Perturbed ground state method for electron transfer

1999 ◽  
Vol 111 (17) ◽  
pp. 7818-7827 ◽  
Author(s):  
Oleg V. Prezhdo ◽  
James T. Kindt ◽  
John C. Tully
Keyword(s):  
Electron Transfer ◽  
Ground State ◽  
State Method

Redox Thermodynamics for Oxygen Species (O3, O2, HOO·, O2-, HOOH, HOO-, O, O-, and HO-); Effects of Media and pH

1992 ◽  
Author(s):  
Donald T. Sawyer ◽  
R. J. P. Williams
Keyword(s):  
Electron Transfer ◽  
Photosystem Ii ◽  
Oxygen Atom ◽  
Ground State ◽  
Energy Transduction ◽  
Oxygen Species ◽  
Oxygen Atom Transfer ◽  
Green Plants ◽  
Redox Thermodynamics ◽  
Effects Of Media

Biological systems activate ground-state dioxygen (3O2) for controlled energy transduction and chemical syntheses via electron-transfer and hydrogen-atomtransfer reduction to O2-, HOO·, and HOOH. These reduction products are further activated with metalloproteins to accomplish oxygen atom-transfer chemistry. Conversely, green plants via photosystem II facilitate the oxidation of chemistry.

scholarly journals Halogen-Bond Assisted Photoinduced Electron Transfer

Molecules ◽  
2019 ◽  
Vol 24 (23) ◽  
pp. 4361
Author(s):  
Bogdan Dereka ◽  
Ina Fureraj ◽  
Arnulf Rosspeintner ◽  
Eric Vauthey
Keyword(s):  
Electron Transfer ◽  
Excited State ◽  
Ground State ◽  
Halogen Bond ◽  
Quenching Rate ◽  
Excited Complex ◽  
Diffusion Controlled ◽  
Donor Acceptor ◽  
Quenching Rate Constant ◽  
Excited State Population

The formation of a halogen-bond (XB) complex in the excited state was recently reported with a quadrupolar acceptor–donor–acceptor dye in two iodine-based liquids (J. Phys. Chem. Lett. 2017, 8, 3927–3932). The ultrafast decay of this excited complex to the ground state was ascribed to an electron transfer quenching by the XB donors. We examined the mechanism of this process by investigating the quenching dynamics of the dye in the S1 state using the same two iodo-compounds diluted in inert solvents. The results were compared with those obtained with a non-halogenated electron acceptor, fumaronitrile. Whereas quenching by fumaronitrile was found to be diffusion controlled, that by the two XB compounds is slower, despite a larger driving force for electron transfer. A Smoluchowski–Collins–Kimball analysis of the excited-state population decays reveals that both the intrinsic quenching rate constant and the quenching radius are significantly smaller with the XB compounds. These results point to much stronger orientational constraint for quenching with the XB compounds, indicating that electron transfer occurs upon formation of the halogen bond.

Ground-state electron transfer in all-polymer donor–acceptor heterojunctions

2020 ◽  
Vol 19 (7) ◽  
pp. 738-744 ◽  
Author(s):  
Kai Xu ◽  
Hengda Sun ◽  
Tero-Petri Ruoko ◽  
Gang Wang ◽  
Renee Kroon ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Ground State ◽  
State Electron ◽  
Donor Acceptor ◽  
Ground State Electron

scholarly journals Role of active site conformational changes in photocycle activation of the AppA BLUF photoreceptor

2017 ◽  
Vol 114 (7) ◽  
pp. 1480-1485 ◽  
Author(s):  
Puja Goyal ◽  
Sharon Hammes-Schiffer
Keyword(s):  
Electron Transfer ◽  
Free Energy ◽  
Excited State ◽  
Charge Transfer ◽  
Conformational Changes ◽  
Ground State ◽  
Active Site ◽  
Locally Excited ◽  
Proton Relay ◽  
Locally Excited State

Blue light using flavin adenine dinucleotide (BLUF) proteins are essential for the light regulation of a variety of physiologically important processes and serve as a prototype for photoinduced proton-coupled electron transfer (PCET). Free-energy simulations elucidate the active site conformations in the AppA (activation of photopigment and puc expression) BLUF domain before and following photoexcitation. The free-energy profile for interconversion between conformations with either Trp104 or Met106 closer to the flavin, denoted Trpin/Metout and Trpout/Metin, reveals that both conformations are sampled on the ground state, with the former thermodynamically favorable by ∼3 kcal/mol. These results are consistent with the experimental observation of both conformations. To analyze the proton relay from Tyr21 to the flavin via Gln63, the free-energy profiles for Gln63 rotation were calculated on the ground state, the locally excited state of the flavin, and the charge-transfer state associated with electron transfer from Tyr21 to the flavin. For the Trpin/Metout conformation, the hydrogen-bonding pattern conducive to the proton relay is not thermodynamically favorable on the ground state but becomes more favorable, corresponding to approximately half of the configurations sampled, on the locally excited state. The calculated energy gaps between the locally excited and charge-transfer states suggest that electron transfer from Tyr21 to the flavin is more facile for configurations conducive to proton transfer. When the active site conformation is not conducive to PCET from Tyr21, Trp104 can directly compete with Tyr21 for electron transfer to the flavin through a nonproductive pathway, impeding the signaling efficiency.

5d and 4f electron configuration of CeB6 at 340 and 535 K

2008 ◽  
Vol 64 (5) ◽  
pp. 534-549 ◽  
Author(s):  
Ryoko Makita ◽  
Kiyoaki Tanaka ◽  
Yoshichika Ōnuki
Keyword(s):  
Electron Transfer ◽  
Crystal Field ◽  
Ground State ◽  
Room Temperature ◽  
Atomic Orbital ◽  
Energy Levels ◽  
Electron Configuration ◽  
Acta Cryst ◽  
X Ray ◽  
The Difference

X-ray atomic orbital (XAO) analysis revealed that at both temperatures the electrons are transferred from B 2px (= py ) to Ce 5d and 4f orbitals. At 340 K 5d(j = 5/2)Γ8 orbitals are occupied partially, but 4f(j = 5/2)Γ8 orbitals are more populated than 4f(j = 5/2)Γ7 orbitals, in contrast to our observation at 430 K [Makita et al. (2007). Acta Cryst. B63, 683–692]. At 535 K the XAO analysis revealed clearly that the order of the energy levels of 4f(j = 5/2)Γ8 and Γ7 states reversed again and is the same as that at room temperature. It also limited the possible 5d configurations to three models among the nine possible ones. However, the XAO analysis could not decide which of the three models was the best with the present accuracy of the measurement. Two of them have partially and fully occupied 5d(j = 5/2)Γ7 orbitals and the remaining one has a fully occupied 5d(j = 3/2)Γ8 orbital. Since the lobes of 5d(j = 3/2)Γ8 or 5d(j = 5/2)Γ7 orbitals do not overlap with the 4f(j = 5/2)Γ8 orbitals as well as the 5d(j = 5/2)Γ8 orbitals, the order of the energy levels of the 4f(j = 5/2) orbitals became the same as that at room temperature. These results indicate that the crystal field varies with temperature due to the electron transfer from B 2p to Ce 5d orbitals. The difference densities after the spherical-atom refinement at the three temperatures clearly revealed the different combinations of 4f and 5d orbitals which are occupied. In the present study positive peaks due to the 4f electrons appear near the Ce nucleus and those due to 5d orbitals are found in the area outside the 4f peaks. Between the two areas there is a negative area distributed spherically at 340 K. The negative area produced by the contraction of 4f(j = 5/2)Γ8 orbitals seems to reduce the electron repulsion of the 5d(j = 5/2)Γ8 orbitals and helps the 4f(j = 5/2)Γ8 orbitals to remain as the ground state.

Electron-transfer biradical intermediates in ground-state reactions

1976 ◽  
Vol 40 (2) ◽  
pp. 347-352 ◽  
Author(s):  
Teruhiro Takabe ◽  
Kizashi Yamaguchi
Keyword(s):  
Electron Transfer ◽  
Ground State
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