Sparse-Stochastic Fragmented Exchange for Large-Scale Hybrid Time-Dependent Density Functional Theory Calculations.

We extend our recently developed sparse-stochastic fragmented exchange formalism for ground-state near-gap hybrid DFT to calculate absorption spectra within linear-response time-dependent generalized Kohn-Sham DFT (LR-GKS-TDDFT) for systems consisting of thousands of valence electrons within a grid-based/plane-wave representation. A mixed deterministic/fragmented-stochastic compression of the exchange kernel, here using long-range explicit exchange functionals, provides an efficient method for accurate optical spectra. Both real-time propagation as well as frequency-resolved Casida-equation-type approaches for spectra are presented, and the method is applied to large molecular dyes.

Optimized attenuated interaction: Enabling stochastic Bethe-Salpeter spectra for large systems.

We develop an improved stochastic formalism for the Bethe-Salpeter equation (BSE), based on an exact separation of the effective-interaction W into two parts, W = (W - vW) + vW, where the latter is formally any translationally invariant interaction, vW(r - r'). When optimizing the fit of the exchange kernel vW to W, using a stochastic sampling W, the difference W - vW becomes quite small. Then, in the main BSE routine, this small difference is stochastically sampled.

Tempering stochastic density functional theory.

We introduce a tempering approach with stochastic density functional theory (sDFT), labeled t-sDFT, which reduces the statistical errors in the estimates of observable expectation values. This is achieved by rewriting the electronic density as a sum of a "warm" component complemented by "colder" correction(s). Since the warm component is larger in magnitude but faster to evaluate, we use many more stochastic orbitals for its evaluation than for the smaller-sized colder correction(s).

Shot-noise limited single-molecule FRET histograms: comparison between theory and experiments.

We describe a simple approach and present a straightforward numerical algorithm to compute the best fit shot-noise limited proximity ratio histogram (PRH) in single-molecule fluorescence resonant energy transfer diffusion experiments. The key ingredient is the use of the experimental burst size distribution, as obtained after burst search through the photon data streams. We show how the use of an alternated laser excitation scheme and a correspondingly optimized burst search algorithm eliminates several potential artifacts affecting the calculation of the best fit shot-noise limited PRH.