We develop a new model to simulate nonradiative relaxation and dephasing by combining real-time Hartree-Fock and density functional theory (DFT) with our recent open-systems theory of electronic dynamics. The approach has some key advantages: it has been systematically derived and properly relaxes noninteracting electrons to a Fermi-Dirac distribution. This paper combines the new dissipation theory with an atomistic, all-electron quantum chemistry code and an atom-centered model of the thermal environment. The environment is represented nonempirically and is dependent on molecular structure in a nonlocal way. A production quality, O(N(3)) closed-shell implementation of our theory applicable to realistic molecular systems is presented, including timing information. This scaling implies that the added cost of our nonadiabatic relaxation model, time-dependent open self-consistent field at second order (OSCF2), is computationally inexpensive, relative to adiabatic propagation of real-time time-dependent Hartree-Fock (TDHF) or time-dependent density functional theory (TDDFT). Details of the implementation and numerical algorithm, including factorization and efficiency, are discussed. We demonstrate that OSCF2 approaches the stationary self-consistent field (SCF) ground state when the gap is large relative to k(b)T. The code is used to calculate linear-response spectra including the effects of bath dynamics. Finally, we show how our theory of finite-temperature relaxation can be used to correct ground-state DFT calculations.

We introduce an atomistic, all-electron, black-box electronic structure code to simulate transient absorption (TA) spectra and apply it to simulate pyrazole and a GFP-chromophore derivative. The method is an application of OSCF2, our dissipative extension of time-dependent density functional theory. We compare our simulated spectra directly with recent ultrafast spectroscopic experiments. We identify features in the TA spectra to Pauli-blocking, which may be missed without a first-principles model. An important ingredient in this method is the stationary-TDDFT correction scheme recently put forward by Fischer, Govind, and Cramer that allows us to overcome a limitation of adiabatic TDDFT. We demonstrate that OSCF2 is able to reproduce the energies of bleaches and induced absorptions as well as the decay of the transient spectrum with only the molecular structure as input.

It is important that any dynamics method approaches the correct population distribution at long times. In this paper, we derive a one-body reduced density matrix dynamics for electrons in energetic contact with a bath.We obtain a remarkable equation of motion which shows that in order to reach equilibrium properly, rates of electron transitions depend on the density matrix. Even though the bath drives the electrons towards a Boltzmann distribution, hole blocking factors in our equation of motion cause the electronic populations to relax to a Fermi-Dirac distribution. These factors are an old concept, but we show how they can be derived with a combination of time-dependent perturbation theory and the extended normal ordering of Mukherjee and Kutzelnigg. The resulting non-equilibrium kinetic equations generalize the usual Redfield theory to many-electron systems, while ensuring that the orbital occupations remain between zero and one. In numerical applications of our equations, we show that relaxation rates of molecules are not constant because of the blocking effect. Other applications to model atomic chains are also presented which highlight the importance of treating both dephasing and relaxation. Finally we show how the bath localizes the electron density matrix. 1 arXiv:1411.5324v2 [quant-ph]

We apply our recently developed nonequilibrium real-time time-dependent density functional theory (OSCF2) to investigate the transient spectrum and relaxation dynamics of the tetragonal structure of methylammonium lead triiodide perovskite (MAPbI3). We obtain an estimate of the interband relaxation kinetics and identify multiple ultrafast cooling channels for hot electrons and hot holes that largely corroborate the dual valence-dual conduction model. The computed relaxation rates and absorption spectra are in good agreement with the existing experimental data. We present the first ab initio simulations of the perovskite transient absorption (TA) spectrum, substantiating the assignment of induced bleaches and absorptions including a Pauli-bleach signal. This paper validates both OSCF2 as a good qualitative model of electronic dynamics, and the dominant interpretation of the TA spectrum of this material.

To explore multi-core programming, we re-implement the Lock Free Contention Adapting Search Tree. We follow the structure of the original, using immutable treaps as leaf nodes implemented with an array for better performance with memory caching. The initial re-implementation uses coarse-grained locking with MRLock to provide thread-safety. This will be extended to be lock-free in a future publication.