A mathematical and computational review of Hartree–Fock SCF methods in quantum chemistry

We present a review of the fundamental topics of Hartree–Fock theory in quantum chemistry. From the molecular Hamiltonian, using and discussing the Born–Oppenheimer approximation, we arrive at the Hartree and Hartree–Fock equations for the electronic problem. Special emphasis is placed on the most relevant mathematical aspects of the theoretical derivation of the final equations, and on the results regarding the existence and uniqueness of their solutions. All Hartree–Fock versions with different spin restrictions are systematically extracted from the general case, thus providing a unifying framework. The discretization of the one-electron orbital space is then reviewed and the Roothaan–Hall formalism introduced. This leads to an exposition of the basic underlying concepts related to the construction and selection of Gaussian basis sets, focusing on algorithmic efficiency issues. Finally, we close the review with a section in which the most relevant modern developments (especially those related to the design of linear-scaling methods) are commented on and linked to the issues discussed. The paper is intentionally introductory and rather self-contained, and may be useful for non-experts intending to use quantum chemical methods in interdisciplinary applications. Moreover, much material that can be found scattered in the literature has been put together to facilitate comprehension and to serve as a handy reference.     

Modelling of high-temperature dark current in multi-quantum well structures from MWIR to VLWIR

In this paper, a model to calculate the dark current of quantum well infrared photodetectors at high-temperature regime is presented. The model is derived from a positive-definite quantum probability-flux and considers thermionic emission and thermally-assisted tunnelling as mechanisms of dark current generation. Its main input data are the wave functions obtained by time-independent Schrodinger equation and it does not require empirical parameters related to the transport of carriers. By means of this model, the dark current of quantum well infrared photodetectors at high-temperature regime is investigated with respect to the temperature, the barrier width, the applied electric field and the position of the first excited state. The theoretical results are compared with experimental data obtained from lattice-matched InAlAs/InGaAs, InGaAsP/InP on InP substrate and AlGaAs/GaAs structures with rectangular wells and symmetric barriers, whose absorption peak wavelengths range from MWIR to VLWIR. The corresponding results are in a good agreement with experimental data at different temperatures and at a wide range of applied electric field.     

Reconnection dynamics for quantized vortices

By analyzing trajectories of solid hydrogen tracers in superfluid ⁴He, we identify tens of thousands of individual reconnection events between quantized vortices. We characterize the dynamics by the minimum separation distance δ(t) between the two reconnecting vortices both before and after the events. Applying dimensional arguments, this separation has been predicted to behave asymptotically as δ(t)≈A(κ|t−t₀|)^1/2, where κ=h/m is the quantum of circulation. The major finding of the experiments and their analysis is strong support for this asymptotic form with κ as the dominant controlling feature, although there are significant event to event fluctuations. At the three-parameter level the dynamics may be about equally well-fit by two modified expressions: (a) an arbitrary power-law expression of the form δ(t)=B|t−t₀|^α and (b) a correction-factor expression δ(t)=A(κ|t−t₀|)^1/2(1+c|t−t₀|). The measured frequency distribution of α is peaked at the predicted value α=0.5, although the half-height values are α=0.35 and 0.80 and there is marked variation in all fitted quantities. Accepting (b) the amplitude A has mean values of 1.24±0.01 and half height values of 0.8 and 1.6 while the c distribution is peaked close to c=0 with a half-height range of −0.9 s⁻¹ to 1.5 s⁻¹. In light of possible physical interpretations we regard the correction-factor expression (b), which attributes the observed deviations from the predicted asymptotic form to fluctuations in the local environment and in boundary conditions, as best describing our experimental data. The observed dynamics appear statistically time-reversible, which suggests that an effective equilibrium has been established in quantum turbulence on the time scales (≤0.25 s) investigated. We discuss the impact of reconnection on velocity statistics in quantum turbulence and, as regards classical turbulence, we argue that forms analogous to (b) could well provide an alternative interpretation of the observed deviations from Kolmogorov scaling exponents of the longitudinal structure functions.     

Generalization of the Hellmann-Feynman theorem

The well-known Hellmann-Feynman theorem of quantum mechanics connected with the derivative of the eigenvalues with respect to a parameter upon which the Hamiltonian depends, is generalized to include cases in which the domain of definition of the Hamiltonian of the system also depends on that parameter.     

Aspects of multistation quantum information broadcasting

We study quantum information transmission over multiparty quantum channel. In particular, we show an equivalence of different capacity notions and provide a multiletter characterization of a capacity region for a general quantum channel with k senders and m receivers. We point out natural generalizations to the case of two-way classical communication capacity.     

Lateral electric field effects on quantum size confinement in cylindrical quantum dot under parabolic potential

Within the effective mass approximation, we investigated theoretically the ground-state energy of a single particle and the binding energy of the neutral donor impurity (D⁰) affected by a lateral electric field in a parabolic quantum dot (QD). The results show that the electron and the hole ground-state energy and the band to band transition energies shift to lower values (red shift) by increasing the field intensity. The quantum Stark shift (QSS) for the electron increases rapidly in the quasi spherical QD (QSQD) by increasing the lateral field, whereas for the hole it increases monotony. In the cylindrical QDs (CQDs), we found that the QSS for electron and hole increase monotonically. The quantum size, lateral electric field and impurity position effect on the binding energy of neutral donor (D⁰) is studied. Unexpected behavior of D⁰ in quantum well limit (QW), the binding energy of D⁰ is increasing (blue shift) with increasing QD radius R$R$ at the presence of a lateral electric field. It appears that for a fixed size of the QD, the off-center binding energy decreases when the impurity ion is displaced from the center to the QD borders, while it is shifted to lower energy with increasing the field.     

Strong chaos of fast scrambling yields order: Emergence of decoupled quantum information capsules

The information loss problem in black hole evaporation is one of fundamental issues. Its resolution requires more profound understanding of information storage mechanism in quantum systems. In this Letter, we argue that when multiple unknown parameters are stored in large entangled qudits, strong chaos generated by fast scrambling in high temperature limit yields an ordered information storage structure with decoupled quantum information capsules (QICs). A rotational isometry emerges in the quantum Fisher information metric. The isometry is expected to be observed in future experiments on cold atoms in a pure entangled state. We provide a QIC speculation of black hole evaporation.     

Approximation of quantum assemblages

In this paper, we derive a set of projectors on a large Hilbert space which can universally work for approximating quantum assemblages with binary inputs and outputs. The dimension of the Hilbert space depends on the accuracy of the approximation.     

Pressure of the fluctuating vacuum: Interpretation of the attractive and repulsive Casimir force

We calculate the Casimir force between two magnetodielectric slabs. The force expression is expressed in terms of parameters with which the repulsive effect is more transparent and convenient for numerical analysis. Finally, we propose a physical interpretation of the effect which clarifies the sign of force properly.