Full Wave Function Research Articles

Huzinaga projection embedding for efficient and accurate energies of systems with localized spin-densities.

We demonstrate the accuracy and efficiency of the restricted open-shell and unrestricted formulation of the absolutely localized Huzinaga projection operator embedding method. Restricted open-shell and unrestricted Huzinaga projection embedding in the full system basis is formally exact to restricted open-shell and unrestricted Kohn-Sham density functional theory, respectively. By utilizing the absolutely localized basis, we significantly improve the efficiency of the method while maintaining high accuracy. Furthermore, the absolutely localized basis allows for high accuracy open-shell wave function methods to be embedded into a closed-shell density functional theory environment. The open-shell embedding method is shown to calculate electronic energies of a variety of systems to within 1 kcal/mol accuracy of the full system wave function result. For certain highly localized reactions, such as spin transition energies on transition metals, we find that very few atoms are necessary to include in the wave function region in order to achieve the desired accuracy. This extension further broadens the applicability of our absolutely localized Huzinaga level-shift projection operator method to include open-shell species. Here, we apply our method to several representative examples, such as spin splitting energies, catalysis on transition metals, and radical reactions.

Quantum Theory Improvement of the Photoelectric Effect on Metals

This paper concerns the full interaction of a flux of photons onto any metal whose extraction potential is known. The photons are described with a full wavefunction, including all states of polarization, and the ejected electrons are considered with their two spin states. The purpose is to give a full theoretical description of the interaction of the photoelectric effect, known since a long time, it verifies that the electron of any peculiar metal can escape if a threshold is met. These wavelengths are accessible for many metals, the photoelectrons exist if the condition: . U0 is the extraction potential given in eV, these are tabulated. The system wavefunction (electron + photon) a product of the electron free wave and of the photon, taken as , is defined, and the total Ψ(t) is truncated as required by the condition . It is possible to use any combination of polarization states for the photon, with at maximum a mixture of all possible polarizations, which is linear and right and left circular. The method applied takes into account the basic electron photon interaction, the free electron, which is the ejected electron, is described by a free wave, restricted to the first momenta. The quantum theory of the interaction needs to evaluate the integrals: , where rmax is a cut-off parameter to insert to enable finite values of these integrals. The I is calculated on the variables r, θ, φ, and the r3 concerns the radial volume multiplied by the r coming from the dipolar interaction. It follows that using the Fermi golden rule leads to an estimate of the probability of escape of an electron Pij, assuming that the normalisation factor of the A the electomagnetic vector is . The results for copper metal are given, the probabilty of escape, Pij has the correct dimension .

Quantum dynamics simulation of intramolecular singlet fission in covalently linked tetracene dimer.

In this work, we study singlet fission in tetracene para-dimers, covalently linked by a phenyl group. In contrast to most previous studies, we account for the full quantum dynamics of the combined excitonic and vibrational system. For our simulations, we choose a numerically unbiased representation of the molecule's wave function, enabling us to compare with experiments, exhibiting good agreement. Having access to the full wave function allows us to study in detail the post-quench dynamics of the excitons. Here, one of our main findings is the identification of a time scale t0 ≈ 35fs dominated by coherent dynamics. It is within this time scale that the larger fraction of the singlet fission yield is generated. We also report on a reduced number of phononic modes that play a crucial role in the energy transfer between excitonic and vibrational systems. Notably, the oscillation frequency of these modes coincides with the observed electronic coherence time t0. We extend our investigations by also studying the dependency of the dynamics on the excitonic energy levels that, for instance, can be experimentally tuned by means of the solvent polarity. Here, our findings indicate that the singlet fission yield can be doubled, while the electronic coherence time t0 is mainly unaffected.

High-resolution at 3T for in vivo derivative NMR spectroscopy in medical diagnostics of ovarian tumor: exact quantification by shape estimations

High-resolution at 3T for in vivo derivative NMR spectroscopy in medical diagnostics of ovarian tumor: exact quantification by shape estimations

Dynamical Invariant and Exact Mechanical Analyses for the Caldirola-Kanai Model of Dissipative Three Coupled Oscillators.

We study the dynamical invariant for dissipative three coupled oscillators mainly from the quantum mechanical point of view. It is known that there are many advantages of the invariant quantity in elucidating mechanical properties of the system. We use such a property of the invariant operator in quantizing the system in this work. To this end, we first transform the invariant operator to a simple one by using a unitary operator in order that we can easily manage it. The invariant operator is further simplified through its diagonalization via three-dimensional rotations parameterized by three Euler angles. The coupling terms in the quantum invariant are eventually eliminated thanks to such a diagonalization. As a consequence, transformed quantum invariant is represented in terms of three independent simple harmonic oscillators which have unit masses. Starting from the wave functions in the transformed system, we have derived the full wave functions in the original system with the help of the unitary operators.

Multiple Bonding in Rhodium Monoboride. Quasi-atomic Analyses of the Ground and Low-Lying Excited States.

The bonding structures of the ground state and the lowest five excited states of rhodium monoboride are identified by determining the quasi-atomic orbitals in full valence space MCSCF wave functions and the interactions between these orbitals. A quadruple bond, namely two π-bonds and two σ-bonds, is identified and characterized for the X1Σ+ ground state, in agreement with a previous report (Cheung J. Phys. Chem. Lett. 2020, 11, 659-663). However, in all excited states, the bonding is predicted to be weaker because, in these states, one of the σ-bonding interactions has a small magnitude. In the a3Δ and A1Δ states, the bond order is between a triple and quadruple bond. In the b3Σ+ state, the Rh-B linkage is a triple bond. In the c3Π and B1Π states, the atoms are linked by a double bond due to an additional weakening of the two π-bonds. The decreases in the predicted bond strengths are reflected in the decreases of the predicted binding energies and in the increases of the predicted bond lengths from the X1Σ+ ground state to the c3Π and the B1Π excited states. Notably, the 5pσ orbital of rhodium, which is vacant in the ground state of the atom, plays a significant role in the molecule.

Tunable Three-Body Loss in a Nonlinear Rydberg Medium.

Long-range Rydberg interactions, in combination with electromagnetically induced transparency (EIT), give rise to strongly interacting photons where the strength, sign, and form of the interactions are widely tunable and controllable. Such control can be applied to both coherent and dissipative interactions, which provides the potential for generating novel few-photon states. Recently it has been shown that Rydberg-EIT is a rare system in which three-body interactions can be as strong or stronger than two-body interactions. In this work, we study three-body scattering loss for Rydberg-EIT in a wide regime of single and two-photon detunings. Our numerical simulations of the full three-body wave function and analytical estimates based on Fermi's golden rule strongly suggest that the observed features in the outgoing photonic correlations are caused by the resonant enhancement of the three-body losses.

Solution of two-electron Schrödinger equations using a residual minimization method and one-dimensional basis functions

Distinctive from conventional electronic structure methods, we solve the Schrödinger wave equations of the helium atom and its isoelectronic ions by employing one-dimensional basis functions to separate components. We use full two-electron six-dimensional operators and wavefunctions represented with real-space grids where the refinement of the latter is carried out using a residual minimization method. In contrast to the standard single-electron approach, the current approach results in exact treatment of repulsion energy and, hence, more accurate electron correlation within five centihartrees or better included, with moderate computational cost. A simple numerical convergence between the error to accurate results and the grid-spacing size is found. The obtained two-electron Schrödinger wavefunction that contains vast and elaborating information for the radial correlation function and common one-dimensional functions shows the electron correlation effect on one-electron distributions.

Second Linear Response Theory and the Analytic Calculation of Excited-State Properties.

We present a method based on second linear response time-dependent density functional theory (TDDFT) to calculate permanent and transition multipoles of excited states, which are required to compute excited-state absorption/emission spectra and multiphoton optical processes, among others. In previous work, we examined computations based on second linear response theory in which linear response TDDFT was employed twice. In contrast, the present methodology requires information from only a single linear response calculation to compute the excited-state properties. These are evaluated analytically through various algebraic operations involving electron repulsion integrals and excitation vectors. The present derivation focuses on full many-body wave functions instead of single orbitals, as in our previous approach. We test the proposed method by applying it to several diatomic and triatomic molecules. This shows that the computed excited-state dipoles are consistent with respect to reference equation-of-motion coupled-cluster calculations.

Observation of Pauli Crystals.

The Pauli exclusion principle is a fundamental law underpinning the structure of matter. Because of their antisymmetric wave function, no two fermions can occupy the same quantum state. Here, we report on the direct observation of the Pauli principle in a continuous system of up to six particles in the ground state of a two-dimensional harmonic oscillator. To this end, we sample the full many-body wave function by applying a single atom resolved imaging scheme in momentum space. We find so-called Pauli crystals as a manifestation of higher order correlations. In contrast to true crystalline phases, these unique high-order density correlations emerge even without any interactions present. Our work lays the foundation for future studies of correlations in strongly interacting systems of many fermions.

Full-Bloch beams and ultrafast Rabi-rotating vortices

Strongly-coupled quantum fields, such as multi-component atomic condensates, optical fields and polaritons, are remarkable systems where the simple dynamics of coupled oscillators can meet the intricate phenomenology of quantum fluids. When the coupling between the components is coherent, not only the particles number, but also their phase texture that maps the linear and angular momentum, can be exchanged. Here, on a system of exciton-polaritons, we have realized a so-called full-Bloch beam: a configuration in which all superpositions of the upper and the lower polariton -- all quantum states of the associated Hilbert space -- are simultaneously present at different points of the physical space, evolving in time according to Rabi-oscillatory dynamics. As a result, the light emitted by the cavity displays a peculiar dynamics of spiraling vortices endowed with oscillating linear and angular momentum and exhibiting ultrafast motion of their cores with striking accelerations to arbitrary speeds. This remarkable vortex motion is shown to result from distortions of the trajectories by a homeomorphic mapping between the Rabi rotation of the full wavefunction on the Bloch sphere and Apollonian circles in the real space where the observation is made. Such full-Bloch beams offer new prospects at a fundamental level regarding their topological properties or in the interpretation of quantum mechanics, and the Rabi-rotating vortices they yield should lead to interesting applications such as ultrafast optical tweezers.

Steinmann relations and the wavefunction of the Universe

The physical principles of causality and unitarity put strong constraints on the analytic structure of the flat-space S-matrix. In particular, these principles give rise to the Steinmann relations, which require that the double discontinuities of scattering amplitudes in partially-overlapping momentum channels vanish. Conversely, at cosmological scales, the imprint of causality and unitarity is in general less well understood---the wavefunction of the universe lives on the future space-like boundary, and has all time evolution integrated out. In the present work, we show how the flat-space Steinmann relations emerge from the structure of the wavefunction of the universe, and derive similar relations that apply to the wavefunction itself. This is done within the context of scalar toy models whose perturbative wavefunction has a first-principles definition in terms of cosmological polytopes. In particular, we use the fact that the scattering amplitude is encoded in the scattering facet of cosmological polytopes, and that cuts of the amplitude are encoded in the codimension-one boundaries of this facet. As we show, the flat-space Steinmann relations are thus implied by the non-existence of codimension-two boundaries at the intersection of the boundaries associated with pairs of partially-overlapping channels. Applying the same argument to the full cosmological polytope, we also derive Steinmann-type constraints that apply to the full wavefunction of the universe. These arguments show how the combinatorial properties of cosmological polytopes lead to the emergence of flat-space causality in the S-matrix, and provide new insights into the analytic structure of the wavefunction of the universe.

Bootstrap embedding with an unrestricted mean-field bath.

A suite of quantum embedding methods have recently been developed where the Schmidt decomposition is applied to the full system wavefunction to derive basis states that preserve the entanglement between the fragment and the bath. The quality of these methods can depend heavily on the quality of the initial full system wavefunction. Most of these methods, including bootstrap embedding (BE) [M. Welborn et al; J. Chem. Phys. 145, 074102 (2016)], start from a spin-restricted mean-field wavefunction [call this restricted BE (RBE)]. Given that spin-unrestricted wavefunctions can capture a significant amount of strong correlation at the mean-field level, we suspect that starting from a spin-unrestricted mean-field wavefunction will improve these embedding methods for strongly correlated systems. In this work, BE is generalized to an unrestricted Hartree-Fock bath [call this unrestricted BE (UBE)], and UBE is applied to model hydrogen ring systems. UBE's improved versatility over RBE is utilized to calculate high spin symmetry states that were previously unattainable with RBE. Ionization potentials, electron affinities, and spin-splittings are computed using UBE with accuracy on par with spin-unrestricted coupled cluster singles and doubles. Even for cases where RBE is viable, UBE converges more reliably. We discuss the limitations or weaknesses of each calculation and how improvements to RBE and density matrix embedding theory these past few years can also improve UBE.

A cautionary tale: Problems in the valence-CASSCF description of the ground state (X1Σ+) of BF.

In the full optimized reaction space and valence-complete active space self-consistent field (vCAS) methods, a set of active orbitals is defined as the union of the valence orbitals on the atoms, all possible configurations involving the active orbitals are generated, and the orbitals and configuration coefficients are self-consistently optimized. Such wave functions have tremendous flexibility, which makes these methods incredibly powerful but can also lead to inconsistencies in the description of the electronic structure of molecules. In this paper, the problems that can arise in vCAS calculations are illustrated by calculations on the BH and BF molecules. BH is well described by the full vCAS wave function, which accounts for molecular dissociation and 2s-2p near-degeneracy in the boron atom. The same is not true for the full vCAS wave function for BF. There is mixing of core and active orbitals at short internuclear distances and swapping of core and active orbitals at large internuclear distances. In addition, the virtual 2π orbitals, which were included in the active space to account for the 2s-2p near degeneracy effect, are used instead to describe radial correlation of the electrons in the F2pπ-like pairs. Although the above changes lead to lower vCAS energies, they lead to higher vCAS+1+2 energies as well as irregularities and/or discontinuities in the potential energy curves. All of the above problems can be addressed by using the spin-coupled generalized valence bond-inspired vCAS wave function for BF, which includes only a subset of the atomic valence orbitals in the active space.

Why is Si2H2 Not Linear? An Intrinsic Quasi-Atomic Bonding Analysis.

The molecular energy of Si2H2 geometric structures increases in the order dibridged < trans-bent < linear, in contrast to acetylene, C2H2, for which the linear structure is the global minimum. In this study, the intra-atomic (antibonding) and bonding contributions to the total molecular energy of these valence isoelectronic molecules are computed by expressing the density matrices of the full valence space multiconfiguration self-consistent field wave function in terms of quasi-atomic orbitals. The analysis shows that the intra-atomic contributions to the molecular energy become less favorable in the order dibridged → trans-bent → linear for both C2H2 and Si2H2. By contrast, the inter-atomic bonding contributions become energetically more favorable in that order for both C2H2 and Si2H2. The two systems differ as follows. For Si2H2, the antibonding intra-atomic energy changes that occur when the dibridged molecule reconstructs into the trans-bent and linear structures prevail over the interatomic interactions that induce bond formation. In contrast, for C2H2, the interatomic interactions that create bonds prevail over the intra-atomic energy changes that occur when the dibridged molecule reconstructs into the trans-bent and linear structures. The intra-atomic energy changes that occur in these systems are related to the hybridization of the heavy atoms in an analogous manner to the hybridization of C in CH4 from (2s)2(2p)2 to sp3 hybrid orbitals.

Resolving a puzzling anomaly in the spin-coupled generalized valence bond description of benzene.

In an earlier study of benzene, Small and Head-Gordon found that the spin-coupled generalized valence bond (SCGVB) wave function for the π system predicted a distorted (non-D6h ) geometry, one with alternating CC bond lengths. However, the variations in the energy were very small and the predictions were made using a very small basis set (STO-3G). We re-examined this prediction using a much larger basis set (aug-cc-pVTZ) to determine the dependence of the energy of benzene on the distortion angle, ΔθCXC (ΔθCXC = 0° corresponds to the D6h structure). We also found a distorted geometry with the optimum ΔθCXC being 0.31° with an energy 0.040 kcal mol-1 lower than that for the D6h structure. In the optimum geometry, adjacent CC bond lengths are 1.3861 Å and 1.4004 Å. Analysis of the SCGVB wave function led us to conclude that the cause of the unusual non-D6h geometry predicted by the SCGVB calculations seems to be a result of the interaction between the Kekulé and Dewar components of the full SCGVB wave function. The addition of doubly ionic configurations to the SCGVB wave function leads to the prediction of a D6h geometry for benzene and a dependence on ΔθCXC essentially the same as that predicted by the complete active space self-consistent field wave function.

Systematic and variational truncation of the configuration space in the multiconfiguration time-dependent Hartree method: The MCTDH[n] hierarchy.

The multiconfiguration time-dependent Hartree (MCTDH) method is a powerful method for solving the time-dependent Schrödinger equation in quantum molecular dynamics. It is, however, hampered by the so-called curse of dimensionality which results in exponential scaling with respect to the number of degrees of freedom in the system and, thus, limits its applicability to small- and medium-sized molecules. To avoid this scaling, we derive equations of motion for a series of truncated MCTDH methods using a many-mode second-quantization formulation where the configuration space is restricted based on mode-combination levels as also done in the vibrational configuration interaction and vibrational coupled cluster methods for solving the time-independent Schrödinger equation. The full MCTDH wave function is invariant with respect to the choice of constraint (or gauge) operators, but restricting the configuration space removes this invariance. We, thus, analyze the remaining redundancies and derive equations for variationally optimizing the non-redundant matrix elements of the constraint operators. As an alternative, we also present a constraint that keeps the density matrices block diagonal during the propagation and the two choices are compared. Example calculations are performed on formyl fluoride and a series of high-dimensional Henon-Heiles potentials. The results show that the MCTDH[n] methods can be applied to large systems and that an optimal choice of constraint operators is key to obtaining the correct physical behavior of the wave function.

Measuring the time–frequency properties of photon pairs: A short review

Encoding information in the time–frequency domain demonstrates its potential for quantum information processing. It offers a novel scheme for communications with large alphabets, computing with large quantum systems, and new approaches to metrology. It is then crucial to secure full control on the generation of time–frequency quantum states and their properties. Here, the authors present an overview of the theoretical background and the technical aspects related to the characterization of time–frequency properties of two-photon states. The authors provide a detailed account of the methodologies that have been implemented for measuring frequency correlations and for the retrieval of the full spectral wavefunction. This effort has benefited enormously from the adaptation of classical metrology schemes to the needs of operating at the single-photon level.

Dynamic stress concentration and failure characteristics around elliptical cavity subjected to impact loading

Wave function expansion method is used to solve the scattering and dynamic stress concentration around the elliptic cavity in the full plane under steady state linear elastic stationary incident SH wave with arbitrary angle. Under the elliptical coordinate system, Mathieu equation is obtained by separating variables from Helmholtz equation. Considering the simplicity of Mathieu function in solving elliptic boundary problem, the incident plane wave is expanded into the series of Mathieu function, and the full wave function is obtained from the stress boundary condition of the elliptic cavity, then the response of the elliptic cavity subjected to the steady state linear elastic stationary incident SH wave is obtained. Through the Fourier integral transformation of transient impact, the dynamic stress concentration of transient incident SH wave around an elliptical cavity can be obtained. In addition, the finite element method (FEM) numerical simulation software LS-DYNA is used to calculate the dynamic stress concentration and plastic deformation around the elliptical cavity with transient impact. Furthermore, the influence of the initial stress on plastic deformation is obtained. The results show that the incident angel, wave number and the ellipse axis ratio have great influence on the distribution of dynamic stress concentration and the failure of the elliptical cavity.

Full Wave Function Optimization with Quantum Monte Carlo-A Study of the Dissociation Energies of ZnO, FeO, FeH, and CrS.

The dissociation energies of four transition-metal dimers are determined using diffusion Monte Carlo. The Jastrow, configuration interaction, and molecular orbital parameters of the wave function are both partially and fully optimized with respect to the variational energy. The pivotal role is thereby ascribable to the optimization of the molecular orbital parameters of a complete active space wave function in the presence of a Jastrow correlation function. Excellent results are obtained for ZnO, FeO, FeH, and CrS. In addition, potential energy curves are computed for the first three compounds at the multireference diffusion Monte Carlo (MR-DMC) level, from which spectroscopic constants such as the equilibrium bond distance, the harmonic frequency, and the anharmonicity are extracted. All of these quantities agree well with the experiment. Furthermore, it is shown for CrS that a restricted active space calculation can yield improved initial orbitals by including single and double excitations from the original active space into a set of virtual orbitals. We demonstrated in this study that the fixed-node error in DMC can be systematically reduced for multireference systems by orbital optimization in compact active spaces. Although DMC calculations with a large number of determinants are possible and very accurate, our results demonstrate that compact wave functions may be sufficient in order to obtain accurate nodal surfaces, which determine the accuracy of DMC, even in the case of transition-metal compounds.