scholarly journals Internal conversion of the anionic GFP chromophore: in and out of the I-twisted S1/S0 conical intersection seam

2022 ◽  
Author(s):  
Nanna H. List ◽  
Chey M. Jones ◽  
Todd J. Martínez
Keyword(s):  
Quantum Yield ◽  
Internal Conversion ◽  
Conical Intersection ◽  
Statistical Dynamics ◽  
Statistical Behavior ◽  
Gfp Chromophore

The Z–E photoisomerization quantum yield of the HBDI− chromophore is a result of early, non-statistical dynamics around a less reactive I-twisted intersection and later, statistical behavior around the more reactive, near-enantiomeric counterpart.

scholarly journals Communication: Autodetachment versus internal conversion from the S1 state of the isolated GFP chromophore anion

2013 ◽  
Vol 139 (7) ◽  
pp. 071104 ◽  
Author(s):  
Christopher W. West ◽  
Alex S. Hudson ◽  
Steven L. Cobb ◽  
Jan R. R. Verlet
Keyword(s):  
Internal Conversion ◽  
Gfp Chromophore

Internal Conversion with 3,5-Dimethyl-4-(methylamino)benzonitrile in Alkane Solvents

2000 ◽  
Vol 214 (11) ◽  
Author(s):  
I. Rückert ◽  
A. Hebecker ◽  
A.B.J. Parusel ◽  
K.A. Zachariasse
Keyword(s):  
Quantum Yield ◽  
Fluorescence Quantum Yield ◽  
Internal Conversion ◽  
Alkane Solvents

With 3,5-dimethyl-4-(methylamino)benzonitrile (MHD) in n-hexane and n-hexadecane at 25°C, relatively small values are obtained for the fluorescence quantum yield Φ

Dramatic reduction in fluorescence quantum yield in mutants of Green Fluorescent Protein due to fast internal conversion

1998 ◽  
Vol 237 (1-2) ◽  
pp. 183-193 ◽  
Author(s):  
Andreas D Kummer ◽  
Christian Kompa ◽  
Harald Lossau ◽  
Florian Pöllinger-Dammer ◽  
Maria E Michel-Beyerle ◽  
...  
Keyword(s):  
Green Fluorescent Protein ◽  
Quantum Yield ◽  
Fluorescence Quantum Yield ◽  
Internal Conversion ◽  
Fluorescent Protein ◽  
Dramatic Reduction ◽  
Green Fluorescent

Delayed vibrational modulation of the solvated GFP chromophore into a conical intersection

2019 ◽  
Vol 21 (19) ◽  
pp. 9728-9739 ◽  
Author(s):  
Miles A. Taylor ◽  
Liangdong Zhu ◽  
Nikita D. Rozanov ◽  
Kenneth T. Stout ◽  
Cheng Chen ◽  
...  
Keyword(s):  
Conical Intersection ◽  
Gfp Chromophore

Upon photoexcitation, a delayed structural bending motion facilitates the “dark” GFP chromophore ring-twisting isomerization in reaching a conical intersection in solution.

Impact of Vibrational Coherence on the Quantum Yield at a Conical Intersection

2016 ◽  
Vol 7 (17) ◽  
pp. 3491-3496 ◽  
Author(s):  
Hong-Guang Duan ◽  
R. J. Dwayne Miller ◽  
Michael Thorwart
Keyword(s):  
Quantum Yield ◽  
Conical Intersection ◽  
Vibrational Coherence

scholarly journals Toward Prediction of Nonradiative Decay Pathways in Organic Compounds II: Two Internal Conversion Channels in BODIPYs

2019 ◽  
Author(s):  
Zhou Lin ◽  
Alexander Kohn ◽  
Troy Van Voorhis
Keyword(s):  
Quantum Yield ◽  
Rational Design ◽  
Internal Conversion ◽  
Photophysical Properties ◽  
Data Driven ◽  
Laser Dyes ◽  
Intermediate Structure ◽  
Sensing Applications ◽  
Aided Design ◽  
Semi Empirical

<div>Boron-dipyrromethene (BODIPY) molecules are widely used as laser dyes and have therefore become a popular research topic within recent decades. Numerous studies have been reported for the rational design of BODIPY derivatives based on their spectroscopic and photophysical properties, including absorption and fluorescence wavelengths (<i>λ</i><sub>abs</sub> and <i>λ</i><sub>fl</sub>), oscillator strength (<i>f</i>), nonradiative pathways, and quantum yield (<i>ϕ</i>). In the present work, we illustrate a theoretical, semi-empirical model that accurately predicts <i>ϕ</i> for various BODIPY compounds based on inexpensive electronic structure calculations, following the data-driven algorithm proposed and tested on the naphthalene family by us [Kohn, Lin, and Van Voorhis, <i>J. Phys. Chem. C.</i> <b>2019</b>, <i>123</i>, 15394]. The model allows us to identify the dominant nonradiative channel of any BODIPY molecule using its structure exclusively and to establish a correlation between the activation energy (<i>E</i><sub>a</sub>) and the fluorescence quantum yield (<i>ϕ</i><sub>fl</sub>). Based on our calculations, either the S<sub>1</sub> → S<sub>0</sub> or <i>L<sub>a</sub></i> → <i>L<sub>b</sub></i> internal conversion (IC) mechanism dominates in the majority of BODIPY derivatives, depending on the structural and electronic properties of the substituents. In both cases, the nonradiative rate (<i>k</i><sub>nr</sub>) exhibits a straightforward Arrhenius-like relation with the associated <i>E</i><sub>a</sub>. More interestingly, the S<sub>1</sub> → S<sub>0</sub> mechanism proceeds via a highly distorted intermediate structure in which the core BODIPY plane and the substituent at the 1-position are forced to bend, while the internal rotation of the very same substituent induces the <i>La </i>→<i> Lb</i> transition. Our model reproduces <i>k</i><sub>fl</sub>, <i>k</i><sub>nr</sub>, and <i>ϕ</i><sub>fl</sub> to mean absolute errors (MAE) of 0.16 decades, 0.87 decades, and 0.26, when all outliers are considered. These results allow us to validate the predictive power of the proposed data-driven algorithm in <i>ϕ</i><sub>fl</sub>. They also indicate that the model has a great potential to facilitate and accelerate the machine learning aided design of BODIPY dyes for imaging and sensing applications, given sufficient experimental data and appropriate molecular descriptors.</div>

scholarly journals Toward Prediction of Nonradiative Decay Pathways in Organic Compounds II: Two Internal Conversion Channels in BODIPYs

2019 ◽  
Author(s):  
Zhou Lin ◽  
Alexander Kohn ◽  
Troy Van Voorhis
Keyword(s):  
Quantum Yield ◽  
Rational Design ◽  
Internal Conversion ◽  
Photophysical Properties ◽  
Data Driven ◽  
Laser Dyes ◽  
Intermediate Structure ◽  
Sensing Applications ◽  
Aided Design ◽  
Semi Empirical

<div>Boron-dipyrromethene (BODIPY) molecules are widely used as laser dyes and have therefore become a popular research topic within recent decades. Numerous studies have been reported for the rational design of BODIPY derivatives based on their spectroscopic and photophysical properties, including absorption and fluorescence wavelengths (<i>λ</i><sub>abs</sub> and <i>λ</i><sub>fl</sub>), oscillator strength (<i>f</i>), nonradiative pathways, and quantum yield (<i>ϕ</i>). In the present work, we illustrate a theoretical, semi-empirical model that accurately predicts <i>ϕ</i> for various BODIPY compounds based on inexpensive electronic structure calculations, following the data-driven algorithm proposed and tested on the naphthalene family by us [Kohn, Lin, and Van Voorhis, <i>J. Phys. Chem. C.</i> <b>2019</b>, <i>123</i>, 15394]. The model allows us to identify the dominant nonradiative channel of any BODIPY molecule using its structure exclusively and to establish a correlation between the activation energy (<i>E</i><sub>a</sub>) and the fluorescence quantum yield (<i>ϕ</i><sub>fl</sub>). Based on our calculations, either the S<sub>1</sub> → S<sub>0</sub> or <i>L<sub>a</sub></i> → <i>L<sub>b</sub></i> internal conversion (IC) mechanism dominates in the majority of BODIPY derivatives, depending on the structural and electronic properties of the substituents. In both cases, the nonradiative rate (<i>k</i><sub>nr</sub>) exhibits a straightforward Arrhenius-like relation with the associated <i>E</i><sub>a</sub>. More interestingly, the S<sub>1</sub> → S<sub>0</sub> mechanism proceeds via a highly distorted intermediate structure in which the core BODIPY plane and the substituent at the 1-position are forced to bend, while the internal rotation of the very same substituent induces the <i>La </i>→<i> Lb</i> transition. Our model reproduces <i>k</i><sub>fl</sub>, <i>k</i><sub>nr</sub>, and <i>ϕ</i><sub>fl</sub> to mean absolute errors (MAE) of 0.16 decades, 0.87 decades, and 0.26, when all outliers are considered. These results allow us to validate the predictive power of the proposed data-driven algorithm in <i>ϕ</i><sub>fl</sub>. They also indicate that the model has a great potential to facilitate and accelerate the machine learning aided design of BODIPY dyes for imaging and sensing applications, given sufficient experimental data and appropriate molecular descriptors.</div>

Time-resolved photoelectron imaging of ultrafast S2→S1 internal conversion through conical intersection in pyrazine

2010 ◽  
Vol 132 (17) ◽  
pp. 174302 ◽  
Author(s):  
Yoshi-Ichi Suzuki ◽  
Takao Fuji ◽  
Takuya Horio ◽  
Toshinori Suzuki
Keyword(s):  
Internal Conversion ◽  
Conical Intersection ◽  
Photoelectron Imaging ◽  
Time Resolved

scholarly journals Fluorescence Quantum Yield and Free Rotor Effect

1984 ◽  
Vol 4 (1-6) ◽  
pp. 305-310 ◽  
Author(s):  
M. S. A. Abdel-Mottaleb
Keyword(s):  
Quantum Yield ◽  
Fluorescence Quantum Yield ◽  
Internal Conversion ◽  
Structural Changes ◽  
Wave Length ◽  
Solvent Viscosity ◽  
Dependent Rate ◽  
Picosecond Time Scale ◽  
Viscous Media ◽  
Different Parts

It was found that the weakly fluorescent trans-2(4′-N,N-dimethylaminostyryl)- pyridinium betaine dyestuff (1) becomes efficiently fluorescent in very viscous media. The fluorescence quantum yield (φF) for dyestuff (1) approaches unity in ethanol–ether (1 : 1) glass at 98 K. Moreover, the fluorescence wave-length is blue shifted (1874 cm−1) when the temperature is lowered to 98 K. The results are rationalized as being due to solvent viscosity dependent rate constant for a radiationless internal conversion process, involving rotation of the different parts of the molecule, a free rotor effect. The rate of internal rotation was estimated to be 3.4 × 1011 s−1. The results suggest that this molecule can be used as a fluorescent probe to study microscopic structural changes in surrounding media occurring on the picosecond time scale.

Sign in / Sign up

Export Citation Format

Share Document