We report efficient nonradiative energy transfer (NRET) from core-shell, semiconducting quantum dots to adjacent two-dimensional sheets of graphene and MoS2 single- few-layer thickness. observe quenching the photoluminescence (PL) individual enhanced PL decay rates in time-resolved PL, corresponding 1-10 ns(-1). Our measurements reveal contrasting trends NRET rate dot van der Waals material as a function The increases significantly with increasing layer thickness graphene, but decreases...

Simulating optical spectra in the condensed phase remains a challenge for theory due to need capture spectral signatures arising from anharmonicity and dynamical effects, such as vibronic progressions asymmetry. As such, numerous simulation methods have been developed that invoke different approximations vary their ability physical regimes. Here, we use several models of chromophores ab initio molecular dynamics simulations rigorously assess applicability simulate absorption spectra....

Generalized quantum master equations (GQMEs) are an important tool in modeling chemical and physical processes. For a large number of problems it has been shown that exact approximate dynamics methods can be made dramatically more efficient, the latter case accurate, by proceeding via GQME formalism. However, there many situations where utilizing approach seems to offer no advantage over direct evaluation property interest. Here we provide detailed understanding conditions under which these...

We present a formalism that explicitly unifies the commonly used Nakajima-Zwanzig approach for reduced density matrix dynamics with more versatile Mori theory in context of nonequilibrium dynamics. Employing Dyson-type expansion to circumvent difficulty projected dynamics, we obtain self-consistent equation memory kernel which requires only knowledge normally evolved auxiliary kernels. To illustrate properties current approach, focus on spin-boson model and limit our attention use simple...

Biomolecular dynamics play an important role in numerous biological processes. Markov State Models (MSMs) provide a powerful approach to study these dynamic processes by predicting long time scale based on many short molecular (MD) simulations. In MSM, protein are modeled as kinetic process consisting of series Markovian transitions between different conformational states at discrete intervals (called “lag time”). To achieve this, master equation must be constructed with sufficiently lag...

The ability to predict and understand complex molecular motions occurring over diverse timescales ranging from picoseconds seconds even hours in biological systems remains one of the largest challenges chemical theory. Markov state models (MSMs), which provide a memoryless description transitions between different states biochemical system, have provided numerous important physically transparent insights into function. However, constructing these often necessitates performing extremely long...

Hydrogen bonding interactions with chromophores in chemical and biological environments play a key role determining their electronic absorption relaxation processes, which are manifested linear multidimensional optical spectra. For the condensed phase, large number of atoms needed to simulate environment has traditionally prohibited use high-level excited-state structure methods. By leveraging transfer learning, we show how construct machine-learned models accurately predict excitation...

Modern 4-wave mixing spectroscopies are expensive to obtain experimentally and computationally. In certain cases, the unfavorable scaling of quantum dynamics problems can be improved using a generalized master equation (GQME) approach. However, inclusion multiple (light–matter) interactions complicates motion leads seemingly unavoidable cubic in time. this paper, we present formulation that greatly simplifies reduces computational cost previous work extended GQME framework treat arbitrary...

We present a new, computationally inexpensive method for the calculation of reduced density matrix dynamics systems with potentially large number subsystem degrees freedom coupled to generic bath. The approach consists propagation weak-coupling Redfield-like equations high-frequency bath only, while low-frequency modes are dynamically arrested but statistically sampled. examine improvements afforded by this approximation comparing exact results spin-boson model over wide range parameter...

Methods derived from the generalized quantum master equation (GQME) framework have provided basis for elucidating energy and charge transfer in systems ranging molecular solids to photosynthetic complexes. Recently, nonperturbative combination of GQME with quantum-classical methods has resulted approaches whose accuracy efficiency exceed those original schemes while offering significant improvements over perturbative expansions GQME. Here, we show that, non-Markovian memory kernel required...

Hot carrier-based energy conversion systems could double the efficiency of conventional solar technology or drive photochemical reactions that would not be possible using fully thermalized, ``cool'' carriers, but current strategies require expensive multi-junction architectures. Using an unprecedented combination photoelectrochemical and in situ transient absorption spectroscopy measurements, we demonstrate ultrafast (<50 fs) hot exciton free carrier extraction under applied bias a...

Elucidating transport mechanisms is crucial for advancing material design, yet state-of-the-art theory restricted to exact simulations of small lattices with severe finite-size effects or approximate ones that assume the nature transport. We leverage algorithmic advances tame and exactly simulate polaron formation in Holstein model. further analyze applicability ubiquitously used equilibrium-based Green-Kubo relations nonequilibrium methods predict charge mobility. find these can converge...

Superconductivity in doped SrTiO$_3$ was discovered 1964, the first superconducting transition observed a semiconductor. However, mechanism behind electron pairing remains subject of debate. By developing theoretical framework to incorporate dynamical lattice screening electronic Coulomb interactions semiconductors and insulators, we demonstrate analytically that long-range electron-phonon described by generalized multi-phonon Fr\"ohlich result phonon-mediated electron-electron attraction...

Ab initio downfolding describes the electronic structure of materials within a low-energy subspace, often around Fermi level. Typically starting from mean-field calculations, this framework allows for calculation one- and two-electron interactions, parametrization many-body Hamiltonian representing active space interest. The subsequent solution such Hamiltonians can provide insights into physics strongly-correlated materials. While phonons substantially screen electron-electron...

The exact quantum dynamics of lattice models can be computationally intensive, especially when aiming for large system sizes and extended simulation times necessary to converge transport coefficients. By leveraging finite memory access long-time using only short-time data, generalized master equations offer a route simulating the problems efficiently. However, such simulations are limited small lattices whose exhibit finite-size artifacts that contaminate coefficient predictions. To address...

Generalized master equations provide a theoretically rigorous framework to capture the dynamics of processes ranging from energy harvesting in plants and photovoltaic devices qubit decoherence quantum technologies even protein folding. At their center is concept memory. The explicit time-nonlocal description memory both protracted elaborate. When physical intuition at premium, one would desire more compact, yet complete, description. Here, we demonstrate how when time-convolutionless...

While dark transitions made bright by molecular motions determine the optoelectronic properties of many materials, simulating such non-Condon effects in condensed phase spectroscopy remains a fundamental challenge. We derive Gaussian theory to predict and analyze optical spectra beyond Condon limit. Our introduces novel quantities that encode how nuclear modulate energy gap transition dipole electronic form spectral densities. By formulating through statistical framework thermal averages...

Abstract Spectral characterization of noise environments that lead to the decoherence qubits is critical developing robust quantum technologies. While dynamical decoupling offers one most successful approaches characterize spectra, it necessitates applying large sequences π pulses increase complexity and cost method. Here, we introduce a spectroscopy method utilizes only Fourier transform free induction decay or spin echo measurements, thus removing need for application many pulses. We show...

The ability to efficiently and accurately calculate equilibrium time correlation functions of many-body condensed phase quantum systems is one the outstanding problems in theoretical chemistry. Nakajima-Zwanzig-Mori formalism coupled self-consistent solution memory kernel has recently proven be highly successful for computation nonequilibrium dynamical averages. Here, we extend this treat symmetrized spin-boson model. Following first paper series [A. Montoya-Castillo D. R. Reichman, J. Chem....

Monolayer transition metal dichalcogenides (TMDs) have the potential to unlock novel photonic and chemical technologies if their optoelectronic properties can be understood controlled. Yet, recent work has offered contradictory explanations for how TMD absorption spectra change with carrier concentration, fluence, time. Here, we test our hypothesis that large broadening shifting of strong band-edge features observed in optical arise from formation negative trions. We do this by fitting an ab...

Diabatic states and the couplings between them are important for quantifying, elucidating, predicting rates mechanisms of many chemical biochemical processes. Here, we propose investigate approaches to accurately compute diabatic from density functional theory (DFT) using absolutely localized molecular orbitals (ALMOs). ALMOs provide an appealing approach generate variationally optimized obtain their associated forces, which allows relaxation donor acceptor in a way that is internally...

This work presents a computational study of charge hopping dynamics along one-dimensional chain with Gaussian site energy disorder and linearly coupled quantum bath. Time-dependent square displacements are calculated directly from numerical solutions Pauli master equations, for five different rate kernels: exact Fermi golden rule (FGR) expression, stationary phase interpolation (SPI) approximation, semiclassical (SC) classical Marcus Miller-Abrahams expression. All results demonstrate...