Two-dimensional vibronic spectroscopy of molecular aggregates: Trimers, dimers, and monomers

Keß, Martin; Worth, Graham A.; Engel, Volker

doi:10.1063/1.4961388

Cited by 7 publications

(6 citation statements)

References 83 publications

(89 reference statements)

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“…They are particularly well suited for studying IC and ISC dynamics on the time scale of a few hundred femtoseconds in rigid systems. Fields of applications range from polycyclic aromatic fused rings ,− and DNA nucleobases − to transition-metal complexes − to molecular aggregates. − …”

Section: Theorymentioning

confidence: 99%

“… 26 , 27 The MCTDH scheme has been previously utilized in the nonperturbative approach to computing transient absorption (TA) and two-dimensional (2D) electronic spectroscopy. 4 , 28 , 29 Recently, applications of the Gaussian-based MCTDH (G-MCTDH) approach to describe nonlinear spectroscopy have also been demonstrated. 30 The ingredients required to parametrize the molecular Hamiltonian are similar to those utilized in the approximate expressions described above (knowledge of the electronic and nuclear degrees of freedom and their coupling), with the addition of the interstate couplings, which may also be obtained from QM calculations.…”

Section: Introductionmentioning

confidence: 99%

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Nonlinear Molecular Electronic Spectroscopy via MCTDH Quantum Dynamics: From Exact to Approximate Expressions

Segatta

Aranda

Aleotti

et al. 2023

J. Chem. Theory Comput.

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We present an accurate and efficient approach to computing the linear and nonlinear optical spectroscopy of a closed quantum system subject to impulsive interactions with an incident electromagnetic field. It incorporates the effect of ultrafast nonadiabatic dynamics by means of explicit numerical propagation of the nuclear wave packet. The fundamental expressions for the evaluation of first- and higher-order response functions are recast in a general form that can be used with any quantum dynamics code capable of computing the overlap of nuclear wave packets evolving in different states. Here we present the evaluation of these expressions with the multiconfiguration time-dependent Hartree (MCTDH) method. Application is made to pyrene, excited to its lowest bright excited state S 2 which exhibits a sub-100-fs nonadiabatic decay to a dark state S 1. The system is described by a linear vibronic coupling Hamiltonian, parametrized with multiconfiguration electronic structure methods. We show that the ultrafast nonadiabatic dynamics can have a remarkable effect on the spectral line shapes that goes beyond simple lifetime broadening. Furthermore, a widely employed approximate expression based on the time scale separation of dephasing and population relaxation is recast in the same theoretical framework. Application to pyrene shows the range of validity of such approximations.

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Section: Theorymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Nonlinear Molecular Electronic Spectroscopy via MCTDH Quantum Dynamics: From Exact to Approximate Expressions

Segatta

Aranda

Aleotti

et al. 2023

J. Chem. Theory Comput.

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“…To this end, we follow the prescription used in ref . In this section, we outline the procedure (the reader is referred to refs , − , and for a more detailed discussion).…”

Section: Theorymentioning

confidence: 99%

“…Resolving the signal field into components based on their overall phase can be achieved by using the method of Seidner et al, which is analogous to the experimental measurement of those spectra via the phase-cycling method. − This method is based on simulating the overall signal field for different combinations of interpulse intervals and pulse phases without treating the field–matter interaction perturbatively . Components with the overall phase of interest such as the rephasing and nonrephasing signals can then be obtained by performing an inverse Fourier transform (FT). ,,− …”

Section: Introductionmentioning

confidence: 99%

A Nonperturbative Methodology for Simulating Multidimensional Spectra of Multiexcitonic Molecular Systems via Quasiclassical Mapping Hamiltonian Methods

Gao

Geva

2020

J. Chem. Theory Comput.

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We present a new methodology for simulating multidimensional electronic spectra of complex multiexcitonic molecular systems within the framework of quasiclassical mapping Hamiltonian (QC/MH) methods. The methodology is meant to be cost-effective for molecular systems with a large number of nuclear degrees of freedom undergoing nonequilibrium nonadiabatic dynamics on multiple coupled anharmonic electronic potential energy surfaces, for which quantum-mechanically exact methods are not feasible. The methodology is based on a nonperturbative approach to field−matter interaction, which mimics the experimental measurement of those nonlinear timeresolved spectra via phase cycling and can accommodate laser pulses of arbitrary shape and intensity. The ability of different QC/ MH methods to accurately simulate two-dimensional and pump−probe electronic spectra within the proposed methodology is compared in the context of a biexcitonic benchmark model that includes both the singly excited and doubly excited electronic states. The QC/MH methods compared include five variations of the linearized semiclassical (LSC) method and the mean-field (Ehrenfest) method. The results show that LSC-based methods are significantly more accurate than the mean-field method and can yield quantitatively accurate two-dimensional and pump−probe spectra when nuclear degrees of freedom can be treated as classicallike.

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“…50 Also, the appearance of the 2D spectra will change when including the vibrational motion. 51,52 In particular, the spectral peaks discussed in Sec. III are no longer resolved.…”

Section: The Journal Of Chemical Physicsmentioning

confidence: 99%

Mapping of exciton–exciton annihilation in a molecular dimer via fifth-order femtosecond two-dimensional spectroscopy

Suss

Wehner

Dostál³

et al. 2019

The Journal of Chemical Physics

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We present a theoretical study on exciton-exciton annihilation (EEA) in a molecular dimer. This process is monitored using a fifth-order coherent two-dimensional (2D) spectroscopy as was recently proposed by Dostál et al. [Nat. Commun. 9, 2466 (2018)]. Using an electronic three-level system for each monomer, we analyze the different paths which contribute to the 2D spectrum. The spectrum is determined by two entangled relaxation processes, namely, the EEA and the direct relaxation of higher lying excited states. It is shown that the change of the spectrum as a function of a pulse delay can be linked directly to the presence of the EEA process.

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Two-dimensional vibronic spectroscopy of molecular aggregates: Trimers, dimers, and monomers

Cited by 7 publications

References 83 publications

Nonlinear Molecular Electronic Spectroscopy via MCTDH Quantum Dynamics: From Exact to Approximate Expressions

Nonlinear Molecular Electronic Spectroscopy via MCTDH Quantum Dynamics: From Exact to Approximate Expressions

A Nonperturbative Methodology for Simulating Multidimensional Spectra of Multiexcitonic Molecular Systems via Quasiclassical Mapping Hamiltonian Methods

Mapping of exciton–exciton annihilation in a molecular dimer via fifth-order femtosecond two-dimensional spectroscopy

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