Block2: A comprehensive open source framework to develop and apply state-of-the-art DMRG algorithms in electronic structure and beyond.

block2 is an open source framework to implement and perform density matrix renormalization group and matrix product state algorithms. Out-of-the-box it supports the eigenstate, time-dependent, response, and finite-temperature algorithms. In addition, it carries special optimizations for ab initio electronic structure Hamiltonians and implements many quantum chemistry extensions to the density matrix renormalization group, such as dynamical correlation theories. The code is designed with an emphasis on flexibility, extensibility, and efficiency and to support integration with external numerical packages. Here, we explain the design principles and currently supported features and present numerical examples in a range of applications.

Manipulating Lone-Pair-Driven Luminescence in 0D Tin Halides by Pressure-Tuned Stereochemical Activity from Static to Dynamic.

The excellent luminescence properties and structural dynamics driven by the stereoactivity of the lone pair in a variety of low-dimensional ns2 metal halides have attracted growing investigations for optoelectronic applications. However, the structural and photophysical aspects of the excited state associated with the lone pair expression are currently open questions. Herein, zero-dimensional Sn-based halides with static stereoactive 5 s2 lone pairs are selected as a model system to understand the correlations between the distinctive lone pair expression and the excited-state structural relaxation and charge carrier dynamics by continuous lattice manipulation. Lattice compression drives 5 s2 lone pair active switching and self-trapped exciton (STE) redistribution by suppressing excited-state structural deformation of the isolated SnBr4 2- units. Our results demonstrate that the static expression of the 5 s2 lone pair results in a red broadband triplet STE emission with a large Stokes shift, while its dynamic expression creates a sky-blue narrowband emission dominated by the radiative recombination of singlet STEs. Our findings and the photophysical mechanism proposed highlight the stereochemical effects of lone pair expression in controlling light emission properties and offer constructive guidelines for tuning the optoelectronic properties in diverse ns2 metal halides.

Revealing the Mechanism of Pressure-Induced Emission in Layered Silver-Bismuth Double Perovskites.

Pressure-induced emission (PIE) associated with self-trapping excitons (STEs) in low-dimensional halide perovskites has attracted great attention for better materials-by-design. Here, using 2D layered double perovskite (C6 H5 CH2 CH2 NH3 + )4 AgBiBr8 as a model system, we advance a fundamental physicochemical mechanism of the PIE from the perspective of carrier dynamics and excited-state behaviors of local lattice distortion. We observed a pressure-driven STE transformation from dark to bright states, corresponding a strong broadband Stokes-shifted emission. Further theoretical analysis demonstrated that the suppressed lattice distortion and enhanced electronic dimensionality in the excited-state play an important role in the formation of stabilized bright STEs, which could manipulate the self-trapping energy and lattice deformation energy to form an energy barrier between the potential energy curves of ground- and excited-state, and enhance the electron-hole orbital overlap, respectively.

Pros and cons of the time-dependent hybrid density functional approach for calculating the optical spectra of solids: a case study of CeO2.

The prediction of optical spectra of complex solids remains a great challenge for first-principles calculations due to the huge computational cost of the state-of-the-art many-body perturbation theory based GW-Bethe Salpeter equation (BSE) approach. An alternative method is the time-dependent density-functional theory (TDDFT) based on hybrid exchange-correlation functionals, which involves the essential ingredients of electron-hole interactions in its formalism in contrast to its local/semi-local functional counterparts. In this work, we investigate the optical absorption spectra of ceria (CeO2), a prototypical lanthanide oxide with a 4f0 configuration, utilizing TDDFT based on four well-established hybrid functionals for ground state DFT calculations. All four functionals reproduce well the excitonic features of the experimental optical spectra, in spite of the significant differences in their band structures arising from different hybridization parameters (i.e. the fraction of the Hartree-Fock exchange and the screening parameter). It is demonstrated that the apparently weak dependence of the resulting optical spectra on the employed functionals is quite universal and applies to simple semiconductors such as Si and GaAs and insulator LiF as well. This study highlights the feasibility of TDDFT based on existing hybrids to describe optical spectra of solids, and also, points out the difficulty of obtaining accurate exciton binding energies using these hybrid functionals due to the strong functional dependence of quasi-particle band structures.