发的影响时, 激光强度越强, 分子吸收的能量越多, 电离也越早, 最终电离的电子也越多, 而且沿激光极化方向的偶极矩的变化及峰值也越大. 关于激光极化方向对C₅分子线激发的影响的研究表明, 当激光极化方向沿着C₅分子线轴向时, 分子的电离大大增强, x方向的激光脉冲仅能激发起x方向的偶极振荡, 而y方向的激光脉冲仅能激发起y方向的偶极振荡, 而且x方向的激光脉冲激发的偶极振荡强. 研究还表明, 当激光极化方向沿着C₅分子线轴向时, 尽管由于电离增强而导致C₅分子线C–C键振动的同步性变差, 但在两种激光极化方向情况下, C₅分子线的振动模式与中性C₅分子线的振动模式相同. 关键词： 含时密度泛函理论 分子动力学 分子电离 碳分子线     

The polarisability of atoms and molecules: a comparison between a conceptual density functional theory approach and time-dependent density functional theory

We investigate the local polarisability or polarisability density using both a conceptual density functional theory approach based on the linear response function and time-dependent density functional theory. Using a zero frequency in the latter, we can immediately compare both approaches. Using an analytical expression for the linear response kernel, we are able to systematically analyse α(r) throughout the periodic table. An extension to molecules is also made with a study of the CO molecule retrieving the connection between local softness and local polarisability.     

质子与羟基碰撞的含时密度泛函理论研究

采用将含时密度泛函理论和分子动力学非绝热耦合的方法,研究了不同入射速度下质子与羟基碰撞的反应动力学.计算了碰撞前后质子动能和羟基动能的变化及羟基电子和质子的运动.计算结果表明,质子沿垂直羟基分子轴方向入射时,质子与羟基碰撞后,质子被反弹且动能损失并俘获了羟基中氧的一部分电子,而丢失部分电子的羟基则获得动能以伸缩振动的形式向计算边界平动.随着入射质子的初动能增加,质子从羟基中俘获的电子增多,碰撞后羟基的键长变长,羟基振动变强而伸缩振动频率降低.此外,还发现质子的入射方向对碰撞过程的激发动力学有很大的影响.质子从不同的方向入射时,质子的入射初动能越大,其损失的动能越多且损失的动能与入射初动能呈线性关系,而入射方向对质子动能损失的影响很小.在质子入射初动能较低(小于25 eV)的情况下,羟基获得的动能与质子入射初动能呈线性关系且与入射方向无关;在质子入射初动能较高(大于25 eV)时,当质子沿羟基分子轴方向入射时,羟基动能的增量远大于质子沿垂直于羟基分子轴方向入射时羟基动能的增量.     

Dynamical deformations of the electron density in an H2 molecule under strong,oscillating magnetic fields: an application of time-dependent quantum fluid density functional theory

Following the time-dependent quantum fluid density functional theory developed in our laboratory, the present quantum-mechanical, dynamical study of the H₂ molecule under strong, oscillating magnetic fields reveals a coexistence of both slow and fast dynamics, as seen earlier in the cases of hydrogen and helium atoms. Using the Deb–Chattaraj equation of motion we find that, contrary to the situation with static magnetic fields, the electron density now transiently expands. Consequently, the fate of the H–H bond under such strong TD magnetic fields has been addressed through detailed and accurate TD density profiles computed by direct numerical solution of the real-time evolution equation. A detailed interpretation of the slow dynamics has been made.     

Secondary plasmon resonance in graphene nanostructures

The plasmon characteristics of two graphene nanostructures are studied using time-dependent density functional theory (TDDFT). The absorption spectrum has two main bands, which result from π and σ + π plasmon resonances. At low energies, the Fourier transform of the induced charge density maps exhibits anomalous behavior, with a π phase change in the charge density maps in the plane of the graphene and those in the plane 0.3 ? from the graphene. The charge density fluctuations close to the plane of the graphene are much smaller than those above and beneath the graphene plane. However, this phenomenon disappears at higher energies. By analyzing the electronic properties, we may conclude that the restoring force for the plasmon in the plane of the graphene does not result from fixed positive ions, but rather the Coulomb interactions with the plasmonic oscillations away from the plane of the graphene, which extend in the surface-normal direction. The collective oscillation in the graphene plane results in a forced vibration. Accordingly, the low-energy plasmon in the graphene can be split into two components: a normal component, which corresponds to direct feedback of the external perturbation, and a secondary component, which corresponds to feedback of the Coulombic interaction with the normal component.     

Local scaling transformation function and atomic shell structure in density functional theory

The method of local scaling transformation in density functional theory calculates a transformation function (TRF) in order to generate an optimized atomic N-electron wave function from a trial density and a reference density/wave function. The TRFsf(r) for several atomic systems are studied and it is observed that the number of minima in df(r)/dr equals the number of atomic shells, except whenρ=ρ ₀ andf=r.     

分子对飞秒激光场响应的含时密度泛函理论研究

采用含时密度泛函理论方法研究线性分子碳化锂(Li2C2)对飞秒激光场响应的电子-离子动力学行为.在典型的近共振和非共振的激光频率作用下,分别对比分析了分子的共振和非共振电离过程.研究发现:分子在共振频率激光场的作用下发生更强的电离过程,并倾向于发生库伦爆炸,键长的振荡断裂与电离相互促进影响,而分子在较弱的激光场作用下发生单光子电离过程;随着双脉冲时间间隔的增加,离化电子数在一定范围内呈振荡上升趋势,随后趋于常数.     

分子对飞秒激光场响应的含时密度泛函理论研究

采用含时密度泛函理论方法研究线性分子碳化锂（Li2C2）对飞秒激光场响应的电子-离子动力学行为。在典型的近共振和非共振的激光频率作用下,分别对比分析了分子的共振和非共振电离过程。研究发现：分子在共振频率激光场的作用下发生更强的电离过程,并倾向于发生库伦爆炸,键长的振荡断裂与电离相互促进影响,而分子在较弱的激光场作用下发生单光子电离过程;随着双脉冲时间间隔的增加,离化电子数在一定范围内呈振荡上升趋势,随后趋于常数。     

Universality principle and the development of classical density functional theory

The universality principle of the free energy density functional and the ‘test particle' trick by Percus are combined to construct the approximate free energy density functional or its functional derivative. Information about the bulk fluid radial distribution function is integrated into the density functional approximation directly for the first time in the present methodology. The physical foundation of the present methodology also applies to the quantum density functional theory.     

Electron dynamics triggered by double attosecond pulses: Simulations based on time-dependent density functional theory

In order to observe the high-field effect, the external laser field must reach its peak intensity before the electron ionization. To this end, it is important to reduce pulse duration to typical attosecond timescale. In this paper, the interaction electron dynamics between attosecond pulses and dielectric is investigated within the time-dependent density functional theory. Taking the CaF₂ crystal as an example, we give a comparison of electron dynamics response between single and double pulses. Moreover, the nonlinear energy absorption and electron excitation processes are simulated by adjusting the polarization direction of the sub-pulse. Present results demonstrate that the double pulses show lower electron excitation and energy absorption than the single pulse, which is in accordance with experimental higher ablation threshold and smaller heat-affected zones of the double pulses. In addition, the curves of final excited electron number and energy absorption exhibit the quasi-symmetry about the axis of 180°, which has not been reported yet.     

A comparative investigation of an AB- and AA-stacked bilayer graphene sheet under an applied electric field: A density functional theory study

An AB- and AA-stacked bilayer graphene sheet(BLG) under an electric field is investigated by ab initio calculation.The interlayer distance between the two layers,band structures,and atomic charges of the system are investigated in the presence of different electric fields normal to the BLG.The AB- stacked BLG is able to tune the bandgap into 0.234 eV with the increase of the external electronic field to 1 V/nm,however,the AA-stacked BLG is not sensitive to the external electric field.In both the cases,the spacing between the BLG slightly change in terms of the electric field.The charges in the AB- stacked BLG are increased with the increase of the electric field,which is considered to be the reason that causes the bandgap opening in the AB- stacked BLG.     

Computational studies of CO and CO: Density functional theory and time-dependent density functional theory

Potential energy curves, equilibrium interatomic distances, term energies and harmonic vibration frequencies for the 16 lowest states of neutral carbon monoxide and the six lowest states of singly ionized carbon monoxide are calculated by density functional theory (DFT) and linear-response time-dependent density functional (LR-TDDFT) theory. The results are compared with experimental data. The two theories, DFT and LR-TDDFT, are described briefly.     

A new study of associating inhomogeneous fluids with classical density functional theory

ABSTRACT

A new density functional for the study of associating inhomogeneous fluids based on Wertheim's first-order thermodynamic perturbation theory is presented and compared to the most currently used associating density functionals. This functional is developed using the weighted density approximation in the range of association of hard spheres. We implement this functional within the framework of classical density functional theory together with modified fundamental measure theory to account for volume exclusion of hard spheres. This approach is tested against molecular simulations from literature of pure associating hard spheres and mixtures of non-associationg and associating hard spheres with different number of bonding sites close to a hard uniform wall. Furthermore, we compare and review our results with the performance of associating functionals from literature, one based on fundamental measure theory and the inhomogeneous version of Wertheim's perturbation theory. Results obtained with classical DFT and the three functionals show excellent agreement with molecular simulations in systems with one hard wall. For the cases of small pores where only one or two layers of fluid are allowed discrepancies between results with classical DFT and molecular simulations were found.     

Single-particle energies and density of states in density functional theory

Time-dependent density functional theory (TD-DFT) is commonly used as the foundation to obtain neutral excited states and transition weights in DFT, but does not allow direct access to density of states and single-particle energies, i.e. ionisation energies and electron affinities. Here we show that by extending TD-DFT to a superfluid formulation, which involves operators that break particle-number symmetry, we can obtain the density of states and single-particle energies from the poles of an appropriate superfluid response function. The standard Kohn– Sham eigenvalues emerge as the adiabatic limit of the superfluid response under the assumption that the exchange– correlation functional has no dependence on the superfluid density. The Kohn– Sham eigenvalues can thus be interpreted as approximations to the ionisation energies and electron affinities. Beyond this approximation, the formalism provides an incentive for creating a new class of density functionals specifically targeted at accurate single-particle eigenvalues and bandgaps.     

特丁基对苯二酚的光谱及密度泛函研究

特丁基对苯二酚是重要的食品抗氧化剂.理论上,基于密度泛函理论,采用B3LYP泛函及6-311G(d,p)基组在气相环境下优化分子的结构并进行频率计算.在此基础上,基于含时密度泛函理论,选用SMD(solvation model based on density)溶剂模型,利用B3LYP泛函并结合def2-TZVP基组计...     

Vibrational analysis of L-serine using the density functional theory

In this paper, we present a computational study of L-serine using ab initio molecular dynamics simulation based on density functional theory (DFT) within the ultrasoft pseudopotentials and generalized-gradient approximation. Taking into account the intermolecular interactions, we can indeed simulate the features of the experimental results very well for L-serine zwitterions in its solid state. The vibrational spectrum of L-serine performed by DFT was in excellent agreement with our previous inelastic incoherent neutron scattering spectra measured at 20K for L-serine in the 10--200meV region on HET spectrometers at ISIS, Rutherford Appleton Laboratory.