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Fluorescent probes have become an indispensable tool in the detection and imaging of biological and disease-related analytes due to their sensitivity and technical simplicity. In particular, fluorescent probes with far-red to near-infrared (FR-NIR) emissions are very attractive for biomedical applications. However, many available FR-NIR fluorophores suffer from small Stokes shifts and sometimes low quantum yields, resulting in self-quenching and low contrast. In this work, we describe the rational design and engineering of FR-NIR 2,4,6-triphenylpyrylium-based fluorophores (TPP-Fluors) with the help of theoretical calculations. Our strategy is based on the appending of electron-donating substituents and fusing groups onto 2,4,6-triphenylpyrylium. In contrast to the parent TPP with short emission wavelength, weak quantum yields, and low chemical stability, the obtained novel TPP-Fluors display some favorable properties, such as long-wavelength emission, large Stokes shifts, moderate to high quantum yields, and chemical stability. TPP-Fluors demonstrate their biological value as mitochondria-specific labeling reagents due to their inherently positive nature. In addition, TPP-Fluors can also be applied to develop ratiometric fluorescent probes, as the electron-donating ability of the 2,6-phenyl substituents is closely correlated with their emission wavelength. A proof-of-concept ratiometric probe has been developed by derivatizing the amino groups of TPP-Fluor for the detection and imaging of nitroreductase in vitro and in hypoxic cells.

The technique of multimode absorption spectroscopy (MUMAS) is reviewed in the context of laser-based methods for gas sensing of multiple species. The principles and practical implementation of the method are outlined with examples of applications using lasers with outputs in spectral ranges from the visible to the mid-infrared, including interband cascade lasers (ICLs) and quantum cascade lasers (QCLs). The advantages and limitations of MUMAS are considered relative to other laser-based methods, and potential future developments and applications are suggested.

In a generic synthesis approach, all three CsPbX3 (X=Cl, Br and I) perovskite nanocrystals having near unity quantum yields is reported. This has been achieved by injecting the desired amount of preformed alkylammonium halide salts which acted as a dual source providing halide ions and the capping agent to an equimolar amount of non-halide Pb and Cs precursors in a reaction flask at an optimized reaction temperature. The composition sensitivity of Pb to Cs ratio, high temperature reaction, and injection of ammonium halide remained the key parameters for obtaining the high quantum yields. Details of the reaction process, use of different reagents and setting up the reaction parameters are reported.

Dcdftbmd is a Fortran 90/95 program that enables efficient quantum mechanical molecular dynamics (MD) simulations using divide-and-conquer density functional tight-binding (DC-DFTB) method. Based on the remarkable performance of previous massively parallel DC-DFTB energy and gradient calculations for huge systems, the code has been specialized to MD simulations. Recent implementations and modifications including DFTB extensions, improved computational speed in the DC-DFTB computational steps, algorithms for efficient initial guess charge prediction, and free energy calculations via metadynamics technique have enhanced the capability to obtain atomistic insights in novel applications to nanomaterials and biomolecules. The energy, structure, and other molecular properties are also accessible through the single-point calculation, geometry optimization, and vibrational frequency analysis. The available functionalities are outlined together with efficiency tests and simulation examples. © 2019 Wiley Periodicals, Inc.

Bis(acetylido) aurates(I) and thallium(I) trifluoromethylsulfonates were used to synthesize AuI -TlI metallopolymers, displaying novel and unusual structural motifs of the metal-metal backbones in the solid state: a discrete molecular cluster, 1D chains of interconnected dimers, tetramers, or dodecamers of Au-Tl units, and a 2D-plane network, consisting of alternating edge-linked (AuTl)6 and (AuTl)4 cycles. The formation of the different architectures was primarily controlled by the steric demand of the acetylide-substituent groups. Thus, the bulkiest 2,6-diisopropylphenyl derivative yielded a molecular cluster [Tl2 Au3 ]. Most compounds showed bright visible photoluminescence with quantum yields of up to 25 % at ambient temperature. The color of the emitted light significantly differs with the network structure. Furthermore, theoretical studies of singlet excitations in the molecular cluster, as well as NMR and mass-spectrometric investigations of the fragmentation of the metallopolymers in solution are described in detail.

DFT methods are routinely used to predict the excited-state structure of phosphorescent triplet emitters. However, sometimes they fail: different functionals predict diverse lowest adiabatic emissive states. An evaluation is undertaken to determine whether it is possible to use DFT methods to investigate the triplet emitter's hypersurfaces and to explain the experimental observation that similar ligands lead to remarkably diverse phosphorescence quantum yields.

We show that the mutual, through‐space compression of atomic volume experienced by approaching topological atoms causes an exponential increase in the intra‐atomic energy of those atoms, regardless of approach orientation. This insight was obtained using the modern energy partitioning method called interacting quantum atoms (IQA). This behaviour is consistent for all atoms except hydrogen, which can behave differently depending on its environment. Whilst all atoms experience charge transfer when they interact, the intra‐atomic energy of the hydrogen atom is more vulnerable to these changes than larger atoms. The difference in behaviour is found to be due to hydrogen's lack of a core of electrons, which, in heavier atoms, consistently provide repulsion when compressed. As such, hydrogen atoms do not always provide steric hindrance. In accounting for hydrogen's unusual behaviour and demonstrating the exponential character of the intra‐atomic energy in all other atoms, we provide evidence for IQA's intra‐atomic energy as a quantitative description of steric energy.

The energy profiles of hydrogen-bonded heterocyclic aromatics have been decomposed into atomistic energy contributions using the Interacting Quantum Atoms (IQA) method. The resulting energy contributions have been sequenced by the Relative Energy Gradient (REG) approach in order to determine their influence upon the shape of these energy profiles. The results show inadequacies in Jorgensen’s secondary interaction hypothesis (SIH). A novel method of finding a condensed analogy for the interaction between the molecules is presented. The findings of this work further doubt the validity of the SIH, and reinforce previous warnings against its misguided use.

Proteins are not locked in a single structure but often interconvert with other conformers that are critical for function. When such conformers are sparsely populated and transiently formed they become invisible to routine biophysical methods, however they can be studied in detail by NMR spin-relaxation experiments. Few experiments are available in the NMR toolkit, however, for characterizing the hydrodynamic properties of invisible states. Herein we describe a CPMG-based experiment for measuring translational diffusion constants of invisible states using a pulsed-field gradient approach that exploits methyl 1 H triple-quantum coherences. An example, involving diffusion of a sparsely populated and hence invisible unfolded protein ensemble is presented, without the need for the addition of denaturants that tend to destroy weak interactions that can be involved in stabilizing residual structure in the unfolded state.

The OH + HCl → H2 O + Cl reaction is one of the most studied four-body systems, extensively investigated by both experimental and theoretical approaches. Here, as a continuation of our previous work on the OH + HBr and OH + HI reactions, which manifest an anti-Arrhenius behavior that was explained by stereodynamic and roaming effects, we extend the strategy to understand the transition to the sub-Arrhenius behavior occurring for the HCl case. As previously, we perform first-principles on-the-fly Born-Oppenheimer molecular dynamics calculations, thermalized at four temperatures (50, 200, 350, and 500 K), but this time we also apply a high-level transition-state-theory, modified to account for tunneling conditions. We find that the theoretical rate constants calculated with Bell tunneling corrections are in good agreement with extensive experimental data available for this reaction in the ample temperature range: (i) simulations show that the roles of molecular orientation in promoting this reaction and of roaming in finding the favorable path are minor than in the HBr and HI cases, and (ii) dominating is the effect of quantum mechanical penetration through the energy barrier along the reaction path on the potential energy surface. The discussion of these results provides clarification of the origin on different non-Arrhenius mechanisms observed along this series of reactions. © 2018 Wiley Periodicals, Inc.

Messenger infrared predissociation spectroscopy is an powerful technique to investigate elusive molecules. Despite accumulating evidence that 4 He-tagging has a minor effect on structure due to its weak interactions, its impact on intramolecular large-amplitude motion is much less clear. Using one of the most floppy molecules known, protonated methane, we investigate to what extent helium tags perturb its salient fluxionality, underlying full hydrogen scrambling. Bosonic path integral quantum simulations show that the impact of attaching up to four 4 He messengers to CH5+ is negligible compared to the non-tagged bare species. This non-invasive nature is unrelated to the bosonic character of 4 He. Yet, hydrogen scrambling has a pronounced effect on the microsolvation shell pattern of CH5+ ⋅Hen that emerges as a result of tagging. These findings should provide impetus to explore the power of He-tagging, particularly in the realm of weakly bound intermolecular complexes.

In this work an approach to investigate the properties of strongly localized vibrational modes of functional groups in bulk material and on solid‐state surfaces is presented. The associated normal mode vectors are approximated solely on the basis of structural information and obtained via diagonalization of a reduced Hessian. The grid‐based Numerov procedure in one and two dimensions is then applied to an adequate scan of the respective potential surface yielding the associated vibrational wave functions and energy eigenvalues. This not only provides a detailed description of anharmonic effects but also an accurate inclusion of the coupling between the investigated vibrational states on a quantum mechanical level. All results obtained for the constructed normal modes are benchmarked against their analytical counterparts obtained from the diagonalization of the total Hessian of the entire system. Three increasingly complex systems treated at quantum chemical level of theory have been considered, namely the symmetric and asymmetric stretch vibrations of an isolated water molecule, hydroxyl groups bound to the surface of GeO2 (001), α‐quartz(001) and Rutil (001) as well as crystalline Li2NH serving as an example for a bulk material. While the data obtained for the individual systems verify the applicability of the proposed methodology, comparison to experimental data demonstrates the accuracy of this methodology despite the restriction to limit this methodology to a few selected vibrational modes. The possibility to investigate vibrational phenomena of localized normal modes without the requirement of executing costly harmonic frequency calculations of the entire system enables the application of this method to cases in which the determination of normal modes is prohibitively expensive or not available for a particular level of theory. © 2018 Wiley Periodicals, Inc.

Diffusion Monte Carlo (DMC) simulations have been used to obtain quantum zero-point energies of methanol and all its isotopologs and isotopomers, using a new, accurate semi-global potential energy surface. This potential energy surface is a precise, permutationally invariant fit to 6676 ab initio energies, obtained at the CCSD(T)-F12b/aug-cc-pVDZ level of theory. Quantum zero-point energies of deuterated methanol isotopomers are very close to each other and so a simple statistical argument can be used to estimate the populations of each isotopomer at very low-temperatures. The DMC simulations also indicate that there is virtually zero probability for H/D exchange in the zero-point state. © 2019 Wiley Periodicals, Inc.

This work concerns the typical conformational behaviors for di-substituted cyclohexanes that inherently depend on spatial orientations of side chains in flexible cyclic ring. The 1,3-dimethylcyclohexane and 1,4-dimethylcyclohexane in both cis- and trans-configurations were focused here to unravel their conformational inversion-topomerization mechanisms. Full geometry optimizations were performed at B3LYP/6-311++G(d,p) level of theory to explicitly identify all distinguishable molecular structures, and thus explore potential energy surfaces (PES) of the complete interconversion routes for two stereoisomers of 1,3-dimethylcyclohexane and 1,4-dimethylcyclohexane. Additional quantum calculations were carried out by separately applying MP2/6-311++G(d,p), G4, and CCSD(T)/6-311++G(d,p) methods to further refine all PES’ stationary points. With respect to quantum results, the conformational analysis was conducted to gain insight into the determination, thermodynamic stabilities, and relative energies of distinct molecular geometric structures. On base of highly biased conformational equilibria, the temperature-dependent populations of stable local minima for four studied dimethylcyclohexanes were obtained by utilizing Boltzmann distribution within 300-2500 K. Moreover, two unique interconversion processes for them, including inversion and topomerization, were fully investigated, and their potential energy surfaces were illustrated with the rigorous descriptions in two or three-dimensional schemes for clarify.

Fundamental information on the behavior of excited chlorophyll molecules packed within the confinements of nanosized photosystems I and II, following absorption of light, is presented. Using a 100 femtosecond laser with nanojoule (nJ) pulse energy and a one picosecond streak camera, we observed the light emitted from the nanostructured photosystems without oscillations or hops. The fluorescent exponential decay profiles and high efficiency within the nanostructure suggest that light coherently drains out as a unit. This implies that "quantumness" is linked to quantum confinement on the nano scale.

We first establish two new identities, based on the kernel functions with either two section or three sections, involving quantum integrals by using new definition of quantum derivative. Then, some new inequalities related to Simpson's 1/3 formula for convex mappings are provided. In addition, Newton type inequalities, for functions whose quantum derivatives in modulus or their powers are convex, are deduced. We also mention that the results in this work generalize inequalities given in earlier study. WOS:000549775300001 2-s2.0-85088105141

Integrating nanophotonics and cold atoms has drawn increasing interest in recent years due to diverse applications in quantum information science and the exploration of quantum many‐body physics. For example, dispersion‐engineered photonic crystal waveguides (PCWs) permit not only stable trapping and probing of ultracold neutral atoms via interactions with guided‐mode light, but also the possibility to explore the physics of strong, photon‐mediated interactions between atoms, as well as atom‐mediated interactions between photons. While diverse theoretical opportunities involving atoms and photons in 1D and 2D nanophotonic lattices have been analyzed, a grand challenge remains the experimental integration of PCWs with ultracold atoms. Here, an advanced apparatus that overcomes several significant barriers to current experimental progress is described, with the goal of achieving strong quantum interactions of light and matter by way of single‐atom tweezer arrays strongly coupled to photons in 1D and 2D PCWs. Principal technical advances relate to efficient free‐space coupling of light to and from guided modes of PCWs, silicate bonding of silicon chips within small glass vacuum cells, and deterministic, mechanical delivery of single‐atom tweezer arrays to the near fields of photonic crystal waveguides.

Author(s): Hernandez, Taylor M; Van Beeumen, Roel; Caprio, Mark A; Yang, Chao | Abstract: We present a greedy algorithm for computing selected eigenpairs of a large sparse matrix $H$ that can exploit localization features of the eigenvector. When the eigenvector to be computed is localized, meaning only a small number of its components have large magnitudes, the proposed algorithm identifies the location of these components in a greedy manner, and obtains approximations to the desired eigenpairs of $H$ by computing eigenpairs of a submatrix extracted from the corresponding rows and columns of $H$. Even when the eigenvector is not completely localized, the approximate eigenvectors obtained by the greedy algorithm can be used as good starting guesses to accelerate the convergence of an iterative eigensolver applied to $H$. We discuss a few possibilities for selecting important rows and columns of $H$ and techniques for constructing good initial guesses for an iterative eigensolver using the approximate eigenvectors returned from the greedy algorithm. We demonstrate the effectiveness of this approach with examples from nuclear quantum many-body calculations and many-body localization studies of quantum spin chains.

Disorder‐induced Griffiths singularity of quantum phase transition (QPT) is a crucial issue in 2D superconductors (2DSC). In a superconducting system, the strength of disorder is found to be associated with the vortex pinning energy, which is closely related to the quantum Griffiths singularity; however, a direct study to elucidate the role of vortex pinning energy on the quantum Griffiths singularity in 2DSC remains to be undertaken. Here, an artificial 2DSC system is designed by randomly depositing superconducting nanoislands on 2Delectron gas (2DEG). Quantum Griffiths singularity is present in a graphene/Pb‐islands‐array hybrid, where the superconducting behavior transits to weakly localized metallic behavior induced by the vertical magnetic field and exhibits critical behavior with a diverging dynamical critical exponent approaching zero temperature. Compared to the study of graphene/Sn‐islands‐array hybrid where the sharp QPT is observed, the vortex pinning energy acquired from the Arrhenius plot analysis is greater in graphene/Pb‐islands‐array hybrid, which may contribute to the presence of the quantum Griffiths singularity. This work may provide a comprehensive interpretation of the QPT in 2DSC., The disorder‐induced Griffiths type quantum phase transition is observed in 2D graphene/Pb‐islands‐array hybrid at ultralow temperature. Compared to the similar graphene/Sn‐islands‐array hybrid with sharp quantum phase transition, the larger vortex pinning energy of graphene/Pb‐islands‐array hybrid is believed to be responsible for the observed quantum Griffiths singularity.

2030-12-30 The structural, electronic, and vibrational properties of two leading representatives of the Zn-based spinel oxides class, normal ZnX2O4 (X = Al, Ga, In) and inverse Zn2MO4 (M = Si, Ge, Sn) crystals, were investigated. In particular, density functional theory (DFT) was combined with different exchange-correlation functionals: B3LYP, HSE06, PBE0, and PBESol. Our calculations showed good agreement with the avail- able experimental data, showing a mean percentage error close to 3% for structural parameters. For the electronic structure, the obtained HSE06 band-gap values overcome previous theoretical results, exhibiting a mean percentage error smaller than 10.0%. In particular, the vibrational properties identify the significant differences between normal and inverse spinel configurations, offering compelling evidence of a structure-property relationship for the investigated materials. Therefore, the combined results confirm that the range-separated HSE06 hybrid functional performs the best in spinel oxides. Despite some points that cannot be directly compared to experimental results, we expect that future experimental work can confirm our predictions, thus opening a new avenue for understanding the structural, electronic, and vibrational properties in spinel oxides

openaire: EC/H2020/862644/EU//QUARTET Simulation of materials by using quantum processors is envisioned to be a major direction of development in quantum information science. Here, the mathematical analogies between a triangular spin lattice with Dzyaloshinskii-Moriya coupling on one edge and a three-level system driven by three fields in a loop configuration are exploited to emulate spin-transport effects. It is shown that the spin transport efficiency, seen in the three-level system as population transfer, is enhanced when the conditions for superadiabaticity are satisfied. It is demonstrated experimentally that phenomena characteristic to spin lattices due to gauge invariance, non-reciprocity, and broken time-reversal symmetry can be reproduced in the three-level system.