Accurate predictions of the electronic excited states of BODIPY based dye sensitizers using spin-component-scaled double-hybrid functionals: a TD-DFT benchmark study

The excitation energies of 13 BODIPY dye sensitizers are benchmarked by means of TD-DFT, using 36 functionals. Spin-component-scaled double-hybrid (DSD) functionals are found to show the best performance.

Method to evaluate systematic uncertainties due to magnet misalignments in Electric Dipole Moment measurements using a storage ring

Various scenarios of measurements of Electric Dipole Moment (EDM) of light hadrons with the use of a storage ring were proposed. Most of these methods are based on the measurement of the vertical spin component for an initially horizontal polarized beam. Since the expected EDM effect is very small, one has to payattention to various sources of systematic uncertainties. One of the most important sources are misalignments of the magnets forming the storage ring lattice, which may produce an effect that mimics an EDM. This false signal could be much larger than the expected EDM signal, even for very small magnet misalignments. This paper describes a novel method for the determination of the contribution of magnets misalignments to the expected EDM signal. It is shown that the magnitude of this effect could be estimated via a Fourier analysis of the time-dependent vertical polarization. This could be achieved by sampling the vertical polarization with a frequency larger than the beam revolution frequency, which corresponds to polarization measurements in at least two positions in the storage ring. The presented method can be applied to any scenario proposed for EDM measurements using a storage ring.

Design of Metasurface with Nanoslits on Elliptical Curves for Generation of Dual-Channel Vector Beams

The manipulations of nanoscale multi-channel vector beams (VBs) by metasurfaces hold potential applications in various important fields. In this paper, the metasurface with two sets of nanoslits arranged on elliptic curves was proposed to generate the dual-channel focused vector beams (FVBs). Each set of nanoslits was composed of the in-phase and the out-of-phase groups of nanoslits to introduce the constructive interference and destructive interference of the output light field of the nanoslits, focusing the converted spin component and eliminating the incident spin component at the focal point. The two sets of nanoslits for the channels at the two focal points were interleaved on the same ellipses, and by setting their parameters independently, the FVBs in the two channels are generated under illumination of linearly polarized light, while their orders and polarization states of FVBs were controlled independently. The generation of the FVBs with the designed metasurfaces was demonstrated by the finite-difference time domain (FDTD) simulations and by the experimental verifications. The work in this paper is of great significance for the generation of miniaturized multi-channel VBs and for broadening the applications of metasurfaces.

Spin-component-scaled and dispersion-corrected second-order Møller-Plesset perturbation theory: A path toward chemical accuracy

Second-order Møller-Plesset perturbation theory (MP2) provides a valuable alternative to density functional theory for modeing problems in organic and biological chemistry. However, MP2 suffers from known lim- itations in the description of van der Waals dispersion interactions and reaction thermochemistry. Here, a spin-component-scaled, dispersion-corrected MP2 model (SCS-MP2D) is proposed that addresses these weaknesses. The dispersion correction, which is based on Grimme’s D3 formalism, replaces the uncoupled Hartree-Fock dispersion inherent in MP2 with a more robust coupled Kohn-Sham treatment. The spin- component scaling of the residual MP2 correlation energy then reduces the remaining errors in the model. This two-part correction strategy solves the problem found in earlier spin-component-scaled MP2 models where completely different spin-scaling parameters were needed for describing reaction energies versus in- termolecular interactions. Results on 18 benchmark data sets and two challenging potential energy curves demonstrate that SCS-MP2D considerably improves upon the accuracy of MP2 for intermolecular interac- tions, conformational energies, and reaction energies. Its accuracy and computational cost are competitive with state-of-the-art density functionals such as DSD-BLYP-D3(BJ), revDSD-PBEP86-D3(BJ), ωB97X-V, and ωB97M-V for systems with ∼100 atoms.

Metal–insulator transitions of fermionic mixtures with mass imbalance in disordered optical lattice

We study the metal–insulator transitions in the half-filled Anderson–Hubbard model with mass imbalance by the typical medium theory using the equation of motion method as an impurity solver. The nonmagnetic ground state phase diagram of the system with mass imbalance is constructed numerically. In addition to the three phases showed up in the balanced case, the phase diagram of the mass imbalanced case contains a spin-selective localized phase, where one spin component is metallic while the other spin component is insulating. We find that if one increases the mass imbalance the metal region in the phase diagram is reduced, while both Anderson and Mott insulator regions are enlarged.

Time-Dependent Long-Range-Corrected Double-Hybrid Density Functionals with Spin-Component and Spin-Opposite Scaling: A Comprehensive Analysis of Singlet-Singlet and Singlet-Triplet Excitation Energies

<div> <div> <div> <p>Following the work on spin-component and spin-opposite scaled (SCS/SOS) global double hybrids for singlet-singlet excitations by Schwabe and Goerigk [J. Chem. Theory Comput. 2017, 13, 4307-4323] and our own works on new long-range corrected (LC) double hybrids for singlet-singlet and singlet-triplet excitations [J. Chem. Theory Comput. 2019, 15, 4735- 4744; J. Chem. Phys. 2020, 153, 064106], we present new LC double hybrids with SCS/SOS that demonstrate further improvement over previously published results and methods. We introduce new unscaled and scaled versions of different global and LC double hybrids based on Becke88 or PBE exchange combined with LYP, PBE or P86 correlation. For singlet-singlet excitations, we cross-validate them on six benchmark sets that cover small to medium-sized chromophores with different excitation types (local valence, Rydberg, and charge transfer). For singlet-triplet excitations, we perform the cross-validation on three different benchmark sets following the same analysis as in our previous work in 2020. In total, 203 unique excitations are analyzed. Our results confirm and extend those of Schwabe and Goerigk regarding the superior performance of SCS and SOS variants compared to their unscaled parents by decreasing mean absolute deviations, root-mean-square deviations or error spans by more than half and bringing absolute mean deviations closer to zero. Our SCS/SOS variants show to be highly efficient and robust for the computation of vertical excitation energies, which even outperform specialized double hybrids that also contain an LC in their perturbative part. In particular, our new SCS/SOS-ωPBEPP86 and SCS/SOS-ωB88PP86 functional are four of the most accurate and robust methods tested in this work and we fully recommend them for future applications. However, if the relevant SCS and SOS algorithms are not available to the user, we suggest ωB88PP86 as the best unscaled method in this work. </p> </div> </div> </div>

Time-Dependent Long-Range-Corrected Double-Hybrid Density Functionals with Spin-Component and Spin-Opposite Scaling: A Comprehensive Analysis of Singlet-Singlet and Singlet-Triplet Excitation Energies

<div> <div> <div> <p>Following the work on spin-component and spin-opposite scaled (SCS/SOS) global double hybrids for singlet-singlet excitations by Schwabe and Goerigk [J. Chem. Theory Comput. 2017, 13, 4307-4323] and our own works on new long-range corrected (LC) double hybrids for singlet-singlet and singlet-triplet excitations [J. Chem. Theory Comput. 2019, 15, 4735- 4744; J. Chem. Phys. 2020, 153, 064106], we present new LC double hybrids with SCS/SOS that demonstrate further improvement over previously published results and methods. We introduce new unscaled and scaled versions of different global and LC double hybrids based on Becke88 or PBE exchange combined with LYP, PBE or P86 correlation. For singlet-singlet excitations, we cross-validate them on six benchmark sets that cover small to medium-sized chromophores with different excitation types (local valence, Rydberg, and charge transfer). For singlet-triplet excitations, we perform the cross-validation on three different benchmark sets following the same analysis as in our previous work in 2020. In total, 203 unique excitations are analyzed. Our results confirm and extend those of Schwabe and Goerigk regarding the superior performance of SCS and SOS variants compared to their unscaled parents by decreasing mean absolute deviations, root-mean-square deviations or error spans by more than half and bringing absolute mean deviations closer to zero. Our SCS/SOS variants show to be highly efficient and robust for the computation of vertical excitation energies, which even outperform specialized double hybrids that also contain an LC in their perturbative part. In particular, our new SCS/SOS-ωPBEPP86 and SCS/SOS-ωB88PP86 functional are four of the most accurate and robust methods tested in this work and we fully recommend them for future applications. However, if the relevant SCS and SOS algorithms are not available to the user, we suggest ωB88PP86 as the best unscaled method in this work. </p> </div> </div> </div>

Anomalous weak values via a single photon detection

Is it possible that a measurement of a spin component of a spin-1/2 particle yields the value 100? In 1988 Aharonov, Albert and Vaidman argued that upon pre- and postselection of particular spin states, weakening the coupling of a standard measurement procedure ensures this paradoxical result1. This theoretical prediction, called weak value, was realised in numerous experiments2–9, but its meaning remains very controversial10–19, since its “anomalous” nature, i.e., the possibility to exceed the eigenvalue spectrum, as well as its “quantumness” are debated20–22. We address these questions by presenting the first experiment measuring anomalous weak values with just a single click, without the need for statistical averaging. The measurement uncertainty is significantly smaller than the gap between the measured weak value and the nearest eigenvalue. Beyond clarifying the meaning of weak values, demonstrating their non-statistical, single-particle nature, this result represents a breakthrough in understanding the foundations of quantum measurement, showing unprecedented measurement capability for further applications of weak values to quantum photonics.