We develop an accurate and numerically efficient non-adiabatic path-integral approach to simulate the non-linear spectroscopy of exciton-polariton systems. This is based on partial linearized density matrix model exciton dynamics with explicit propagation phonon bath environment, combined a stochastic Lindblad cavity loss dynamics. Through simulating both linear polariton two-dimensional electronic spectra, we systematically investigate how light-matter coupling strength rate influence...

Computation of nonlinear optical response functions allows for an in-depth connection between theory and experiment. Experimentally recorded spectra provide a high density information, but to objectively disentangle overlapping signals reach detailed reliable understanding the system dynamics, measurements must be integrated with theoretical approaches. Here, we present new, highly accurate efficient trajectory-based semiclassical path integral method computing higher order non-Markovian...

The recent surge of interest in polaritons has prompted fundamental questions about the role dark states strong light-matter coupling phenomena. Here, we systematically vary relative number by controlling stacked CdSe nanoplatelets confined a Fabry-Pérot cavity. We find emission spectrum to change significantly with an increasing nanoplatelets, gradual shift dominant intensity from lower polariton branch manifold states. Through accompanying calculations based on kinetic model, this is...

The symmetrical quasi-classical approach for propagation of a many degree freedom density matrix is explored in the context computing linear spectra. Calculations on simple two state model which exact results are available suggest that gives qualitative description peak positions, relative amplitudes, and line broadening. Short time details computed dipole autocorrelation function result exaggerated tails spectrum.

The recent surge of interest in polaritons has prompted fundamental questions about the role dark states strong light-matter coupling phenomena. Here, we systematically vary relative number state by controlling stacked CdSe nanoplatelets confined a Fabry-Pérot cavity. We find emission spectrum to change significantly with an increasing nanoplatelets, gradual shift dominant intensity from lower polariton branch manifold states. Through accompanying calculations based on kinetic model, this is...

We describe a matrix product state (MPS) extension for the Fermionic Quantum Emulator (FQE) software library. discuss theory behind symmetry-adapted MPSs approximating many-body wave functions of spin-1/2 Fermions, and we present an open-source, MPS-enabled implementation FQE interface (MPS-FQE). The uses open-source pyblock3 block2 libraries most elementary tensor operations, it can largely be used as drop-in replacement that allows more efficient but approximate emulation larger circuits....

The partially linearized density matrix formalism for nonadiabatic dynamics is adapted to incorporate a classical external electromagentic field into the system Hamiltonian. This advancement encompasses possibility of describing field-driven and computing variety linear nonlinear spectroscopic signals beyond perturbative limit. capabilities developed approach are demonstrated on simple two-state vibronic model coupled bath, which we (a) perform an exhaustive search in parameter space optimal...

Abstract This work proposes a photophysical phenomenon whereby ultraviolet/visible (UV/vis) excitation of molecule involving Franck-Condon (FC) active vibration yields infrared (IR) emission by strong coupling to an optical cavity. The resulting UV/vis-to-IR photonic down conversion process is mediated vibrational polaritons in the electronic excited state potential. It shown that formation (ESVP) via UV/vis only involve modes with both non-zero FC activity and IR state. Density functional...

We derive a formulation of mixed quantum–classical dynamics for modeling electronic carriers interacting with phonons in reciprocal space. For dispersionless phonons, we start by expressing the real-space classical coordinates terms complex variables. Taking these variables as Fourier series then yields reciprocal-space coordinates. Evaluating electron–phonon interaction term through Ehrenfest’s theorem, arrive at formalism that is equivalent to mean-field real This equivalence numerically...

Ensembles of ab initio parameterized Frenkel-exciton model Hamiltonians for different perylene diimide dimer systems are used, together with various dissipative quantum dynamics approaches, to study the influence solvation environment and fluctuations in chromophore relative orientation packing on vibronic spectra two systems: a π-stacked aqueous solution which geometry is strongly confined by phosphate bridge side-by-side dichloromethane involving more flexible alkyne that allows quasi-free...

The truncated Wigner approximation to quantum dynamics in phase space is explored the context of computing vibronic line shapes for monomer linear optical spectra. We consider multiple model potential forms including a shifted harmonic oscillator with both equal and unequal frequencies on ground excited state potentials as well Morse model. For equal-frequency model, we derive an analytic expression exact shape that emphasizes importance using mechanical distribution initial conditions....

The emergence of experiments capable probing quantum dynamics at the single-molecule level requires development new theoretical tools simulating and analyzing these beyond an ensemble-averaged description. In this article, we present efficient method for sampling individual systems that make up ensemble apply it to study nonequilibrium ubiquitous spin-boson model. We generate single-system trajectories, analyze trajectory using from classical statistical mechanics. Our results demonstrate...

A new approximate coherent state path integral approach, which enables accurate and efficient dynamical treatment of model Hamiltonians that incorporate excited electronic states multiple chromophores are coupled to discrete high frequency harmonic vibrational modes, is presented. The approach based on the mapping Hamiltonian formalism for together with semiclassical expressions forward backward propagators describing quantum bath modes. density matrix dynamics propagated in full basis mode...

Quantum decoherence is the disappearance of simple phase relations within a discrete quantum system as result interactions with an environment. For many applications, question not necessarily how to avoid (inevitable) system-environment interactions, but rather design environments that optimally preserve system's in spite such interactions. The formation entanglement major driving mechanism for decoherence, and detailed understanding this process could inform strategies conserving coherence...

We develop an accurate and numerically efficient non-adiabatic path-integral approach to simulate the non- linear spectroscopy of exciton-polariton systems. This is based on partial linearized density matrix (PLDM) model exciton dynamics with explicit propagation phonon bath environment, combined a stochastic Lindblad cavity loss dynamics. Through simulating both polariton 2-dimensional electronic spectra (2DES), we systematically investigate how light-matter coupling strength rate influence...

We describe a matrix product state (MPS) extension for the Fermionic Quantum Emulator (FQE) software library. discuss theory behind symmetry adapted states approximating many-body wavefunctions of spin-1/2 fermions, and we present an open-source, MPS-enabled implementation FQE interface (MPS-FQE). The uses open-source pyblock3 block2 libraries most elementary tensor operations, it can largely be used as drop-in replacement that allows more efficient, but approximate, emulation larger...

RETURN TO ISSUEViewpointNEXTViewpoints on the 2017 American Conference Theoretical ChemistryZachary K. Goldsmith*†, Justin Provazza*‡, and Stefan Seritan*§∥View Author Information† Department of Chemistry, University Illinois at Urbana−Champaign, Urbana, 61801, United States‡ Boston University, Boston, Massachusetts 02215, States§ Chemistry PULSE Institute, Stanford Stanford, California 94305, States∥ SLAC National Accelerator Laboratory, Menlo Park, 94025, States*E-mail: [email protected]....

Growing experimental and theoretical evidence points to the key role of cryptochrome proteins in magnetoreception by migratory birds insects. Cryptochrome photoactivation is achieved through a cascade electron transfer events leading formation long-lived spin-correlated radical pair. The initiated photoexcitation FAD cofactor subsequent three conserved tryptophan residues, so-called triad. Presence ATP was shown increase yield semireduced form FAD. While triad well characterized both...

<div>Growing experimental and theoretical evidence points to the key role of cryptochrome proteins in magnetoreception by migratory birds insects. Cryptochrome photoactivation is achieved through a cascade electron transfer events leading formation long-lived spin-correlated radical pair. The initiated photoexcitation FAD cofactor subsequent three conserved tryptophan residues, so-called triad. Presence ATP was shown increase yield semireduced form FAD. While triad well characterized...

This work proposes a new photophysical phenomenon whereby UV/vis excitation of molecule involving Franck-Condon (FC) active vibration yields infrared (IR) emission by strong coupling to an optical cavity. The resulting UV/vis-to-IR photonic down conversion process is mediated vibrational polaritons in the electronic excited state potential. It shown that formation such (ESVP) via only occurs with molecules having modes both non-zero FC activity and IR state. Density functional theory...