Gope, K. ; Livshits, E. ; Bittner, D. M. ; Baer, R. ; Strasser, D. An “inverse” harpoon mechanism
. Science Advances 2022
eabq8084. Publisher's VersionAbstract
Electron-transfer reactions are ubiquitous in chemistry and biology. The electrons quantum nature allows its transfer across long distances. In the well-known harpoon mechanism, electron-transfer results in Coulombic attraction between initially neutral reactants that leads to dramatic increase in the reaction rate. Here we present a different mechanism, in which electron-transfer from a neutral reactant to a multiply charged cation results in strong repulsion that encodes the electron-transfer distance in the kinetic energy release. 3D coincidence-imaging allows to identify such “inverse” harpoon products, predicted by non adiabatic molecular dynamics simulations to occur between H2 and HCOH2+ following double-ionization of isolated methanol molecules. Detailed comparison of measured and simulated data indicates that while the relative probability of long-range electron-transfer events is correctly predicted, theory overestimates the electron-transfer distance.
Fabian, M. D. ; Shpiro, B. ; Baer, R. Linear Weak Scalability of Density Functional Theory Calculations without Imposing Electron Localization
. J. Chem. Theory Comput. 2022
, acs.jctc.1c00829. Publisher's VersionAbstract
Linear scaling density functional theory (DFT) approaches to the electronic structure of materials are often based on the tendency of electrons to localize in large atomic and molecular systems. However, in many cases of actual interest, such as semiconductor nanocrystals, system sizes can reach a substantial extension before signiﬁcant electron localization sets in, causing a considerable deviation from linear scaling. Herein, we address this class of systems by developing a massively parallel DFT approach which does not rely on electron localization and is formally quadratic scaling yet enables highly eﬃcient linear wall-time complexity in the weak scalability regime. The method extends from the stochastic DFT approach described in Fabian et al. (WIRES: Comp. Mol. Sci. 2019, e1412) but is entirely deterministic. It uses standard quantum chemical atomcentered Gaussian basis sets to represent the electronic wave functions combined with Cartesian real-space grids for some operators and enables a fast solver for the Poisson equation. Our main conclusion is that when a processor-abundant high-performance computing (HPC) infrastructure is available, this type of approach has the potential to allow the study of large systems in regimes where quantum conﬁnement or electron delocalization prevents linear scaling.
Baer, R. ; Neuhauser, D. ; Rabani, E. Stochastic Vector Techniques in Ground-State Electronic Structure
. Annu. Rev. Phys. Chem. 2022
, annurev–physchem–090519–045916. Publisher's VersionAbstract
We review a suite of stochastic vector computational approaches for studying the electronic structure of extended condensed matter systems. These techniques help reduce algorithmic complexity, facilitate efficient parallelization, simplify computational tasks, accelerate calculations, and diminish memory requirements. While their scope is vast, we limit our study to ground-state and finite temperature density functional theory (DFT) and second-order perturbation theory. More advanced topics, such as quasiparticle (charge) and optical (neutral) excitations and higher-order processes, are covered elsewhere. We start by explaining how to use stochastic vectors in computations, characterizing the associated statistical errors. Next, we show how to estimate the electron density in DFT and discuss highly effective techniques to reduce statistical errors. Finally, we review the use of stochastic vector techniques for calculating correlation energies within the secondorder Møller-Plesset perturbation theory and its finite temperature variational form. Example calculation results are presented and used to demonstrate the efficacy of the methods.
Shpiro, B. ; Fabian, M. D. ; Rabani, E. ; Baer, R. Forces from Stochastic Density Functional Theory under Nonorthogonal Atom-Centered Basis Sets
. J. Chem. Theory Comput. 2022
, 1458–1466. Publisher's VersionAbstract
We develop a formalism for calculating forces on the nuclei within the linear-scaling stochastic density functional theory (sDFT) in a nonorthogonal atomcentered basis set representation (Fabian et al. Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2019, 9, e1412, 10.1002/wcms.1412) and apply it to the Tryptophan Zipper 2 (Trpzip2) peptide solvated in water. We use an embedded-fragment approach to reduce the statistical errors (ﬂuctuation and systematic bias), where the entire peptide is the main fragment and the remaining 425 water molecules are grouped into small fragments. We analyze the magnitude of the statistical errors in the forces and ﬁnd that the systematic bias is of the order of 0.065 eV/Å (∼1.2 × 10−3Eh/a0) when 120 stochastic orbitals are used, independently of system size. This magnitude of bias is suﬃciently small to ensure that the bond lengths estimated by stochastic DFT (within a Langevin molecular dynamics simulation) will deviate by less than 1% from those predicted by a deterministic calculation.
Nazarov, V. U. ; Baer, R. High frequency limit of spectroscopy
. Journal of Chemical Physics 2022
We consider an arbitrary quantum mechanical system, initially in its ground-state, exposed to a time-dependent electromagnetic pulse with a carrier frequency ω0 and a slowly varying envelope of finite duration. By working out a solution to the time-dependent Schrödinger equation in the high-ω0 limit, we find that, to the leading order in ω−10, a perfect self-cancellation of the system’s linear response occurs as the pulse switches off. Surprisingly, the system’s observables are, nonetheless, describable in terms of a combination of its linear density response function and nonlinear functions of the electric field. An analysis of a jellium slab and jellium sphere models reveals a very high surface sensitivity of the considered setup, producing a richer excitation spectrum than accessible within the conventional linear response regime. On this basis, we propose a new spectroscopic technique, which we provisionally name the Nonlinear High-Frequency Pulsed Spectroscopy (NLHFPS). Combining the advantages of the extraordinary surface sensitivity, the absence of constraints by the traditional dipole selection rules, and the clarity of theoretical interpretation utilizing the linear response time-dependent density functional theory, NLHFPS has a potential to evolve into a powerful characterization method for nanoscience and nanotechnology