Interplay Between Locally Excited and Charge Transfer States Governs the Photoswitching Mechanism in Fluorescent Protein Dreiklang

<div>We present the results of high-level electronic structure and dynamics simulations</div><div>of the photoactive protein Dreiklang. With the goal to understand the details of</div><div>Dreiklang's photocycle, we carefully characterize the excited states of the ON- and</div><div>OFF-forms of Dreiklang. The key ?nding of our study is the existence of a lowlying</div><div>excited state of a charge-transfer (CT) character in the neutral ON form and</div><div>that population of this state, which is nearly isoenergetic with the locally excited</div><div>(LE) bright state, initiates series of steps ultimately leading to the formation of</div><div>the hydrated dark chromophore (OFF state). These results allow us to re?ne the</div><div>mechanistic picture of the Dreiklang's photocycle and photoactivation.</div>

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Locally-Excited (LE) versus Charge-Transfer (CT) Excited State Competition in a Series of Para-Substituted Neutral Green Fluorescent Protein (GFP) Chromophore Models

The Journal of Physical Chemistry B ◽

10.1021/jp508723d ◽

2014 ◽

Vol 119 (6) ◽

pp. 2566-2575 ◽

Cited By ~ 19

Author(s):

Seth Olsen

Keyword(s):

Excited State ◽

Charge Transfer ◽

Green Fluorescent Protein ◽

Fluorescent Protein ◽

Locally Excited ◽

Gfp Chromophore ◽

Green Fluorescent

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Tracking DNA Excited States by Picosecond-Time-Resolved Infrared Spectroscopy: Signature Band for a Charge-Transfer Excited State in Stacked Adenine–Thymine Systems

The Journal of Physical Chemistry Letters ◽

10.1021/jz401258n ◽

2013 ◽

Vol 4 (16) ◽

pp. 2739-2744 ◽

Cited By ~ 63

Author(s):

Gerard W. Doorley ◽

Michal Wojdyla ◽

Graeme W. Watson ◽

Michael Towrie ◽

Anthony W. Parker ◽

...

Keyword(s):

Infrared Spectroscopy ◽

Excited State ◽

Charge Transfer ◽

Excited States ◽

Time Resolved ◽

A Charge ◽

Time Resolved Infrared Spectroscopy ◽

Adenine Thymine

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The electronic structure and charge transfer excited states of the endohedral trimetallic nitride C80 (Ih) fullerenes–Zn-tetraphenyl porphyrin dyads

Physical Chemistry Chemical Physics ◽

10.1039/c4cp04583a ◽

2015 ◽

Vol 17 (8) ◽

pp. 5832-5839 ◽

Cited By ~ 13

Author(s):

Luis Basurto ◽

Fatemeh Amerikheirabadi ◽

Rajendra Zope ◽

Tunna Baruah

Keyword(s):

Electronic Structure ◽

Excited State ◽

Charge Transfer ◽

Excited States ◽

Tetraphenyl Porphyrin

Replacing C60 or C70 by an M3N@C80 (M = Sc, Y) in co-facial dyads with ZnTPP increases charge transfer excited state energies.

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Excited-State Electronic Structure of Molecules Using Many-Body Green's Functions: Quasiparticles and Electron-Hole Excitations with VOTCA-XTP

10.26434/chemrxiv.11477895 ◽

2019 ◽

Author(s):

Gianluca Tirimbò ◽

Vivek Sundaram ◽

Onur Çaylak ◽

Wouter Scharpach ◽

Javier Sijen ◽

...

Keyword(s):

Electronic Structure ◽

Excited State ◽

Excited States ◽

Green's Functions ◽

Green’S Functions ◽

Molecular Architecture ◽

Many Body ◽

Electron Hole ◽

Structure Of Molecules ◽

Dynamics Simulations

<div>We present the open-source VOTCA-XTP software for the calculation of the excited-state electronic structure of molecules using many-body Green’s functions theory in the GW approximation with the Bethe–Salpeter Equation (BSE). This work provides a summary of the underlying theory and discusses details of its implementation based on Gaussian orbitals, including, i.a., resolution-of-identity techniques, different approaches to the frequency integration of the self-energy or acceleration by offloading compute-intensive matrix operations using GPUs in a hybrid OpenMP/Cuda scheme. A distinctive feature of VOTCA-XTP is the capability to couple the calculation of electronic excitations to a classical polarizable environment on atomistic level in a coupled quantum- and molecular-mechanics (QM/MM) scheme, where a complex morphology can be imported from Molecular Dynamics simulations. The capabilities and limitations of the GW -BSE implementation are illustrated with two examples. First, we study the dependence of optically active electron-hole excitations in a series of diketopyrrolopyrrole-based oligomers on molecular-architecture modifications and the number of repeat units. Second, we use the GW -BSE/MM setup to investigate the effect of polarization on localized and intermolecular charge-transfer excited states in morphologies of low-donor content rubrene-fullerene mixtures. These showcases demonstrate that our implementation currently allows to treat systems with up to 2500 basis functions on regular shared-memory workstations, providing accurate descriptions of quasiparticle and coupled electron-hole excited states of various character on an equal footing.</div>

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Excited-State Electronic Structure of Molecules Using Many-Body Green's Functions: Quasiparticles and Electron-Hole Excitations with VOTCA-XTP

10.26434/chemrxiv.11477895.v1 ◽

2019 ◽

Author(s):

Gianluca Tirimbò ◽

Vivek Sundaram ◽

Onur Çaylak ◽

Wouter Scharpach ◽

Javier Sijen ◽

...

Keyword(s):

Electronic Structure ◽

Excited State ◽

Excited States ◽

Green's Functions ◽

Green’S Functions ◽

Molecular Architecture ◽

Many Body ◽

Electron Hole ◽

Structure Of Molecules ◽

Dynamics Simulations

<div>We present the open-source VOTCA-XTP software for the calculation of the excited-state electronic structure of molecules using many-body Green’s functions theory in the GW approximation with the Bethe–Salpeter Equation (BSE). This work provides a summary of the underlying theory and discusses details of its implementation based on Gaussian orbitals, including, i.a., resolution-of-identity techniques, different approaches to the frequency integration of the self-energy or acceleration by offloading compute-intensive matrix operations using GPUs in a hybrid OpenMP/Cuda scheme. A distinctive feature of VOTCA-XTP is the capability to couple the calculation of electronic excitations to a classical polarizable environment on atomistic level in a coupled quantum- and molecular-mechanics (QM/MM) scheme, where a complex morphology can be imported from Molecular Dynamics simulations. The capabilities and limitations of the GW -BSE implementation are illustrated with two examples. First, we study the dependence of optically active electron-hole excitations in a series of diketopyrrolopyrrole-based oligomers on molecular-architecture modifications and the number of repeat units. Second, we use the GW -BSE/MM setup to investigate the effect of polarization on localized and intermolecular charge-transfer excited states in morphologies of low-donor content rubrene-fullerene mixtures. These showcases demonstrate that our implementation currently allows to treat systems with up to 2500 basis functions on regular shared-memory workstations, providing accurate descriptions of quasiparticle and coupled electron-hole excited states of various character on an equal footing.</div>

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Exploring the Franck-Condon region of a photoexcited charge transfer complex in solution to interpret femtosecond stimulated Raman spectroscopy: excited state electronic structure methods to unveil non-radiative pathways

Chemical Science ◽

10.1039/d1sc01238j ◽

2021 ◽

Author(s):

Federico Coppola ◽

Paola Cimino ◽

Umberto Raucci ◽

Maria Gabriella Chiariello ◽

Alessio Petrone ◽

...

Keyword(s):

Raman Spectroscopy ◽

Electronic Structure ◽

Excited State ◽

Charge Transfer ◽

Charge Transfer Complex ◽

Main Role ◽

Photoinduced Charge Transfer ◽

Electronic Structure Methods ◽

Franck Condon ◽

Photoinduced Charge

We present electronic structure methods to unveil non-radiative pathways of photoinduced charge transfer (CT) reactions that play a main role in photophysics and light harvesting technologies. A prototypical π-stacked molecular...

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