Kretchmer Group

In this work, we derive a multi-fragment real-time extension of the projected density matrix embedding theory (pDMET) designed to treat non-equilibrium electron dynamics in strongly correlated systems. As in the previously developed static pDMET, the real time pDMET partitions the total system into many fragments; the coupling between each fragment and the rest of the system is treated through a compact representation of the environment in terms of a quantum bath. The real-time pDMET involves simultaneously propagating the wavefunctions for each separate fragment–bath embedding system along with an auxiliary mean-field wavefunction of the total system. The equations of motion are derived by (i) projecting the time-dependent Schrödinger equation in the fragment and bath space associated with each separate fragment and by (ii) enforcing the pDMET matching conditions between the global 1-particle reduced density matrix (1-RDM) obtained from the fragment calculations and the mean-field 1-RDM at all points in time. The accuracy of the method is benchmarked through comparisons to time-dependent density-matrix renormalization group and time-dependent Hartree–Fock (TDHF) theory; the methods were applied to a one- and two-dimensional single-impurity Anderson model and multi-impurity Anderson models with ordered and disordered distributions of the impurities. The results demonstrate a large improvement over TDHF and rapid convergence to the exact dynamics with an increase in fragment size. Our results demonstrate that the real-time pDMET is a promising and flexible method that balances accuracy and efficiency to simulate the non-equilibrium electron dynamics in heterogeneous systems of large size.

In this work, we investigate the capability of using real-time time-dependent density functional theory (RT-TDDFT) in conjunction with a complex absorbing potential (CAP) to simulate the intermolecular Coulombic decay (ICD) processes following the ionization of an inner-valence electron. We examine the ICD dynamics in a series of noncovalent bonded dimer systems, including hydrogen-bonded and purely van der Waals (VdW)-bonded systems. In comparison to previous work, we show that RT-TDDFT simulations with a CAP correctly capture the ICD phenomenon in systems exhibiting a stronger binding energy. The calculated time scales for ICD of the studied systems are in the range of 5–50 fs, in agreement with previous studies. However, there is a breakdown in the accuracy of the methodology for the pure VdW-bonded systems. Overall, the presented RT-TDDFT/CAP methodology provides a powerful tool for differentiating between competing electronic relaxation pathways following inner-valence or core ionization without necessitating any a priori assumptions.

Ionizing radiation can trigger ultrafast proton transfer, a central mechanism in many chemical and biological functions, that in turn can enable or suppress electron relaxation processes and consequently cause abrupt changes in the reaction pathway. This study combines theory and experiment to probe ultrafast relaxation and dissociation in water dimers following inner- and outer-valence photoionization. By tracking electron and nuclear motion simultaneously, we reveal competing fragmentation pathways that produce low-energy electrons, which are key agents in radiation-induced chemistry, including DNA damage. While low-energy electrons are known to arise via intermolecular Coulombic decay, here we identify a faster relaxation mechanism gated by proton transfer following inner-valence ionization, which we call proton-transfer-mediated autoionization. Occurring within 10 femtoseconds, this process alters fragmentation outcomes, yielding either D3O+ + OD+ or D2O+ + D2O+, depending on the interplay of proton migration and hydrogen back-transfer. Our findings underscore the intricate coupling between electronic and nuclear dynamics in hydrogen-bonded systems and establish proton-transfer-mediated autoionization as a significant pathway for low-energy electron generation.

In this work, we present the TiDES (Time-Dependent Electronic Structure) code, an open-source real-time electronic structure theory package. The software is written in Python and interfaces with the Python-based Simulations of Chemistry Framework (PySCF), an open-source quantum chemistry library. The philosophy of the TiDES software package is to provide an incredibly modular real-time software package to allow for easy development and implementation of new methodology. The package allows for explicit time propagation of chemical systems within the spin-restricted, unrestricted, and generalized frameworks of both real-time time-dependent Hartree–Fock and real-time time-dependent density functional theory. Additional features include the ab initio Ehrenfest dynamics method for the simulation of coupled electronic and nuclear motion and the incorporation of a complex absorbing potential that enables the simulation of ionization events. To illustrate both the value of real-time dynamics and the intuitive nature of TiDES, we simulate spectroscopic properties and non-equilibrium electron and spin dynamics in several example systems. We also show how general external potentials can be defined and easily applied during time propagation. Lastly, the features within PySCF, such as spin–orbit coupling, interface readily with the real-time calculations, providing a powerful tool for simulating electron and spin dynamics with the capacity for extensive customization.