Calculating Two-Dimensional Spectra with the Mixed Quantum-Classical Ehrenfest Method

Vegte, C. P. van der; Dijkstra, Arend G.; Knoester, Jasper; Jansen, Thomas L. C.

doi:10.1021/jp311668r

Cited by 57 publications

(68 citation statements)

References 49 publications

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“…426 Alternatively, 2DES simulated with either hierarchy equations of motion (HEOM) or numerical integration of Schrodinger equation (NISE) methods using MFE and TSH dynamics has been described in Refs. 307,427 .…”

Section: Two-dimensional Electronic Spectrummentioning

confidence: 99%

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Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

2018

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Nonadiabatic mixed quantum-classical (NA-MQC) dynamics methods form a class of computational theoretical approaches in quantum chemistry tailored to investigate the time evolution of nonadiabatic phenomena in molecules and supramolecular assemblies. NA-MQC is characterized by a partition of the molecular system into two subsystems: one to be treated quantum mechanically (usually but not restricted to electrons) and another to be dealt with classically (nuclei). The two subsystems are connected through nonadiabatic couplings terms to enforce self-consistency. A local approximation underlies the classical subsystem, implying that direct dynamics can be simulated, without needing precomputed potential energy surfaces. The NA-MQC split allows reducing computational costs, enabling the treatment of realistic molecular systems in diverse fields. Starting from the three most well-established methods-mean-field Ehrenfest, trajectory surface hopping, and multiple spawning-this review focuses on the NA-MQC dynamics methods and programs developed in the last 10 years. It stresses the relations between approaches and their domains of application. The electronic structure methods most commonly used together with NA-MQC dynamics are reviewed as well. The accuracy and precision of NA-MQC simulations are critically discussed, and general guidelines to choose an adequate method for each application are delivered.

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Section: Two-dimensional Electronic Spectrummentioning

confidence: 99%

“…[303][304] This is a well-known problem related to the asymptotic behavior of xc  . 35,[305][306][307] The standard solution has been to adopt range-separated functionals. [308][309] • Failure to describe states with double and higher excitations.…”

mentioning

confidence: 99%

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

2018

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“…Effectively, the spectra of the individual snapshots are subject to a constant line broadening of 1000 cm -1 , which has been set so that the broadenings along Ω 1 for the total ApA spectrum mimic the experimental broadening recently measured in 2DUV experiments for adenine. 17 Although several computational approaches have been devised recently to consider spectral diffusion and non-adiabatic effects on the simulated 2DES, [45][46][47][48][49] the size of the current system prevents the usage of more sophisticated approaches. Quasi-absorptive signals were simulated for the condition of a collinear pump pulse pair (thus recording simultaneously rephrasing and non-rephasing contributions).…”

Section: 40mentioning

confidence: 99%

Two-dimensional electronic spectroscopy as a tool for tracking molecular conformations in DNA/RNA aggregates

et al. 2018

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A computational strategy to simulate two-dimensional electronic spectra (2DES) is introduced, which allows us to analyse ground state dynamics and to sample and measure different conformations attained by flexible molecular systems in solution. An explicit mixed quantum mechanics/molecular mechanics (QM/MM) approach is employed for the evaluation of the necessary electronic excited state energies and transition dipole moments. The method is applied towards a study of the highly flexible water-solvated adenine-adenine monophosphate (ApA), a system featuring two interacting adenine moieties that display various intermolecular arrangements, known to deeply affect their photochemical outcome. Molecular dynamics simulations and cluster analysis have been used to select the molecular conformations, reducing the complexity of the flexible ApA conformational space. By using our sum-over-states (SOS) approach to obtain the 2DES spectra for each of these selected conformations, we can discern spectral changes and relate them to specific nuclear arrangements: close lying π-stacked bases exhibit a splitting of their respective 1La signal traces; T-stacked bases exhibit the appearance of charge transfer states in the low-energy Vis probing window while displaying no 1La splitting, being particularly favoured when promoting amino to 5-ring interactions; unstacked and distant adenine moieties exhibit signals similar to those of the adenine monomer, as is expected for non-interacting nucleobases. 2DES maps reveal the spectral fingerprints associated with specific molecular conformations, and are thus a promising option to enable their quantitative spectroscopic detection beyond standard 1D pump-probe techniques. This is expected to aid the understanding of how nucleobase aggregation controls and modulates the photostability and photo-damage of extended DNA/RNA systems.

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“…The capabilities of the method are demonstrated on a system of two coupled electronic states in turn coupled to a harmonic nuclear coordinate and phenomena like dynamic Stokes shift, spectral diffusion and population transfer are compared to accurate NISE and HEOM results. 41,42 Further, we demonstrate that the molecular bichromophore DPM can be described in a fully microscopic fashion by abinitio MD to simulate 2D spectra upon electronic excitation. The microscopic description via trajectory dynamics allows for the investigation of energy fluctuations due to nuclear dynamics and population transfer without beforehand knowledge of the molecular PES.…”

Section: Introductionmentioning

confidence: 84%

“…Article transfer could be observed and accurate available NISE and HEOM reference data 41,42 are reproduced.…”

Section: Journal Of Chemical Theory and Computationmentioning

confidence: 97%

Simulation of Multi-Dimensional Signals in the Optical Domain: Quantum-Classical Feedback in Nonlinear Exciton Propagation

Richter

Fingerhut

2016

J. Chem. Theory Comput.

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We present an algorithm for the simulation of nonlinear 2D spectra of molecular systems in the UV-vis spectral region from atomistic molecular dynamics trajectories subject to nonadiabatic relaxation. We combine the nonlinear exciton propagation (NEP) protocol, that relies on a quasiparticle approach with the surface hopping methodology to account for quantum-classical feedback during the dynamics. Phenomena, such as dynamic Stokes shift due to nuclear relaxation, spectral diffusion, and population transfer among electronic states, are thus naturally included and benchmarked on a model of two electronic states coupled to a harmonic coordinate and a classical heatbath. The capabilities of the algorithm are further demonstrated for the bichromophore diphenylmethane that is described in a fully microscopic fashion including all 69 classical nuclear degrees of freedom. We demonstrate that simulated 2D signals are especially sensitive to the applied theoretical approximations (i.e., choice of active space in the CASSCF method) where population dynamics appears comparable.

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Calculating Two-Dimensional Spectra with the Mixed Quantum-Classical Ehrenfest Method

Cited by 57 publications

References 49 publications

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

Two-dimensional electronic spectroscopy as a tool for tracking molecular conformations in DNA/RNA aggregates

Simulation of Multi-Dimensional Signals in the Optical Domain: Quantum-Classical Feedback in Nonlinear Exciton Propagation

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