Photoinduced Ultrafast Intramolecular Excited-State Energy Transfer in the Silylene-Bridged Biphenyl and Stilbene (SBS) System: A Nonadiabatic Dynamics Point of View

Wang, Jun; Huang, Jing; Du, Likai; Lan, Zhenggang

doi:10.1021/acs.jpca.5b00354

Cited by 12 publications

(13 citation statements)

References 104 publications

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“…Rates based on the energy gap between states and the total kinetic energy have been proposed by Truhlar et al and implemented by Granucci et al − These energy-based decoherence correction (EDC) and/or coherent switching with decay of mixing (CSDM) methods, have the benefit of being more easily calculated, and are the most widely used decoherence corrections. Often, the parameter suggested by Granucci et al is used regardless of the system being studied. ,,,− While simulations using EDC and CSDM performed on models and small molecular systems lead to results that are relatively independent of the predefined set of decoherence time and parameters, this was shown not to be true when applying the methods to large conjugated molecular systems. Results obtained in simulations of non-radiative relaxation in two conjugated oligomer systems, poly(phenylene-vinylene) (PPV) and poly(phenylene-ethynylene) (PPE), have shown a drastic dependence on which parameters are used .…”

Section: Theoretical Developments and Non-adiabatic Excited-state Mol...mentioning

confidence: 99%

Non-adiabatic Excited-State Molecular Dynamics: Theory and Applications for Modeling Photophysics in Extended Molecular Materials

et al. 2020

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Optically active molecular materials, such as organic conjugated polymers and biological systems, are characterized by strong coupling between electronic and vibrational degrees of freedom. Typically, simulations must go beyond the Born− Oppenheimer approximation to account for non-adiabatic coupling between excited states. Indeed, non-adiabatic dynamics is commonly associated with exciton dynamics and photophysics involving charge and energy transfer, as well as exciton dissociation and charge recombination. Understanding the photoinduced dynamics in such materials is vital to providing an accurate description of exciton formation, evolution, and decay. This interdisciplinary field has matured significantly over the past decades. Formulation of new theoretical frameworks, development of more efficient and accurate computational algorithms, and evolution of high-performance computer hardware has extended these simulations to very large molecular systems with hundreds of atoms, including numerous studies of organic semiconductors and biomolecules. In this Review, we will describe recent theoretical advances including treatment of electronic decoherence in surface-hopping methods, the role of solvent effects, trivial unavoided crossings, analysis of data based on transition densities, and efficient computational implementations of these numerical methods. We also emphasize newly developed semiclassical approaches, based on the Gaussian approximation, which retain phase and width information to account for significant decoherence and interference effects while maintaining the high efficiency of surface-hopping approaches. The above developments have been employed to successfully describe photophysics in a variety of molecular materials.

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Section: Theoretical Developments and Non-adiabatic Excited-state Mol...mentioning

confidence: 99%

Non-adiabatic Excited-State Molecular Dynamics: Theory and Applications for Modeling Photophysics in Extended Molecular Materials

et al. 2020

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“…In contrast to previous theoretical studies that put the focus on the vertical excitation properties and couplings of the molecular chromophores, we will explore the full excited-state potential energy surfaces (PES) of the DA-Me dimer system in order to fully elucidate the photophysical dynamics. We propose that this dynamical perspective is crucial in order to reach a general understanding of the complex energy transfer and photoinduced electron transfer dynamics in molecular DA systems, as has been demonstrated in various theoretical studies. − Especially, it is well known that the C–N bond rotation in the aminostyrene could lead to a twisted intramolecular charge transfer (TICT) state, and we believe this TICT formation dynamics should not be overlooked. We will pay extra attention to investigate the effects of the C–N bond rotation on the photophysics of DA-Me .…”

Section: Introductionmentioning

confidence: 94%

C–N Bond Rotation Controls Photoinduced Electron Transfer in an Aminostyrene–Stilbene Donor–Acceptor System

Huang

Cheng

2019

J. Phys. Chem. A

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We investigate energy transfer and electron transfer in a dimethylsilylene-spaced aminostyrene−stilbene donor−acceptor dimer using time-dependent density functional theory calculations. Our results confirm that the vertical S 3 , S 2 , and S 1 excited states are, respectively, a local excitation on the aminostyrene, local excitation on the stilbene, and the charge-transferred (CT) excited state with electron transfer from aminostyrene to stilbene. In addition, an energy minimum with the C−N bond of the amino group twisted at about 90°is also identified on the S 1 potential energy surface. This S 1 state exhibits a twisted intramolecular charge transfer (TICT) character. A potential energy scan along the C−N bond torsional angle reveals a conical intersection between the S 2 stilbene local excitation and the S 1 CT/TICT state at a torsional angle of ∼60°. We thus propose that the conical intersection dominates the electron transfer dynamics in the donor−acceptor dimer and copolymers alike, and the energy barrier along the C−N bond rotation controls the efficiency of such a process. Moreover, we show that despite the zero oscillator strength of the S 1 excited states in the CT and TICT minima, an emissive S 1 state with a V-shaped conformational structure can be located. The energy of this V-shape CT structure is thermally accessible; therefore, it is expected to be responsible for the CT emission band of the dimer observed in polar solvents. Our data provide a clear explanation of the complex solvent-dependent dual emission and photoinduced electron transfer properties observed experimentally in the dimer and copolymer systems. More importantly, the identifications of the conical intersection and energy barrier along the C−N bond rotation provide a novel synthetic route for controlling emissive properties and electron transfer dynamics in similar systems, which might be useful in the design of novel organic optoelectronic materials.

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“…15,16 The advantages of the surface hopping simulations are relatively low computational cost (especially when combined with fast electronic structure methods) and ability to treat explicitly (though classically) all nuclear DoFs for relatively large molecular systems. [17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] However, in order to account for the quantum nature of nuclei and properly describe decoherence the quantum dynamical treatment is needed. 12,14,[33][34][35][36][37] To judge the extent of the spatial exciton (de)localization, in the SH simulations the electronic quantities (transition density matrices, molecular orbitals, particle and hole charges, etc.)…”

Section: Introductionmentioning

confidence: 99%

(De)localization dynamics of molecular excitons: comparison of mixed quantum-classical and fully quantum treatments

Titov

Kopp

Hoche

et al. 2022

Phys. Chem. Chem. Phys.

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Photoinduced Ultrafast Intramolecular Excited-State Energy Transfer in the Silylene-Bridged Biphenyl and Stilbene (SBS) System: A Nonadiabatic Dynamics Point of View

Cited by 12 publications

References 104 publications

Non-adiabatic Excited-State Molecular Dynamics: Theory and Applications for Modeling Photophysics in Extended Molecular Materials

Non-adiabatic Excited-State Molecular Dynamics: Theory and Applications for Modeling Photophysics in Extended Molecular Materials

C–N Bond Rotation Controls Photoinduced Electron Transfer in an Aminostyrene–Stilbene Donor–Acceptor System

(De)localization dynamics of molecular excitons: comparison of mixed quantum-classical and fully quantum treatments

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