Semiclassical Path Integral Calculation of Nonlinear Optical Spectroscopy

Provazza, Justin; Segatta, Francesco; Garavelli, Marco; Coker, David F.

doi:10.1021/acs.jctc.7b01063

Cited by 38 publications

(64 citation statements)

References 42 publications

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“…We would like to mention that treating vibrational diabatic states with MMST mapping variables can certainly improve the accuracy of the dynamics, as been demonstrated with other recent theoretical works. In one example, vib-PLDM is used to compute 2-dimensional electronic spectra 63 in a Frenkel excitons model with a high-frequency vibrational mode. in another example, a new method, so called extended SQC approach 86 is developed based on similar strategy of vib-PLDM, which provides accurate non-adiabatic dynamics when a highly non-harmonic mode is explicitly quantized with its vibrational eigenbasis.…”

Section: Resultsmentioning

confidence: 99%

Investigating photoinduced proton coupled electron transfer reaction using quasi diabatic dynamics propagation

Mandal

Shakib

Huo

2018

The Journal of Chemical Physics

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We investigate photoinduced proton-coupled electron transfer (PI-PCET) reactions through a recently developed quasi-diabatic (QD) quantum dynamics propagation scheme. This scheme enables interfacing accurate diabatic-based quantum dynamics approaches with adiabatic electronic structure calculations for on-the-fly simulations. Here, we use the QD scheme to directly propagate PI-PCET quantum dynamics with the diabatic partial linearized density matrix path-integral approach with the instantaneous adiabatic electron-proton vibronic states. Our numerical results demonstrate the importance of treating protons quantum mechanically in order to obtain accurate PI-PCET dynamics as well as the role of solvent fluctuation and vibrational relaxation on proton tunneling in various reaction regimes that exhibit different kinetic isotope effects. This work opens the possibility to study the challenging PI-PCET reactions through accurate diabatic quantum dynamics approaches combined with efficient adiabatic electronic structure calculations.

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Section: Resultsmentioning

confidence: 99%

Investigating photoinduced proton coupled electron transfer reaction using quasi diabatic dynamics propagation

Mandal

Shakib

Huo

2018

The Journal of Chemical Physics

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“…Louiville equation (QCLE) [85][86][87][88][89][90] , path integral [91][92][93][94][95][96][97] , surface hopping [98][99][100][101] , centroid molecular dynamics (CMD) 102 and ring-polymer molecular dynamics (RPMD) [103][104][105][106][107] .…”

Section: Quantum Classicalmentioning

confidence: 99%

Performance evaluation of the symmetrical quasi-classical dynamics method based on Meyer-Miller mapping Hamiltonian in the treatment of site-exciton models

Xie

Zheng

Lan

2018

The Journal of Chemical Physics

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The symmetrical quasi-classical dynamics method based on the Meyer-Miller mapping Hamiltonian (MM-SQC) shows the great potential in the treatment of the nonadiabatic dynamics of complex systems. We performed the comprehensive benchmark calculations to evaluate the performance of the MM-SQC method in various site-exciton models with respect to the accurate results of quantum dynamics method multilayer multiconfigurational time-dependent Hartree (ML-MCTDH). The parameters of the site-exciton models are chosen to represent a few of prototypes used 2 in the description of photoinduced excitonic dynamics processes in photoharvesting systems and organic solar cells, which include the rather board situations with the fast or slow bath and different system-bath couplings. When the characteristic frequency of the bath is low, the MM-SQC method performs extremely well, and it gives almost the identical results to those of ML-MCTDH. When the fast bath is considered, the deviations exist between the MM-SQC and ML-MCTDH results if the high-frequency bath modes are improperly treated by the classical manner. When the so-called adiabatic renormalization was employed to construct the reduced Hamiltonian by freezing high-frequency modes, the MM-SQC dynamics can give the results comparable to the ML-MCTDH ones. Thus, the MM-SQC method itself provide reasonable results in all test site-exciton models, while the proper treatments of the bath modes must be employed. The possible dependence of the MM-SQC dynamics on the different initial sampling methods for the nuclear degrees of freedom is also discussed.3

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“…Both mechanisms concur in the observed signal of IR pump-probe spectroscopy, although thermal diffusion contribution was predicted to be reduced under short time-scales [104]. In these regards, simulations of two dimensional electronic spectra have been developed [105], together with a semi-classical path integral formalism [106]. Data from pump-probe spectroscopy were connected with molecular conformations, charge transfer and their related photo-responsive properties [107].…”

Section: Selected Applications Of Ab-initio Predictions In Push-pull mentioning

confidence: 64%

Synergistic Approach of Ultrafast Spectroscopy and Molecular Simulations in the Characterization of Intramolecular Charge Transfer in Push-Pull Molecules

et al. 2020

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The comprehensive characterization of Intramolecular Charge Transfer (ICT) stemming in push-pull molecules with a delocalized π-system of electrons is noteworthy for a bespoke design of organic materials, spanning widespread applications from photovoltaics to nanomedicine imaging devices. Photo-induced ICT is characterized by structural reorganizations, which allows the molecule to adapt to the new electronic density distribution. Herein, we discuss recent photophysical advances combined with recent progresses in the computational chemistry of photoactive molecular ensembles. We focus the discussion on femtosecond Transient Absorption Spectroscopy (TAS) enabling us to follow the transition from a Locally Excited (LE) state to the ICT and to understand how the environment polarity influences radiative and non-radiative decay mechanisms. In many cases, the charge transfer transition is accompanied by structural rearrangements, such as the twisting or molecule planarization. The possibility of an accurate prediction of the charge-transfer occurring in complex molecules and molecular materials represents an enormous advantage in guiding new molecular and materials design. We briefly report on recent advances in ultrafast multidimensional spectroscopy, in particular, Two-Dimensional Electronic Spectroscopy (2DES), in unraveling the ICT nature of push-pull molecular systems. A theoretical description at the atomistic level of photo-induced molecular transitions can predict with reasonable accuracy the properties of photoactive molecules. In this framework, the review includes a discussion on the advances from simulation and modeling, which have provided, over the years, significant information on photoexcitation, emission, charge-transport, and decay pathways. Density Functional Theory (DFT) coupled with the Time-Dependent (TD) framework can describe electronic properties and dynamics for a limited system size. More recently, Machine Learning (ML) or deep learning approaches, as well as free-energy simulations containing excited state potentials, can speed up the calculations with transferable accuracy to more complex molecules with extended system size. A perspective on combining ultrafast spectroscopy with molecular simulations is foreseen for optimizing the design of photoactive compounds with tunable properties.

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Semiclassical Path Integral Calculation of Nonlinear Optical Spectroscopy

Cited by 38 publications

References 42 publications

Investigating photoinduced proton coupled electron transfer reaction using quasi diabatic dynamics propagation

Investigating photoinduced proton coupled electron transfer reaction using quasi diabatic dynamics propagation

Performance evaluation of the symmetrical quasi-classical dynamics method based on Meyer-Miller mapping Hamiltonian in the treatment of site-exciton models

Synergistic Approach of Ultrafast Spectroscopy and Molecular Simulations in the Characterization of Intramolecular Charge Transfer in Push-Pull Molecules

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