Ground-state Distribution Research Articles

Persistent Ground-State Planar Alignment of Iodine Molecule through Resonant Excitation.

We demonstrate the generation of a persistent planar molecular alignment by subjecting a relatively warm gas sample to a resonant femtosecond laser pulse. By optically probing I_{2} molecules in their vibronic ground states, we observe a persistent delocalization of their axes near the plane orthogonal to the field direction. This phenomenon is attributed to the one-photon resonant excitation, primarily removing molecules from the thermal ground-state distribution that are initially aligned along the field, i.e., those with small projection of their rotational angular momentum along the field.

Evaluation of the excitation spectra with diffusion Monte Carlo on an auxiliary bosonic ground state.

We aim to improve upon the variational Monte Carlo (VMC) approach for excitations replacing the Jastrow factor by an auxiliary bosonic (AB) ground state and multiplying it by a fermionic component factor. The instantaneous change in imaginary time of an arbitrary excitation in the original interacting fermionic system is obtained by measuring observables via the ground-state distribution of walkers of an AB system that is subject to an auxiliary effective potential. The effective potential is used to (i) drive the AB system's ground-state configuration space toward the configuration space of the excitations of the original fermionic system and (ii) subtract from a diffusion Monte Carlo (DMC) calculation contributions that can be included in conventional approximations, such as mean-field and configuration interaction (CI) methods. In this novel approach, the AB ground state is treated statistically in DMC, whereas the fermionic component of the original system is expanded in a basis. The excitation energies of the fermionic eigenstates are obtained by sampling a fermion-boson coupling term on the AB ground state. We show that this approach can take advantage of and correct for approximate eigenstates obtained via mean-field calculations or truncated interactions. We demonstrate that the AB ground-state factor incorporates the correlations missed by standard Jastrow factors, further reducing basis truncation errors. Relevant parts of the theory have been tested in soluble model systems and exhibit excellent agreement with exact analytical data and CI and VMC approaches. In particular, for limited basis set expansions and sufficient statistics, AB approaches outperform CI and VMC in terms of basis size for the same systems. The implementation of this method in current codes, despite being demanding, will be facilitated by reusing procedures already developed for calculating ground-state properties with DMC and excitations with VMC.

First Double-Differential Measurement of Kinematic Imbalance in Neutrino Interactions with the MicroBooNE Detector.

We report the first measurement of flux-integrated double-differential quasielasticlike neutrino-argon cross sections, which have been made using the Booster Neutrino Beam and the MicroBooNE detector at Fermi National Accelerator Laboratory. The data are presented as a function of kinematic imbalance variables which are sensitive to nuclear ground-state distributions and hadronic reinteraction processes. We find that the measured cross sections in different phase-space regions are sensitive to different nuclear effects. Therefore, they enable the impact of specific nuclear effects on the neutrino-nucleus interaction to be isolated more completely than was possible using previous single-differential cross section measurements. Our results provide precision data to help test and improve neutrino-nucleus interaction models. They further support ongoing neutrino-oscillation studies by establishing phase-space regions where precise reaction modeling has already been achieved.

Deciphering the Influence of Ground-State Distributions on the Calculation of Photolysis Observables.

Nonadiabatic molecular dynamics offers a powerful tool for studying the photochemistry of molecular systems. Key to any nonadiabatic molecular dynamics simulation is the definition of its initial conditions (ICs), ideally representing the initial molecular quantum state of the system of interest. In this work, we provide a detailed analysis of how ICs may influence the calculation of experimental observables by focusing on the photochemistry of methylhydroperoxide (MHP), the simplest and most abundant organic peroxide in our atmosphere. We investigate the outcome of trajectory surface hopping simulations for distinct sets of ICs sampled from different approximate quantum distributions, namely harmonic Wigner functions and ab initio molecular dynamics using a quantum thermostat (QT). Calculating photoabsorption cross-sections, quantum yields, and translational kinetic energy maps from the results of these simulations reveals the significant effect of the ICs, in particular when low-frequency (∼ a few hundred cm-1) normal modes are connected to the photophysics of the molecule. Overall, our results indicate that sampling ICs from ab initio molecular dynamics using a QT is preferable for flexible molecules with photoactive low-frequency modes. From a photochemical perspective, our nonadiabatic dynamics simulations offer an explanation for a low-energy tail observed at high excitation energy in the translational kinetic energy map of MHP.

Ground-state energy distribution of disordered many-body quantum systems.

Extreme-value distributions are studied in the context of a broad range of problems, from the equilibrium properties of low-temperature disordered systems to the occurrence of natural disasters. Our focus here is on the ground-state energy distribution of disordered many-body quantum systems. We derive an analytical expression that, upon tuning a parameter, reproduces with high accuracy the ground-state energy distribution of the systems that we consider. For some models, it agrees with the Tracy-Widom distribution obtained from Gaussian random matrices. They include transverse Ising models, the Sachdev-Ye model, and a randomized version of the PXP model. For other systems, such as Bose-Hubbard models with random couplings and the disordered spin-1/2 Heisenberg chain used to investigate many-body localization, the shapes are at odds with the Tracy-Widom distribution. Our analytical expression captures all of these distributions, thus playing a role to the lowest energy level similar to that played by the Brody distribution to the bulk of the spectrum.

Synthesis and Thermal, Photophysical, Electrochemical Properties of 3,3-di[3-Arylcarbazol-9-ylmethyl]oxetane Derivatives.

Novel oxetane-functionalized derivatives were synthesized to find the impact of carbazole substituents, such as 1-naphtyl, 9-ethylcarbazole and 4-(diphenylamino)phenyl, on their thermal, photophysical and electrochemical properties. Additionally, to obtain the optimized ground-state geometry and distribution of the frontier molecular orbital energy levels, density functional theory (DFT) calculations were used. Thermal investigations showed that the obtained compounds are highly thermally stable up to 360 °C, as molecular glasses with glass transition temperatures in the range of 142–165 °C. UV–Vis and photoluminescence studies were performed in solvents of differing in polarity, in the solid state as a thin film on glass substrate, and in powders, and were supported by DFT calculations. They emitted radiation both in solution and in film with photoluminescence quantum yield from 4% to 87%. Cyclic voltammetry measurements revealed that the materials undergo an oxidation process. Next, the synthesized molecules were tested as hole transporting materials (HTM) in perovskite solar cells with the structure FTO/b-TiO2/m-TiO2/perovskite/HTM/Au, and photovoltaic parameters were compared with the reference device without the oxetane derivatives.

Hydrolysis of Schiff bases with phenyl-ethynyl-phenyl system: The importance for biological and physicochemical studies

A series of new Schiff bases containing the phenyl-ethynyl-phenyl system was synthesized and their thermal stability, photophysical and electrochemical properties were investigated. Moreover, DFT calculations were performed to obtain the optimized ground-state geometry and distribution of the HOMO and LUMO levels as well as IR spectra of the prepared compounds. It was found that, the photoluminescence of synthesized imines was negligible in all investigated organic solvents except for the PBS/ACN mixture. As was proved in further studies, this phenomenon was related to the partial hydrolysis of imines, which is the source of the fluorogenic aldehyde causing the aggreggacion incrased-emision effect. In further research, due to the susceptibility of the azomethines to partial hydrolysis, the biological activity of 2-{(E)-[4-(phenylethynyl) phenyl]imino}phenol (1b), substrate (2-aminophenol) and Cu(II)-1b complex was analyzed. The biological tests showed, that 1b (as example of imine resveratrol analogue), demonstrated its increased cytostatic activity in prostate cancer cellular system. It was proved that the non-hydrolyzed imine was crucial for the cytotoxic effect. This activity could be ascribed to its Cu(II) complexing capability as showed in our previous research.

Analytical Ground-State of an Exciton Trapped in a Circular Parabolic Quantum Dot in the Presence of a Magnetic Field

The quasi-exact properties of an exciton are investigated theoretically in the presence of an external magnetic field using the effective-mass approach in GaAs parabolic quantum dot. The energy spectrum is obtained analytically as a function of the dot radius, interaction strength and magnetic field. It is established that, a steady bound state of an exciton in the ground state exists under the effect of a strong magnetic field; also I noticed that the exciton binding energy decreases by increasing both the radius of the dot and the magnetic field strength and the reduction becomes pronounced for larger dots. As expected, it has been found that the exciton total energy decreases with increasing the size of the dot and it enhances by increasing the magnetic field. It appears that the exciton total energy strongly depends on the magnetic field for dots with big size. The magnetic field effect on the exciton size also has been studied. It is shown that the increase in the magnetic field leads to a reduction in the exciton size; due to magnetic field confinement, while the size of an exciton reach its bulk limit as the dot size increases. Moreover, it is shown that, if the dot radius is sufficiently large the oscillator strength saturates and it becomes insensitive to the magnetic field while the increase in the magnetic field gradually weakened the oscillator strength. I have calculated the ground-state distribution for both the electron and the hole. It is found that the localization of the electron/hole increases in the presence of a magnetic field. Moreover, the ground-state optical-absorption intensity is investigated. Finally, the dependence of the lowest five states of an exciton on both the dot radius and the magnetic field are discussed.

Novel β-ketoenamines versus azomethines for organic electronics: characterization of optical and electrochemical properties supported by theoretical studies

A simple and rapid synthesis of six new, stable β-ketoenamines by coupling 3-amino-1,8-naphthalimide derivatives with 2-(4-pyrimidinyl)-malondialdehyde in the presence of trifluoroacetic acid was developed. Two of the synthesized 3-amino-1,8-naphthalimide derivatives were condensed with 9H-fluorene-2-carboxaldehyde, resulting in azomethine products. The structure of obtained compounds was confirmed by 1H and 13C NMR, COSY, HMQC, FTIR spectroscopy and elemental analysis. The photophysical, electrochemical and thermal properties of the compounds were investigated. Additionally, calculations using density functional theory were performed to obtain the optimized ground-state geometry and distribution of the HOMO and LUMO levels as well as UV–Vis and photoluminescence spectra of the synthesized compounds. DSC measurements revealed that the compounds form amorphous material with glass transition temperature in the range of 41–146 °C and are thermally stable up to 300 °C. β-Ketoenamines have higher glass transition temperature, smaller energy gap (2.11–2.47 eV), higher PL quantum efficiency in solution (5.25–12.97%) and ability to aggregation-induced emission than the azomethines.

A DFT and TD-DFT study on electronic structures and UV-spectra properties of octaethyl-porphyrin with different central metals(Ni, V, Cu, Co)

In this work, the octaethyl-porphyrins with different central metals (M-OEP, M = Ni, VO, Cu, Co) were used to investigate the ground-state molecular structure, electron distribution and UV-spectra properties on molecular level by density functional theory (DFT). The results showed that the calculation structure parameters of metalloporphyrins agreed well with the experimental value. According to the Natural Bond Orbital (NBO) analysis, the charge distribution of different metalloporphyrins was found that the charge values of the central metal M decreased with the order of VO < Ni < Co < Cu, while the bonding strength between M and the coordinating atom N was VO > Ni > Co > Cu. At the same time, the frontier molecular orbital calculations showed that the SOMO energy of VO (OEP) molecules in the open-shell system was higher than that of Co (OEP) and Cu (OEP), which means that its UV absorption characteristic peak would be red-shifted. In addition, the IEFPCM model of Time-dependent Density functional theory (TD-DFT) was further utilized to simulate the four substance in toluene solution: Co (OEP), Ni (OEP), Cu (OEP) and VO (OEP), and the Soret band peaks were calculated respectively as: 382 nm, 383 nm, 391 nm and 401 nm. Furthermore, the quantitative simulation analysis of metalloporphyrins was combined with experimental data. It could be found that the location rules of the four kinds of metalloporphyrins calculated absorption characteristic peaks were consistent with the experimental ones, and the relative errors of each peak were within 3%. These methods used above provide a theoretical path for analyzing and identifying unknown porphyrin compounds in petroleum.

Novel 1,8-naphthalimides substituted at 3-C position: Synthesis and evaluation of thermal, electrochemical and luminescent properties

Novel 1,8-naphthalimides core substituted at 3-C position via imine bond with carbazole, benzothiazole, methylindole, quinoline, benzoindole, phenylmorpholine and triphenylamine derivatives were designed, synthesized and investigated with regard to their thermal, electrochemical, and luminescence behavior. DSC measurements showed that the obtained crystalline compounds can be converted into amorphous materials with glass transition temperatures in the range of 28–54 °C, except for the molecule bearing benzoindole derivative. The prepared compounds were thermally stable with the onset of thermal decomposition in the range of 345–368 °C. Energy band gap electrochemically estimated was modulated from 2.13 to 2.52 eV. Effect of excitation wavelength on the photoluminescence relative intensity of those naphthalimides in solution was detected. Their photoluminescence maximum band was located in the range of 495–560 nm in solution with the quantum yield from 0.2 to 14.0%. In the film, they emitted light in the blue and green spectral region with quantum yields from 1.1 to 3.6%. The electroluminescence ability of core substituted 1,8-naphthalimides was tested in the single-layer diode geometry. They were utilized as an emitting layer for both non-doped and doped single-layer OLEDs fabricated by solution processing. Additionally, calculations using density functional theory were performed to obtain the optimized ground-state geometry and distribution of the HOMO and LUMO levels of the synthesized molecules.

Ground-State Charge-Density Distribution in a Crystal of the Luminescent ortho-Phenylenediboronic Acid Complex with 8-Hydroxyquinoline.

This contribution is devoted to the first electron density studies of a luminescent oxyquinolinato boron complex in the solid state. ortho-Phenylenediboronic acid mixed with 8-hydroxyquinoline in dioxane forms high-quality single crystals via slow solvent evaporation, which allows successful high resolution data collection (sinθ/λ = 1.2 Å-1) and charge density distribution modeling. Particular attention has been paid to the boron-oxygen fragment connecting the two parts of the complex, and to the solvent species exhibiting anharmonic thermal motion. The experiment and theory compared rather well in terms of atomic charges and volumes, except for the boron centers. Boron atoms, as expected, constitute the most electron-deficient species in the complex molecule, whereas the neighboring oxygen and carbon atoms are the most significantly negatively charged ones. This part of the molecule appears to be very much involved in the charge transfer occurring between the acid fragment and oxyquinoline moiety leading to the observed fluorescence, as supported by the time-dependent density functional theory (TDDFT) results and the generated transition density maps. TDDFT calculations indicated that p-type atomic orbitals contributing to the HOMO-1, HOMO, and LUMO play the major role in the lowest energy transitions, and enabled further comparison with the charge density features, which is discussed in details. Furthermore, the results confirmed the known fact the Q ligand character is most important for the spectroscopic properties of this class of complexes.

Intramolecular Electron Transfer in Frozen Solvents: Charge Transfer and Local Triplet States Population Dynamics Revealed by Dual Phosphorescence.

In frozen solvents at 77 K, ultrafast (≤250 fs) photoinduced intramolecular electron transfer (ET) in bichromophoric donor-acceptor ([D-A]) diarylmethane lactones produces a covalently linked radical ion pair, 1[D•+-A•-]. Steady state and time-resolved luminescence measurements reveal that 1[D•+-A•-] decays to charge-separated (3[D•+-A•-]) and donor-centered ([3D*-A]) triplets, which display dual phosphorescence. 3[D•+-A•-] and [3D*-A] are formed in parallel via two intersystem crossing mechanisms: spin orbit charge transfer (SOCT) and hyperfine coupling (HFC), with solvent dependent branching ratio. The solvent drives the D-A alignment during the freezing process to adapt to increasing solvent polarity, producing inhomogeneous ground-state population distribution with solvent-dependent D-A exchange interaction, which plays a key role in partitioning into SOCT and HFC mechanisms. In polar glasses, a third phosphorescence band appears due to dissociative back ET in 3[D•+-A•-] resulting in excited open ring biradical.

Synthesis and Characterization of Quinoidal Diketopyrrolopyrrole Derivatives with Exceptionally High Electron Affinities

Open-shell singlet biradicaloids are short-lived intermediates, but they exhibit fascinating properties for spin-based devices. Therefore, understanding the nature of their electronic structure and stability is critical for harnessing them in optoelectronic or spintronic devices. Toward this goal, we have synthesized a series of diketopyrrolopyrrole-based quinoidal molecules to investigate the contribution and relative importance of the biradical form on the ground-state electronic structure and distribution of spin density. Possibility of crossover from a closed-shell to an open-shell structure with increase in the C═C/C–C conjugation length was investigated. The ground-state properties were systematically investigated by nuclear magnetic resonance (NMR) spectroscopy, single-crystal X-ray diffraction, and electrochemical studies. Furthermore, n-doping has been carried out in solution at ambient conditions to understand the nature of doped species and demonstrate air stability. Doped species were probed b...

Ground-state energy, density profiles, and momentum distribution of attractively interacting 1D Fermi gases with hard-wall boundaries: a Monte Carlo study

Motivated by the realization of hard-wall boundary conditions in experiments with ultracold atoms, we investigate the ground-state properties of spin-1/2 fermions with attractive interactions in a one-dimensional box. We use lattice Monte Carlo methods to determine essential quantities like the energy, which we compute as a function of coupling strength and particle number in the regime from few to many particles. Many-fermion systems bound by hard walls display non-trivial density profiles characterized by so-called Friedel oscillations (which are similar to those observed in harmonic traps). In non-interacting systems, the characteristic length scale of the oscillations is set by , where is the Fermi momentum, while repulsive interactions tend to generate Wigner-crystal oscillations of period . Based on the non-interacting result, we find a remarkably simple parametrization of the density profiles of the attractively interacting case, which we generalize to the one-body density matrix. While the total momentum is not a conserved quantity in the presence of hard walls, the magnitude of the momentum does provide a good quantum number. We are therefore able to provide a detailed characterization of the (quasi-)momentum distribution, which displays rather robust discontinuity at the Fermi surface. In addition, we determine the spatially varying on-site density–density correlation, which in turn yields Tan’s contact density and, upon integration, Tan’s contact. As is well known, the latter fully determines the short-range correlations and plays a crucial role in a multitude of equilibrium and non-equilibrium sum rules.

Ground-State Charge Transfer: Lithium-Benzene and the Role of Hartree-Fock Exchange.

Most approximations to the exchange-correlation functional of Kohn-Sham density functional theory lead to delocalization errors that undermine the description of charge-transfer phenomena. We explore how various approximate functionals and charge-distribution schemes describe ground-state atomic-charge distributions in the lithium-benzene complex, a model system of relevance to carbon-based supercapacitors. To understand the trends, we compare Hartree-Fock (HF) and correlated post-HF calculations, confirming that the HOMO-LUMO gap is narrower in semilocal functionals but widened by hybrid functionals with large fractions of HF exchange. For semilocal functionals, natural bond orbital (NBO) and Mulliken schemes yield opposite pictures of how charge transfer occurs. In PBE, for example, when lithium and benzene are <1.5 Å apart, NBO yields a positive charge on the lithium atom, but the Mulliken scheme yields a negative charge. Furthermore, the partial charges in conjugated materials depend on the interplay between the charge-distribution scheme employed and the underlying exchange-correlation functional, being critically sensitive to the admixture of HF exchange. We analyze and explain why this happens, discuss implications, and conclude that hybrid functionals with an admixture of about one-fourth of HF exchange are particularly useful in describing charge transfer in the lithium-benzene model.

Isotope effects in liquid water probed by transmission mode x-ray absorption spectroscopy at the oxygen K-edge.

The effects of isotope substitution in liquid water are probed by x-ray absorption spectroscopy at the O K-edge as measured in transmission mode. Confirming earlier x-ray Raman scattering experiments, the D2O spectrum is found to be blue shifted with respect to H2O, and the D2O spectrum to be less broadened. Following the earlier interpretations of UV and x-ray Raman spectra, the shift is related to the difference in ground-state zero-point energies between D2O and H2O, while the difference in broadening is related to the difference in ground-state vibrational zero-point distributions. We demonstrate that the transmission-mode measurements allow for determining the spectral shapes with unprecedented accuracy. Owing in addition to the increased spectral resolution and signal to noise ratio compared to the earlier measurements, the new data enable the stringent determination of blue shift and broadening in the O K-edge x-ray absorption spectrum of liquid water upon isotope substitution. The results are compared to UV absorption data, and it is discussed to which extent they reflect the differences in zero-point energies and vibrational zero-point distributions in the ground-states of the liquids. The influence of the shape of the final-state potential, inclusion of the Franck-Condon structure, and differences between liquid H2O and D2O resulting from different hydrogen-bond environments in the liquids are addressed. The differences between the O K-edge absorption spectra of water from our transmission-mode measurements and from the state-of-the-art x-ray Raman scattering experiments are discussed in addition. The experimentally extracted values of blue shift and broadening are proposed to serve as a test for calculations of ground-state zero-point energies and vibrational zero-point distributions in liquid H2O and D2O. This clearly motivates the need for new calculations of the O K-edge x-ray absorption spectrum of liquid water.

Momentum distributions and numerical methods for strongly interacting one-dimensional spinor gases

One-dimensional spinor gases with strong $\ensuremath{\delta}$ interaction fermionize and form a spin chain. The spatial degrees of freedom of this atom chain can be described by a mapping to spinless noninteracting fermions and the spin degrees of freedom are described by a spin-chain model with nearest-neighbor interactions. Here, we compute momentum and occupation-number distributions of up to 16 strongly interacting spinor fermions and bosons as a function of their spin imbalance, the strength of an externally applied magnetic field gradient, the length of their spin, and for different excited states of the multiplet. We show that the ground-state momentum distributions resemble those of the corresponding noninteracting systems, apart from flat background distributions, which extend to high momenta. Moreover, we show that the spin order of the spin chain---in particular antiferromagnetic spin order---may be deduced from the momentum and occupation-number distributions of the system. Finally, we present efficient numerical methods for the calculation of the single-particle densities and one-body density matrix elements and of the local exchange coefficients of the spin chain for large systems containing more than 20 strongly interacting particles in arbitrary confining potentials.

Equilibrium vortex lattices of a binary rotating atomic Bose–Einstein condensate with unequal atomic masses

We perform a detailed numerical study of the equilibrium ground-state structures of a binary rotating Bose–Einstein condensate with unequal atomic masses. Our results show that the ground-state distribution and its related vortex configurations are complex events that differ markedly depending strongly on the strength of rotation frequency, as well as on the ratio of atomic masses. We also discuss the structures and radii of the clouds, the number and the size of the core region of the vortices, as a function of the rotation frequency, and of the ratio of atomic masses, and the analytical results agree well with our numerical simulations. This work may open an alternate way in the quantum control of the binary rotating quantum gases with unequal atomic masses.

Correlation properties of a three-body bosonic mixture in a harmonic trap

We make use of a simple pair correlated wave function approach to obtain results for the ground-state densities and momentum distribution of a one-dimensional three-body bosonic system with different interactions in a harmonic trap. For equal interactions this approach is able to reproduce the known analytical cases of zero and infinite repulsion. We show that our results for the correlations agree with the exact diagonalization in all interaction regimes and with analytical results for the strongly repulsive impurity. This method also enables us to access the more complicated cases of mixed interactions, and the probability densities of these systems are analyzed.