The use of localized and delocalized orbitals in a Rydberg expanded correlation analysis of the cycloaddition of ethylene

1983 ◽  
Vol 61 (2) ◽  
pp. 306-311 ◽  
Author(s):  
Earl M. Evleth ◽  
Emil Kassab
Keyword(s):  
Correlation Analysis ◽  
Ground State ◽  
Rydberg State ◽  
Singlet State ◽  
Correlation Diagram ◽  
State Correlation ◽  
Localized State ◽  
Valence Level

Rydberg expanded orbital and state correlation diagrams are shown for the classical cycloaddition of ethylene. The diagrams are first developed at the localized valence MO level and the origins of the S**-bitriplet correlations are shown. When extended to the Rydberg level, the localized state correlation diagram shows that the π3s Rydberg singlet state of ethylene can interact with the ground state of another ethylene to directly yield the same S** surface as found in the valence-level-only diagram. In this manner the Rydberg state eventually derydbergizes.

The high pressure photochemistry of alkenes. III. The 184.9 nm photoisomerization processes in acyclic alkenes

1985 ◽  
Vol 63 (7) ◽  
pp. 1424-1430 ◽  
Author(s):  
Guy J. Collin ◽  
Hélène Deslauriers
Keyword(s):  
Ground State ◽  
Internal Conversion ◽  
Rydberg State ◽  
Singlet State ◽  
Hydrogen Shift ◽  
Geometric Isomerization ◽  
Trans Isomerization ◽  
Show Evidence ◽  
Structural Isomerization ◽  
Π State

We have made a systematic study of the 184.9 nm photoisomerization of the gaseous acyclic alkenes. Apart from the cis-trans isomerization (geometric isomerization), we have also observed the formation of products arising from the 1,3-hydrogen and methylene shifts (structural isomerization). 1-Alkenes do not show evidence of structural isomerization. This kind of isomerization increases with an increase in the number of alkyl substituents around the double bond. These observations, combined with those from the literature, may be explained on the basis of the following: (a) the 1π,π* state is involved in the cis–trans isomerization process; (b) the 1π,R(3s) state is responsible for the methylene shifts; (c) another singlet state is required for the 1,3-hydrogen shift; (d) this last state is either at an energy level higher than that of the Rydberg state or the hot ground state. Finally, the photoexcited molecules, through internal conversion, may convert from one state to another, and their lifetime is long enough to be stabilized by collision.

Photophysics of trioxatriangulenium ion. Electrophilic reactivity in the ground state and excited singlet state

2002 ◽  
Vol 1 (10) ◽  
pp. 763-773 ◽  
Author(s):  
Jóhannes Reynisson ◽  
Robert Wilbrandt ◽  
Vibeke Brinck ◽  
Bo W. Laursen ◽  
Kasper Nørgaard ◽  
...  
Keyword(s):  
Ground State ◽  
Singlet State ◽  
Excited Singlet State ◽  
Excited Singlet ◽  
Electrophilic Reactivity

On the formation of cavitylike small-polaronic states in solid deuterium

1985 ◽  
Vol 63 (1) ◽  
pp. 94-98 ◽  
Author(s):  
S. K. Bose ◽  
J. D. Poll
Keyword(s):  
Ground State ◽  
Continuum Model ◽  
State Energy ◽  
Stark Shift ◽  
Localized State ◽  
Solid Deuterium ◽  
Vibrational Levels ◽  
Radiation Induced ◽  
Absorption Features ◽  
Ground State Energies

Certain infrared absorption features in tritiated as well as proton-irradiated samples of solid deuterium have been attributed to the formation of bubblelike electronic states localized in the lattice. These bubblelike states are shown to be energetically stable in the Wigner–Seitz model of the crystal and the gap between the ground-state energies in the bubble and the quasi-free states of the electron is calculated. An initial trapping of the electron by a vacancy is assumed in calculating the localized state energy. Calculations based on a continuum model of the solid yield the radius of such bubbles to close agreement with that obtained from the observed Stark shift of the vibrational levels of the neighbouring molecules due to the localized electrons. The model is used to interpret the radiation-induced absorption in proton-irradiated solid deuterium in the spectral region 4000–7500 cm−1.

Sulfamoyl nitrenes: singlet or triplet ground state?

2018 ◽  
Vol 54 (48) ◽  
pp. 6136-6139 ◽  
Author(s):  
Yan Lu ◽  
Hongmin Li ◽  
Manabu Abe ◽  
Didier Bégué ◽  
Huabin Wan ◽  
...  
Keyword(s):  
Triplet State ◽  
Ground State ◽  
Singlet State ◽  
Minimum Energy ◽  
Closed Shell ◽  
Low Energy ◽  
Energy Minimum ◽  
Triplet Ground State ◽  
Crossing Point

Two prototypical sulfamoyl nitrenes R2NS(O)2–N (R = H and Me) in the triplet state were generated via the closed-shell singlet state by passing a low-energy minimum energy crossing point (MECP).

Multi-mode ground state interaction terms in C60-based electron donor-acceptor complexes

Open Physics ◽  
2004 ◽  
Vol 2 (2) ◽  
Author(s):  
Elena Sheka
Keyword(s):  
Ground State ◽  
Singlet State ◽  
Molecular Complexes ◽  
Suggested Approach ◽  
Interaction Terms ◽  
Binary Complexes ◽  
Avoided Crossing ◽  
Donor Acceptor ◽  
Multi Mode ◽  
Chemical Testing

AbstractQuantum-chemical testing of donor-acceptor properties of binary molecular complexes, related to the singlet state, is suggested as QCh calculations of studied systems and their constituents by using both spin-nondependent (RHF) and spindependent (UHF) versions of the exploited computational tool. The avoided crossing of intermolecular interaction terms of neutral moleculesE int(A 0 B 0) and molecular ionsE int(A + B −) causes a multi-mode character of the ground state term. The dependence of D-A complex properties on the type of the term, space positions of the term minimum, and the interrelation of the corresponding energies are discussed. The suggested approach has been applied to binary complexes C60+X (X=TAE, TDAE, DMMA, COANP, 2Li, Mg).

scholarly journals Multipolarity of the2−→1−, ground-state transition inBi210via multivariable angular correlation analysis

2016 ◽  
Vol 94 (1) ◽  
Author(s):  
N. Cieplicka-Oryńczak ◽  
B. Szpak ◽  
S. Leoni ◽  
B. Fornal ◽  
D. Bazzacco ◽  
...  
Keyword(s):  
Correlation Analysis ◽  
Angular Correlation ◽  
Ground State ◽  
State Transition ◽  
Ground State Transition
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