Theoretical Studies on the Ground State and Excited State of 2,7-(Ethylene)-bis-8-hydroxyquinoline

2008 ◽  
Vol 21 (3) ◽  
pp. 263-269 ◽  
Author(s):  
Hui-xue Li ◽  
Su-juan Pan ◽  
Xiao-feng Wang ◽  
Tai Xiao
2010 ◽  
Vol 63 (7) ◽  
pp. 1091 ◽  
Author(s):  
Paul G. Wenthold

The thermochemical properties of the benzynes have been the subject of investigation for nearly 50 years. This work provides an overview and assessment of all the experimental thermochemical properties that have been reported for the benzynes, or can be derived from reported thermochemical data. These properties include enthalpies of formation and thermochemical values that correspond to formation and dissociation of the benzynes by neutral and ionic processes. Thermochemical values are provided for both the ground-state singlet and the excited-state triplet states of the benzynes. The starting point for all the thermochemical consideration of the benzynes are the enthalpies of formation, which, in this work, are recommend to be 107.3 ± 3.5, 121.9 ± 3.1, and 138.0 ± 1.0 kcal mol–1 for ortho-, meta-, and para-benzyne, respectively (1 kcal mol–1 = 4.184 kJ mol–1). Whereas the paper predominantly focuses on the experimentally determined values, it also provides a comparison with theoretical studies that have examined the absolute thermochemical properties of the benzynes.


2021 ◽  
Vol 9 ◽  
Author(s):  
Patrick K. Tamukong ◽  
Mark R. Hoffmann

The generalized Van Vleck second order multireference perturbation theory (GVVPT2) method was used to investigate the low-lying electronic states of Ni2. Because the nickel atom has an excitation energy of only 0.025 eV to its first excited state (the least in the first row of transition elements), Ni2 has a particularly large number of low-lying states. Full potential energy curves (PECs) of more than a dozen low-lying electronic states of Ni2, resulting from the atomic combinations 3F4 + 3F4 and 3D3 + 3D3, were computed. In agreement with previous theoretical studies, we found the lowest lying states of Ni2 to correlate with the 3D3 + 3D3 dissociation limit, and the holes in the d-subshells were in the subspace of delta orbitals (i.e., the so-dubbed δδ-states). In particular, the ground state was determined as X 1Γg and had spectroscopic constants: bond length (Re) = 2.26 Å, harmonic frequency (ωe) = 276.0 cm−1, and binding energy (De) = 1.75 eV; whereas the 1 1Σg+ excited state (with spectroscopic constants: Re = 2.26 Å, ωe = 276.8 cm−1, and De = 1.75) of the 3D3 + 3D3 dissociation channel lay at only 16.4 cm−1 (0.002 eV) above the ground state at the equilibrium geometry. Inclusion of scalar relativistic effects through the spin-free exact two component (sf-X2C) method reduced the bond lengths of both of these two states to 2.20 Å, and increased their binding energies to 1.95 eV and harmonic frequencies to 296.0 cm−1 for X 1Γg and 297.0 cm−1 for 1 1Σg+. These values are in good agreement with experimental values of Re = 2.1545 ± 0.0004 Å, ωe = 280 ± 20 cm−1, and D0 = 2.042 ± 0.002 eV for the ground state. All states considered within the 3F4 + 3F4 dissociation channel proved to be energetically high-lying and van der Waals-like in nature. In contrast to most previous theoretical studies of Ni2, full PECs of all considered electronic states of the molecule were produced.


Author(s):  
Ben O. Spurlock ◽  
Milton J. Cormier

The phenomenon of bioluminescence has fascinated layman and scientist alike for many centuries. During the eighteenth and nineteenth centuries a number of observations were reported on the physiology of bioluminescence in Renilla, the common sea pansy. More recently biochemists have directed their attention to the molecular basis of luminosity in this colonial form. These studies have centered primarily on defining the chemical basis for bioluminescence and its control. It is now established that bioluminescence in Renilla arises due to the luciferase-catalyzed oxidation of luciferin. This results in the creation of a product (oxyluciferin) in an electronic excited state. The transition of oxyluciferin from its excited state to the ground state leads to light emission.


1996 ◽  
Vol 6 (9) ◽  
pp. 1167-1180 ◽  
Author(s):  
A. Gicquel ◽  
M. Chenevier ◽  
Y. Breton ◽  
M. Petiau ◽  
J. P. Booth ◽  
...  

2020 ◽  
Author(s):  
Tomislav Rovis ◽  
Benjamin D. Ravetz ◽  
Nicholas E. S. Tay ◽  
Candice Joe ◽  
Melda Sezen-Edmonds ◽  
...  

We describe a new family of catalysts that undergo direct ground state singlet to excited state triplet excitation with IR light, leading to photoredox catalysis without the energy waste associated with intersystem crossing. The finding allows a mole scale reaction in batch using infrared irradiation.


2019 ◽  
Author(s):  
Matthew M. Brister ◽  
Carlos Crespo-Hernández

<p></p><p> Damage to RNA from ultraviolet radiation induce chemical modifications to the nucleobases. Unraveling the excited states involved in these reactions is essential, but investigations aimed at understanding the electronic-energy relaxation pathways of the RNA nucleotide uridine 5’-monophosphate (UMP) have not received enough attention. In this Letter, the excited-state dynamics of UMP is investigated in aqueous solution. Excitation at 267 nm results in a trifurcation event that leads to the simultaneous population of the vibrationally-excited ground state, a longlived <sup>1</sup>n<sub>O</sub>π* state, and a receiver triplet state within 200 fs. The receiver state internally convert to the long-lived <sup>3</sup>ππ* state in an ultrafast time scale. The results elucidate the electronic relaxation pathways and clarify earlier transient absorption experiments performed for uracil derivatives in solution. This mechanistic information is important because long-lived nπ* and ππ* excited states of both singlet and triplet multiplicities are thought to lead to the formation of harmful photoproducts.</p><p></p>


2021 ◽  
Vol 23 (14) ◽  
pp. 8525-8540
Author(s):  
Mudong Feng ◽  
Michael K. Gilson

Ground-state and excited-state molecular dynamics simulations shed light on the rotation mechanism of small, light-driven molecular motors and predict motor performance. How fast can they rotate; how much torque and power can they generate?


1990 ◽  
Vol 26 (5) ◽  
pp. 320 ◽  
Author(s):  
M. Monerie ◽  
T. Georges ◽  
P.L. Francois ◽  
J.Y. Allain ◽  
D. Neveux

2017 ◽  
Vol 474 (16) ◽  
pp. 2713-2731 ◽  
Author(s):  
Athinoula L. Petrou ◽  
Athina Terzidaki

From kinetic data (k, T) we calculated the thermodynamic parameters for various processes (nucleation, elongation, fibrillization, etc.) of proteinaceous diseases that are related to the β-amyloid protein (Alzheimer's), to tau protein (Alzheimer's, Pick's), to α-synuclein (Parkinson's), prion, amylin (type II diabetes), and to α-crystallin (cataract). Our calculations led to ΔG≠ values that vary in the range 92.8–127 kJ mol−1 at 310 K. A value of ∼10–30 kJ mol−1 is the activation energy for the diffusion of reactants, depending on the reaction and the medium. The energy needed for the excitation of O2 from the ground to the first excited state (1Δg, singlet oxygen) is equal to 92 kJ mol−1. So, the ΔG≠ is equal to the energy needed for the excitation of ground state oxygen to the singlet oxygen (1Δg first excited) state. The similarity of the ΔG≠ values is an indication that a common mechanism in the above disorders may be taking place. We attribute this common mechanism to the (same) role of the oxidative stress and specifically of singlet oxygen, (1Δg), to the above-mentioned processes: excitation of ground state oxygen to the singlet oxygen, 1Δg, state (92 kJ mol−1), and reaction of the empty π* orbital with high electron density regions of biomolecules (∼10–30 kJ mol−1 for their diffusion). The ΔG≠ for cases of heat-induced cell killing (cancer) lie also in the above range at 310 K. The present paper is a review and meta-analysis of literature data referring to neurodegenerative and other disorders.


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