Determination of the highest occupied molecular orbital and cationic structure of 2-chloropyridine by one-photon VUV-MATI spectroscopy and Franck–Condon fitting

2020 ◽  
Vol 22 (36) ◽  
pp. 20858-20866 ◽  
Author(s):  
Yu Ran Lee ◽  
Nayoung Choi ◽  
Chan Ho Kwon
Keyword(s):  
Molecular Orbital ◽  
Chlorine Atom ◽  
Highest Occupied Molecular Orbital ◽  
Mati Spectroscopy ◽  
Franck Condon

Substitution of a chlorine atom for the H in pyridine alters the HOMO of the molecule, which ultimately affects the cationic structure.

Studies of the First Electronically Excited State of 3-Fluoropyridine and its Ionic Structure by Means of REMPI, Two-Photon MATI, One-Photon VUV-MATI Spectroscopy and Franck-Condon Analysis

2021 ◽  
Author(s):  
Niklas Helle ◽  
Tim Raeker ◽  
Jürgen Grotemeyer
Keyword(s):  
Vacuum Ultraviolet ◽  
Ionic Structure ◽  
Two Photon ◽  
Electronically Excited State ◽  
Electronically Excited ◽  
Photon Ionization ◽  
Mati Spectroscopy ◽  
Franck Condon ◽  
Photon Resonance

3-Fluoropyridine (3-FP) has been investigated by means of two-photon resonance-enhanced multi photon ionization (REMPI), mass-analyzed threshold ionization (MATI) and one-photon vacuum-ultraviolet (VUV) MATI spectroscopy. The aim was the determination of...

Determination of the cationic conformational structure of tetrahydrothiophene by one-photon MATI spectroscopy and Franck–Condon fitting

2020 ◽  
Vol 22 (11) ◽  
pp. 6184-6191 ◽  
Author(s):  
Yu Ran Lee ◽  
Hong Lae Kim ◽  
Chan Ho Kwon
Keyword(s):  
Accurate Information ◽  
Conformational Structure ◽  
Conformational Interconversion ◽  
Mati Spectroscopy ◽  
Franck Condon

This study affords more accurate information regarding the pseudorotational PES describing the conformational interconversion of THT.

scholarly journals Isolation and structure determination of missing fullerenes Gd@C 74 (CF 3 ) n through in situ trifluoromethylation

2018 ◽  
Vol 5 (9) ◽  
pp. 181015 ◽  
Author(s):  
Ayano Nakagawa ◽  
Shinobu Aoyagi ◽  
Haruka Omachi ◽  
Katsuma Ishino ◽  
Makiko Nishino ◽  
...  
Keyword(s):  
Molecular Orbital ◽  
High Performance ◽  
Density Functional ◽  
Crystallographic Analysis ◽  
X Ray ◽  
Multi Stage ◽  
Highest Occupied Molecular Orbital ◽  
Lowest Unoccupied Molecular Orbital

Our trifluoromethyl functionalization method enables the dissolution and isolation of missing metallofullerenes of Gd@C 74 (CF 3 ) n . After multi-stage high-performance liquid chromatography purification, Gd@C 74 (CF 3 ) 3 and two regioisomers of Gd@C 74 (CF 3 ) are isolated. X-ray crystallographic analysis reveals that all of the isolated metallofullerenes react with CF 3 groups on pentagons of the D 3 h -symmetry C 74 cages. Highest occupied molecular orbital-lowest unoccupied molecular orbital gaps of these trifluoromethylated derivatives, estimated by absorption spectra, are in the range 0.71–1.06 eV, consistent with density functional calculations.

Radical Enzymes Control the Chemistry of Their Highly Reactive Intermediates Using the Quantum Coulombic Effect

2020 ◽  
Author(s):  
Hossein Khalilian ◽  
Gino A. DiLabio
Keyword(s):  
Hydrogen Bonding ◽  
Molecular Orbital ◽  
Reactive Intermediates ◽  
Hydrogen Bonding Interaction ◽  
Orbital Ordering ◽  
Dynamic Nature ◽  
Radical Intermediate ◽  
Highest Occupied Molecular Orbital ◽  
Bonding Interaction ◽  
Close Proximity

Here, we report an exquisite strategy that the B12 enzymes exploit to manipulate the reactivity of their radical intermediate (Adenosyl radical). Based on the quantum-mechanic calculations, these enzymes utilize a little known long-ranged through space quantum Coulombic effect (QCE). The QCE causes the radical to acquire an electronic structure that contradicts the Aufbau Principle: The singly-occupied molecular orbital (SOMO) is no longer the highest-occupied molecular orbital (HOMO) and the radical is unable to react with neighbouring substrates. The dynamic nature of the enzyme and its structure is expected to be such that the reactivity of the radical is not restored until it is moved into close proximity of the target substrate. We found that the hydrogen bonding interaction between the nearby conserved glutamate residue and the ribose ring of Adenosyl radical plays a crucial role in manipulating the orbital ordering

Radical Enzymes Control the Chemistry of Their Highly Reactive Intermediates Using the Quantum Coulombic Effect

2020 ◽  
Author(s):  
Hossein Khalilian ◽  
Gino A. DiLabio
Keyword(s):  
Hydrogen Bonding ◽  
Molecular Orbital ◽  
Reactive Intermediates ◽  
Hydrogen Bonding Interaction ◽  
Orbital Ordering ◽  
Dynamic Nature ◽  
Radical Intermediate ◽  
Highest Occupied Molecular Orbital ◽  
Bonding Interaction ◽  
Close Proximity

Here, we report an exquisite strategy that the B12 enzymes exploit to manipulate the reactivity of their radical intermediate (Adenosyl radical). Based on the quantum-mechanic calculations, these enzymes utilize a little known long-ranged through space quantum Coulombic effect (QCE). The QCE causes the radical to acquire an electronic structure that contradicts the Aufbau Principle: The singly-occupied molecular orbital (SOMO) is no longer the highest-occupied molecular orbital (HOMO) and the radical is unable to react with neighbouring substrates. The dynamic nature of the enzyme and its structure is expected to be such that the reactivity of the radical is not restored until it is moved into close proximity of the target substrate. We found that the hydrogen bonding interaction between the nearby conserved glutamate residue and the ribose ring of Adenosyl radical plays a crucial role in manipulating the orbital ordering

scholarly journals Electronic Properties of Triangle Molybdenum Disulfide (MoS2) Clusters with Different Sizes and Edges

Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 1157
Author(s):  
Songsong Wang ◽  
Changliang Han ◽  
Liuqi Ye ◽  
Guiling Zhang ◽  
Yangyang Hu ◽  
...  
Keyword(s):  
Quantum Chemistry ◽  
Electronic Properties ◽  
Absorption Spectra ◽  
Molecular Orbital ◽  
Electronic Structures ◽  
Edge States ◽  
Frontier Orbitals ◽  
Edge Structure ◽  
Highest Occupied Molecular Orbital ◽  
Lowest Unoccupied Molecular Orbital

The electronic structures and transition properties of three types of triangle MoS2 clusters, A (Mo edge passivated with two S atoms), B (Mo edge passivated with one S atom), and C (S edge) have been explored using quantum chemistry methods. The highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap of B and C is larger than that of A, due to the absence of the dangling of edge S atoms. The frontier orbitals (FMOs) of A can be divided into two categories, edge states from S3p at the edge and hybrid states of Mo4d and S3p covering the whole cluster. Due to edge/corner states appearing in the FMOs of triangle MoS2 clusters, their absorption spectra show unique characteristics along with the edge structure and size.

scholarly journals Photoconductivity of Low-Bandgap Polymer and Polymer: Fullerene Bulk Heterojunction Studied by Constant Photocurrent Method

2015 ◽  
Vol 3 (1) ◽  
Author(s):  
V. V. Malov ◽  
A. R. Tameev ◽  
S. V. Novikov ◽  
M. V. Khenkin ◽  
A. G. Kazanskii ◽  
...  
Keyword(s):  
Molecular Orbital ◽  
Bulk Heterojunction ◽  
Inorganic Materials ◽  
Fullerene Derivative ◽  
Approximation Procedure ◽  
Photoelectric Properties ◽  
Highest Occupied Molecular Orbital ◽  
Donor Acceptor ◽  
Lowest Unoccupied Molecular Orbital ◽  
Doped Polymers

AbstractOptical and photoelectric properties of modern photosensitive polymers are of great interest due to their prospects for photovoltaic applications. In particular, an investigation of absorption and photoconductivity edge of these materials could provide valuable information. For these purpose we applied the constant photocurrent method which has proved its efficiency for inorganic materials. PCDTBT and PTB7 polymers were used as objects for the study as well as their blends with a fullerene derivative PC71BM. The measurements by constant photocurrent method (CPM) show that formation of bulk heterojunction (BHJ) in the blends increases photoconductivity and results in a redshift of the photocurrent edge in the doped polymers compared with that in the neat polymers. Obtained from CPM data, spectral dependences of absorption coefficient were approximated using Gaussian distribution of density-of-states within HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) bands. The approximation procedure allowed us to evaluate rather optical than electrical bandgaps for the studied materials. Moreover, spectra of polymer:PC71BM blends were fitted well by the sum of two Gaussian peaks which reveal both the transitions within the polymer and the transitions involving charge transfer states at the donor-acceptor interface in the BHJ.

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