One-body Properties Research Articles

Site-Specific Ionization Potentials and Electron Affinities in Large Molecular Systems at Coupled Cluster Level.

A many-body expansion of ionization potentials and electron affinities is developed based on a combination of the fragment molecular orbital method and equation-of-motion coupled-cluster (EOM-CC). In addition to site-specific values, obtained as one-body properties, pair and triple corrections are added to account for nonlocal EOM-CC contributions of the molecular environment of a chromophore. The developed method is applied to carboxylic acids, alkyl cations, a protein ubiquitin (Protein Data Bank ID 1UBQ), and a nano ribbon of white graphene elucidating the effect of environment on ionization potential and electron affinity.

Sensitivity of time-dependent density functional theory to initial conditions

Time-Dependent Density Functional Theory is mathematically formulated through non-linear coupled time-dependent 3-dimensional partial differential equations and it is natural to expect a strong sensitivity of its solutions to variations of the initial conditions, akin to the butterfly effect ubiquitous in classical dynamics. Since the Schr\"odinger equation for an interacting many-body system is however linear and mathematically the exact equations of the Density Functional Theory reproduce the corresponding one-body properties, it would follow that the Lyapunov exponents are also vanishing within a Density Functional Theory framework. Whether for realistic implementations of the Time-Dependent Density Functional Theory the question of absence of the butterfly effect and whether the dynamics provided is indeed a predictable theory was never discussed. At the same time, since the time-dependent density functional theory is a unique tool allowing us the study of non-equilibrium dynamics of strongly interacting many-fermion systems, the question of predictability of this theoretical framework is of paramount importance. Our analysis, for a number of quantum superfluid many-body systems (unitary Fermi gas, nuclear fission, and heavy-ion collisions) with a classical equivalent number of degrees of freedom ${\cal O}(10^{10})$ and larger, suggests that its maximum Lyapunov exponents are negligible for all practical purposes.

Bose-Einstein condensation of correlated atoms in a trap

The Bose-Einstein condensation of correlated atoms in a trap is studied by examining the effect of inter-particle correlations to one-body properties of atomic systems at zero temperature using a simplified formula for the correlated two body density distribution. Analytical expressions for the density distribution and rms radius of the atomic systems are derived using four different expressions of Jastrow type correlation function. In one case, in addition, the one-body density matrix, momentum distribution and kinetic energy are calculated analytically, while the natural orbitals and natural occupation numbers are also predicted in this case. Simple approximate expressions for the mean square radius and kinetic energy are also given.

Elastic magnetic electron scattering from deformed nuclei

Magnetic form factors corresponding to elastic electron scattering from odd-A nuclei are presented. The calculations are carried out in plane-wave Born approximation. The one-body properties are obtained in a deformed self-consistent mean-field calculation based on a Skyrme HF+BCS method. Collective effects are also included in the cranking approximation. Results on several stable nuclei are compared with the available experimental information. It is shown that a deformed formalism improves the agreement with experiment in deformed nuclei, while reproducing equally well spherical nuclei by taking properly the spherical limit of the deformed model and the effect of nucleon-nucleon correlations. Thus, the capability of the model to describe magnetic form factors is demonstrated. This opens the door to explore also unstable nuclei of particular interest that could be measured in future experiments on electron-radioactive beam colliders.

Stochastic method for calculating the ground-state one-body density matrix of trapped Bose particles in one dimension

The one-body density matrix (OBDM) is a fundamental contraction of the Bose-Einstein condensate wave function, encapsulating its one-body properties. It serves as a major analysis tool with which the condensed component of the density can be identified. Despite its cardinal importance, calculating the ground-state OBDM of trapped interacting bosons is a challenge and to date OBDM calculations have been published only for homogeneous systems or for trapped weakly interacting bosons. In this paper we discuss an approach for computing the OBDM based on a double-walker diffusion Monte Carlo random walk coupled with a stochastic permanent calculation. We here describe the method and study some of its statistical convergence and properties applying it to some model systems.

The use of many-body expansions and geometry optimizations in fragment-based methods.

Conspectus Chemists routinely work with complex molecular systems: solutions, biochemical molecules, and amorphous and composite materials provide some typical examples. The questions one often asks are what are the driving forces for a chemical phenomenon? How reasonable are our views of chemical systems in terms of subunits, such as functional groups and individual molecules? How can one quantify the difference in physicochemical properties of functional units found in a different chemical environment? Are various effects on functional units in molecular systems additive? Can they be represented by pairwise potentials? Are there effects that cannot be represented in a simple picture of pairwise interactions? How can we obtain quantitative values for these effects? Many of these questions can be formulated in the language of many-body effects. They quantify the properties of subunits (fragments), referred to as one-body properties, pairwise interactions (two-body properties), couplings of two-body interactions described by three-body properties, and so on. By introducing the notion of fragments in the framework of quantum chemistry, one obtains two immense benefits: (a) chemists can finally relate to quantum chemistry, which now speaks their language, by discussing chemically interesting subunits and their interactions and (b) calculations become much faster due to a reduced computational scaling. For instance, the somewhat academic sounding question of the importance of three-body effects in water clusters is actually another way of asking how two hydrogen bonds affect each other, when they involve three water molecules. One aspect of this is the many-body charge transfer (CT), because the charge transfers in the two hydrogen bonds are coupled to each other (not independent). In this work, we provide a generalized view on the use of many-body expansions in fragment-based methods, focusing on the general aspects of the property expansion and a contraction of a many-body expansion in a formally two-body series, as exemplified in the development of the fragment molecular orbital (FMO) method. Fragment-based methods have been very successful in delivering the properties of fragments, as well as the fragment interactions, providing insights into complex chemical processes in large molecular systems. We briefly review geometry optimizations performed with fragment-based methods and present an efficient geometry optimization method based on the combination of FMO with molecular mechanics (MM), applied to the complex of a subunit of protein kinase 2 (CK2) with a ligand. FMO results are discussed in comparison with experimental and MM-optimized structures.

Semianalytical model for nonlinear absorption in strongly interacting Rydberg gases

Rate equation models are extensively used to describe the many-body states of laser driven atomic gases. We show that the properties of the rate equation model used to describe nonlinear optical effects arising in interacting Rydberg gases can be understood by considering the excitation of individual super-atoms. From this we deduce a simple semi-analytic model that accurately describes the Rydberg density and optical susceptibility for different dimensionalities. We identify the previously reported universal dependence of the susceptibility on the Rydberg excited fraction as an intrinsic property of the rate equation model that is rooted in one-body properties. Benchmarking against exact master equation calculations, we identify regimes in which the semi-analytic model is particularly reliable. The performance of the model improves in the presence of dephasing which destroys higher order atomic coherences.

Intrinsic decoherence and purity in a Bose quantum fluid in a triple well potential

We consider a quantum Bose fluid confined in a triple well potential in 1D within the exact N-body Bose–Hubbard model to investigate the phenomena of intrinsic decoherence and loss of purity. Our study is done by following the time evolution of one-body properties in an N-particle closed environment. We do an exhaustive exploration of initial conditions to characterize these phenomena. Here we illustrate our main findings with a set of relevant Fock and SU(3) coherent states. Our study shows that signatures of stationarity and maximal mixing are a direct consequence of the inter-particle interactions in the closed system and become evident as the number of particles is increased. This fact is confirmed by quantifying the deviations from stationarity by means of a matrix norm.

Quantum fluctuations of a Bose-Josephson junction in a quasi-one-dimensional ring trap

Using a Luttinger-liquid approach we study the quantum fluctuations of a Bose-Josephson junction, consisting of a Bose gas confined to a quasi-one-dimensional ring trap which contains a localized repulsive potential barrier. For an infinite barrier we study the one-particle and two-particle static correlation functions. For the one-body density-matrix we obtain different power-law decays depending on the location of the probe points with respect to the position of the barrier. This quasi-long-range order can be experimentally probed in principle using an interference measurement. The corresponding momentum distribution at small momenta is also shown to be affected by the presence of the barrier and to display the universal power-law behavior expected for an interacting one-dimensional fluid. We also evaluate the particle-density profile, and by comparing with the exact results in the Tonks-Girardeau limit we fix the nonuniversal parameters of the Luttinger-liquid theory. Once the parameters are determined from one-body properties, we evaluate the density-density correlation function, finding a remarkable agreement between the Luttinger-liquid predictions and the exact result in the Tonks-Girardeau limit, even at the length scale of the Friedel-like oscillations which characterize the behavior of the density-density correlation function at intermediate distance. Finally, for a large but finite barrier we use the one-body correlation function to estimate the effect of quantum fluctuations on the renormalization of the barrier height, finding a reduction in the effective Josephson coupling energy, which depends on the length of the ring and on the interaction strength.

Ground-state densities and pair correlation functions in parabolic quantum dots

We present an extensive comparative study of ground-state densities and pair distribution functions for electrons confined in two-dimensional parabolic quantum dots over a broad range of coupling strength and electron number. We first use spin-density-functional theory to determine spin densities that are compared with Diffusion Monte Carlo (DMC) data. This accurate knowledge of one-body properties is then used to construct and test a local approximation for the electron-pair correlations. We find very satisfactory agreement between this local scheme and the available DMC data, and provide a detailed picture of two-body correlations in a coupling-strength regime preceding the formation of Wigner-like electron ordering.

Bose-Einstein condensation of correlated atoms in a trap

The Bose-Einstein condensation of correlated atoms in a trap is studied by examining the effect of inter-particle correlations to one-body properties of atomic systems at zero temperature using a simplified formula for the correlated two body density distribution. Analytical expressions for the density distribution and rms radius of the atomic systems are derived using four different expressions of Jastrow type correlation function. In one case, in addition, the one-body density matrix, momentum distribution and kinetic energy are calculated analytically, while the natural orbitals and natural occupation numbers are also predicted in this case. Simple approximate expressions for the mean square radius and kinetic energy are also given.

One-body properties of nuclear matter with off-shell propagation

Symmetric nuclear matter is studied in the self-consistent, in-medium $T$-matrix approach. One-body spectral function, optical potential, and scattering width are calculated. Properties of quasi-particle excitations at the Fermi surface are discussed. Dispersive self-energies are dominated by contributions from the $^1S_0$, $3S_1-^3D_1$, and $^3P_1$ partial waves.

Evaluation of cluster expansions and correlated one-body properties of nuclei

Three different cluster expansions for the evaluation of correlated one-body properties of s-p and s-d shell nuclei are compared. Harmonic oscillator wave functions and Jastrow type correlations are used, while analytical expressions are obtained for the charge form factor, density distribution, and momentum distribution by truncating the expansions and using a standard Jastrow correlation function f. The harmonic oscillator parameter b and the correlation parameter \beta have been determined by a least-squares fit to the experimental charge form factors in each case. The information entropy of nuclei in position-space (S_r) and momentum-space (S_k) according to the three methods are also calculated. It is found that the larger the entropy sum S=S_r+S_k (the information content of the system) the smaller the values of \chi^2. This indicates that S is a criterion of the quality of a given nuclear model, according to the maximum entropy principle. Only two exceptions to this rule, out of many cases examined, were found. Finally an analytic expression for the so-called "healing" or "wound" integrals is derived with the function f considered, for any state of the relative two-nucleon motion and their values in certain cases are computed and compared.

Short-range correlations and one-body properties of nuclei

We present analytical and numerical results concerning one-bodys-d shell nuclear characteristics within the low-order approximation to the one-body density matrix for a Jastrow groundstate wave function. The correlation effects on the nucleon momentum and density distributions as well as the occupation numbers and the depletion of the Fermi sea are discussed. It is estimated that the use of the low-order approximation leads to a violation of theA-representability condition for the one-body density matrix. The closed analytical expressions obtained for the one-body nuclear characteristics can be used in analyzing the short-range correlation effects observed in the measured experimental data.

Hot nuclear matter in an extended Brueckner approach

The properties of cold and hot nuclear matter are studied in the frame of the Brueckner theory, extended to finite temperature. The basic task is the evaluation of the two-hole line diagram using the Paris potential supplemented by the introduction of three-body forces, coming from the exchange of π and ρ mesons. The latter have an important saturating effect, but not sufficient to reach correct saturation. The latter is achieved by a phenomenological treatment. The properties of hot nuclear matter, for temperatures around 10 MeV, are investigated. Particular attention is paid to one-body properties. The density and temperature dependence of many quantities, like the single-particle energy spectrum, the optical potential, the effective mass, the non-locality of the single-particle field, the mean free path, is displayed and analyzed. The relative importance of the temperature dependence of the g-matrix and of phase space is investigated, especially in relation with the imaginary part of the optical potential and the mean free path. The temperature dependence of the effective mass is particularly studied. It is shown that the peak due to the so-called core polarization effect disappears rapidly as the matter is heated. The evaluation of the entropy and of the level density parameter a, which are closely related, is discussed, and the failure of the Hartree-Fock approach to reproduce the value of a correctly is explained. Two-body properties are also investigated. The temperature and density dependence of the two-body correlations are displayed. Particular attention is paid to the temperature dependence of the effective interaction. The latter is exhibited in a simple manner. It is shown that the effective force felt by low-energy nucleons does not change by more than a few percent when the temperature goes from 0 to 10 MeV. For high-energy nucleons, the change may be as large as ten percent.