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At least 37 records · Page 2

Coherent molecular transistor: Control through variation of the gate wave function

In quantum interference transistors (QUITs), the current through the device is controlled by variation of the gate component of the wave function that interferes with the wave function component joining the source and the sink. Initially, mesoscopic QUITs have been studied and more recently, QUITs at the molecular scale have been proposed and implemented. Typically, in these devices the gate lead is subjected to externally adjustable physical parameters that permit interference control through modifications of the gate wave function. Here, we present an alternative model of a molecular QUIT in which the gate wave function is directly considered as a variable and the transistor operation is discussed in terms of this variable. This implies that we specify the gate current as well as the phase of the gate wave function component and calculate the resulting current through the source-sink channel. Thus, we extend on prior works that focus on the phase of the gate wave function component as a control parameter while having zero or certain discrete values of the current. We address a large class of systems, including finite graphene flakes, and obtain analytic solutions for how the gate wave function controls the transistor.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Wave function for harmonically confined electrons in time-dependent electric and magnetostatic fields

We derive via the interaction “representation” the many-body wave function for harmonically confined electrons in the presence of a magnetostatic field and perturbed by a spatially homogeneous time-dependent electric field—the Generalized Kohn Theorem (GKT) wave function. In the absence of the harmonic confinement – the uniform electron gas – the GKT wave function reduces to the Kohn Theorem wave function. Without the magnetostatic field, the GKT wave function is the Harmonic Potential Theorem wave function. We further prove the validity of the connection between the GKT wave function derived and the system in an accelerated frame of reference. Finally, we provide examples of the application of the GKT wave function.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Intrinsic Resolution of Molecular Electronic Wave Functions and Energies in Terms of Quasi-atoms and Their Interactions

A general intrinsic energy resolution has been formulated for strongly correlated wave functions in the full molecular valence space and its subspaces. The information regarding the quasi-atomic organization of the molecular electronic structure is extracted from the molecular wave function without introducing any additional postulated model state wave functions. To this end, the molecular wave function is expressed in terms of quasi-atomic molecular orbitals, which maximize the overlap between subspaces of the molecular orbital space and the free-atom orbital spaces. As a result, the molecular wave function becomes the superposition of a wave function representing the non-bonded juxtaposed quasi-atoms and a wave function describing the interatomic electron migrations that create bonds through electron sharing. The juxtaposed nonbonded quasi-atoms are shown to consist of entangled quasi-atomic states from different atoms. The binding energy is resolved as a sum of contributions that are due to quasi-atom formation, quasiclassical electrostatic interactions and interatomic interferences caused by electron sharing. The contributions are further resolved according to orbital interactions. The various transformations that generate the analysis are determined by criteria that are independent of the working orbital basis used for calculating the molecular wave function. Lastly, the theoretical formulation of the resolution is quantitatively validated by an application to the C 2 molecule.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Symmetry-projected wave functions in quantum Monte Carlo calculations

Here, we consider symmetry-projected Hartree-Fock trial wave functions in constrained-path Monte Carlo (CPMC) calculations. Previous CPMC calculations have mostly employed Hartree-Fock (HF) trial wave functions, restricted or unrestricted. The symmetry-projected HF approach results in a hierarchy of wave functions with increasing quality: the more symmetries that are broken and restored in a self-consistent manner, the higher the quality of the trial wave function. This hierarchy is approximately maintained in CPMC calculations: the accuracy in the energy increases and the statistical variance decreases when further symmetries are broken and restored. Significant improvement is achieved in CPMC with the best symmetry-projected trial wave functions over those from simple HF. We analyze and quantify the behavior using the two-dimensional repulsive Hubbard model as an example. In the sign-problem-free region, where CPMC can be made exact but a constraint is deliberately imposed here, spin-projected wave functions remove the constraint bias. Away from half filling, spatial symmetry restoration in addition to that of the spin leads to highly accurate results from CPMC. Since the computational cost of symmetry-projected HF trial wave functions in CPMC can be made to scale algebraically with system size, this provides a potentially general approach for accurate calculations in many-fermion systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Auxiliary-field-based trial wave functions in quantum Monte Carlo calculations

Quantum Monte Carlo (QMC) algorithms have long relied on Jastrow factors to incorporate dynamic correlation into trial wave functions. While Jastrow-type wave functions have been widely employed in real-space algorithms, they have seen limited use in second-quantized QMC methods, particularly in projection methods that involve a stochastic evolution of the wave function in imaginary time. Here we propose a scheme for generating Jastrow-type correlated trial wave functions for auxiliary-field QMC methods. The method is based on decoupling the two-body Jastrow into one-body projectors coupled to auxiliary fields, which then operate on a single determinant to produce a multideterminant trial wave function. We demonstrate that intelligent sampling of the most significant determinants in this expansion can produce compact trial wave functions that reduce errors in the calculated energies. Lastly, our technique may be readily generalized to accommodate a wide range of two-body Jastrow factors and applied to a variety of model and chemical systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Communication: A combined periodic density functional and incremental wave-function-based approach for the dispersion-accounting time-resolved dynamics of {sup 4}He nanodroplets on surfaces: {sup 4}He/graphene

In this work we propose a general strategy to calculate accurate He–surface interaction potentials. It extends the dispersionless density functional approach recently developed by Pernal et al. [Phys. Rev. Lett. 103, 263201 (2009)] to adsorbate-surface interactions by including periodic boundary conditions. We also introduce a scheme to parametrize the dispersion interaction by calculating two- and three-body dispersion terms at coupled cluster singles and doubles and perturbative triples (CCSD(T)) level via the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)]. The performance of the composite approach is tested on {sup 4}He/graphene by determining the energies of the low-lying selective adsorption states, finding an excellent agreement with the best available theoretical data. Second, the capability of the approach to describe dispersionless correlation effects realistically is used to extract dispersion effects in time-dependent density functional simulations on the collision of {sup 4}He droplets with a single graphene sheet. It is found that dispersion effects play a key role in the fast spreading of the {sup 4}He nanodroplet, the evaporation-like process of helium atoms, and the formation of solid-like helium structures. These characteristics are expected to be quite general and highly relevant to explain experimental measurements with the newly developed helium droplet mediated deposition technique.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coherent cooling of atoms in a frequency-modulated standing laser wave: Wave function and stochastic trajectory approaches

The wave function of a moderately cold atom in a stationary near-resonant standing light wave delocalizes very fast due to wave packet splitting. However, we show that frequency modulation of the field can suppress packet splitting for some atoms whose specific velocities are in a narrow range. These atoms remain localized in a small space for a long time. We demonstrate and explain this effect numerically and analytically. We also demonstrate that the modulated field can not only trap but also cool the atoms. We perform a numerical experiment with a large atomic ensemble having wide initial velocity and energy distributions. During the experiment, most of atoms leave the wave while the trapped atoms have a narrow energy distribution.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Quantum simulation of molecules without fermionic encoding of the wave function

Abstract Molecular simulations generally require fermionic encoding in which fermion statistics are encoded into the qubit representation of the wave function. Recent calculations suggest that fermionic encoding of the wave function can be bypassed, leading to more efficient quantum computations. Here we show that the two-electron reduced density matrix (2-RDM) can be expressed as a unique functional of the unencoded N -qubit-particle wave function without approximation, and hence, the energy can be expressed as a functional of the 2-RDM without fermionic encoding of the wave function. In contrast to current hardware-efficient methods, the derived functional has a unique, one-to-one (and onto) mapping between the qubit-particle wave functions and 2-RDMs, which avoids the over-parametrization that can lead to optimization difficulties such as barren plateaus. An application to computing the ground-state energy and 2-RDM of H 4 is presented.

74 ATOMIC AND MOLECULAR PHYSICS↗

A Nonorthogonal State-Interaction Approach for Matrix Product State Wave Functions

We present a state-interaction approach for matrix product state (MPS) wave functions in a nonorthogonal molecular orbital basis. Our approach allows us to calculate, for example, transition and spin–orbit coupling matrix elements between arbitrary electronic states, provided that they share the same one-electron basis functions and size of the active orbital space, respectively. The key element is the transformation of the MPS wave functions of different states from a nonorthogonal to a biorthonormal molecular orbital basis representation, by exploiting a sequence of nonunitary transformations, following a proposal by Malmqvist [Int. J. Quantum Chem.1986, 30, 479]. This is well-known for traditional wave function parametrizations but has not yet been exploited for MPS wave functions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Algebraic Theory of Crystal Vibrations: Localization Properties of Wave Functions in Two-Dimensional Lattices

The localization properties of the wave functions of vibrations in two-dimensional (2D) crystals are studied numerically for square and hexagonal lattices within the framework of an algebraic model. The wave functions of 2D lattices have remarkable localization properties, especially at the van Hove singularities (vHs). Finite-size sheets with a hexagonal lattice (graphene-like materials), in addition, exhibit at zero energy a localization of the wave functions at zigzag edges, so-called edge states. The striped structure of the wave functions at a vHs is particularly noteworthy. We have investigated its stability and that of the edge states with respect to perturbations in the lattice structure, and the effect of the boundary shape on the localization properties. We find that the stripes disappear instantaneously at the vHs in a square lattice when turning on the perturbation, whereas they broaden but persist at the vHss in a hexagonal lattice. For one of them, they eventually merge into edge states with increasing coupling, which, in contrast to the zero-energy edge states, are localized at armchair edges. The results are corroborated based on participation ratios, obtained under various conditions.

36 MATERIALS SCIENCE↗

Photon wave function formalism for analysis of Mach–Zehnder interferometer and sum-frequency generation

Biakynicki-Birula introduced a photon wave function similar to the matter wave function that satisfies the Schrödinger equation. Its second quantization form can be applied to investigate nonlinear optics at nearly full quantum level. In this paper, we applied the photon wave function formalism to analyze both linear optical processes in the well-known Mach–Zehnder interferometer and nonlinear optical processes for sum-frequency generation in dispersive and lossless medium. Results by photon wave function formalism agree with the well-established Maxwell treatments and existing experimental verifications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Solving the Trivial Crossing Problem While Preserving the Nodal Symmetry of the Wave Function

In an adiabatic mixed quantum-classical simulation, the avoided crossing of weakly coupled eigenstates can lead to unphysical discontinuities in wave function dynamics, otherwise known as the trivial crossing problem. A standard solution to the trivial crossing problem eliminates spatial discontinuities in wave function dynamics by imposing changes to the eigenstate of the wave function. In this paper, we show that this solution has the side effect of introducing transient discontinuities in the nodal symmetry of the wave function. We present an alternative solution to the trivial crossing problem that preserves both the spatial and nodal structure of the adiabatic wave function. By considering a model of exciton dynamics on conjugated polymer systems, we show that failure to preserve wave function symmetry yields exciton dynamics that depends unphysically on polymer system size. We demonstrate that our symmetry-preserving solution to the trivial crossing problem yields more realistic dynamics and can thus improve the accuracy of simulations of larger systems that are prone to the trivial crossing problem.

74 ATOMIC AND MOLECULAR PHYSICS↗

Atoms and interatomic bonding synergism inherent in molecular electronic wave functions

The chemical model of matter consists of atoms held together by bonds. The success of this model implies that the physical interactions of the electrons and nuclei in molecules combine into compound interactions that create the bonding. In the quantum mechanical description, the modified atoms in molecules and the bonding synergism are contained in the molecular electronic wave function. So far, only part of this information has been recovered from the wave function. Notably, the atoms have remained unidentified in the wave function. One reason is that conventional energy decomposition analyses formulate separate model wave functions, independent of the actual wave function, to represent “prepared atoms” and preconceived interactions and, then, intuitively catenate the parts. In the present work, the embedded modified atoms and the inherent physical synergisms between them are determined by a unified derivation entirely from the actual molecular valence space wave function. By means of a series of intrinsic orbital and configurational transformations of the wave function, the energy of formation of a molecule is additively resolved in terms of intra-atomic energy changes, interference energies, and quasi-classical, non-classical, and charge-transfer Coulombic interactions. Here, the analysis furnishes an algorithm for the quantitative resolution of the energy of formation, which enables analyses elucidating reaction energies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

POSSIBLE EXPERIMENTS ON WAVE FUNCTION LOCALIZATION DUE TO COMPTON SCATTERING

The reduction of a particle s wave function in the process of radiation or light scattering is a longstanding problem. Its solution will give a clue on processes that form, for example, wave functions of electrons constantly emitting synchrotron radiation quanta in storage rings. On a more global scale, it may shed light on wave function collapse due to the process of measurement. In this paper we consider various experimental options using Fermilab electron beams and a possible electron beam from the SNS linac and lasers to detect electron wave function change due to Compton scattering.

Aleksandrov, Alexander V↗

Wave function continuity and the diagonal Born-Oppenheimer correction at conical intersections

We demonstrate that though exact in principle, the expansion of the total molecular wave function as a sum over adiabatic Born-Oppenheimer (BO) vibronic states makes inclusion of the second-derivative nonadiabatic energy term near conical intersections practically problematic. In order to construct a well-behaved molecular wave function that has density at a conical intersection, the individual BO vibronic states in the summation must be discontinuous. When the second-derivative nonadiabatic terms are added to the Hamiltonian, singularities in the diagonal BO corrections (DBOCs) of the individual BO states arise from these discontinuities. In contrast to the well-known singularities in the first-derivative couplings at conical intersections, these singularities are non-integrable, resulting in undefined DBOC matrix elements. Though these singularities suggest that the exact molecular wave function may not have density at the conical intersection point, there is no physical basis for this constraint. Instead, the singularities are artifacts of the chosen basis of discontinuous functions. We also demonstrate that continuity of the total molecular wave function does not require continuity of the individual adiabatic nuclear wave functions. We classify nonadiabatic molecular dynamics methods according to the constraints placed on wave function continuity and analyze their formal properties. Based on our analysis, it is recommended that the DBOC be neglected when employing mixed quantum-classical methods and certain approximate quantum dynamical methods in the adiabatic representation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamical model for longitudinal wave functions in light-front holographic QCD

We construct a Schrödinger-like equation for the longitudinal wave function of a meson in the valence qq{sup -bar} sector, based on the ’t Hooft model for large-N two-dimensional QCD, and combine this with the usual transverse equation from light-front holographic QCD, to obtain a model for mesons with massive quarks. The computed wave functions are compared with the wave function ansatz of Brodsky and de Téramond and used to compute decay constants and parton distribution functions. The basis functions used to solve the longitudinal equation may be useful for more general calculations of meson states in QCD. -- Highlights: •Provide relativistic quark model based on light-front holographic QCD. •Incorporate dependence on quark mass. •Consistent with the Brodsky–de Téramond quark-wave-function ansatz. •Compute meson decay constants and parton distribution functions. •Illustrate use of basis functions that could be convenient for more general numerical calculations in light-front QCD.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Factorized molecular wave functions: Analysis of the nuclear factor

The exact factorization of molecular wave functions leads to nuclear factors which should be nodeless functions. We reconsider the case of vibrational perturbations in a diatomic species, a situation usually treated by combining Born-Oppenheimer products. It was shown [R. Lefebvre, J. Chem. Phys. 142, 074106 (2015)] that it is possible to derive, from the solutions of coupled equations, the form of the factorized function. By increasing artificially the interstate coupling in the usual approach, the adiabatic regime can be reached, whereby the wave function can be reduced to a single product. The nuclear factor of this product is determined by the lowest of the two potentials obtained by diagonalization of the potential matrix. By comparison with the nuclear wave function of the factorized scheme, it is shown that by a simple rectification, an agreement is obtained between the modified nodeless function and that of the adiabatic scheme.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗