scholarly journals Electronic structure and time-dependent description of rotational predissociation of LiH

2017 ◽  
Vol 19 (30) ◽  
pp. 19777-19783 ◽  
Author(s):  
P. Jasik ◽  
J. E. Sienkiewicz ◽  
J. Domsta ◽  
N. E. Henriksen
Keyword(s):  
Electronic Structure ◽  
Potential Energy ◽  
Adiabatic Potential ◽  
Time Dependent ◽  
Potential Energy Curves ◽  
First Time ◽  
Π State ◽  
Classical Experiment

The adiabatic potential energy curves of the LiH molecule have been calculated. By solving the TDSE, the classical experiment of Velasco on dissociation in the 1Π state has been explained for the first time in detail.

scholarly journals Electronic structure and rovibrational predissociation of the 21Π state in KLi

2018 ◽  
Vol 20 (27) ◽  
pp. 18663-18670
Author(s):  
P. Jasik ◽  
J. Kozicki ◽  
T. Kilich ◽  
J. E. Sienkiewicz ◽  
N. E. Henriksen
Keyword(s):  
Electronic Structure ◽  
Potential Energy ◽  
Internuclear Distance ◽  
Adiabatic Potential ◽  
Potential Energy Curves ◽  
Time Propagation ◽  
Rovibrational States ◽  
Π State

Adiabatic potential energy curves of the 31Σ+, 33Σ+, 21Π and 23Π states correlating for large internuclear distance with the K(4s) + Li(2p) atomic asymptote were calculated. Lifetimes of the quasi-bound rovibrational states of the 21Π state were determined by explicit time propagation.

scholarly journals Vibronic Origin of the “SKEWED” Anticline Configuration of the Hydrogen Peroxide Molecule

2008 ◽  
Vol 3 (1) ◽  
pp. 105-111
Author(s):  
N. N. Gorinchoy ◽  
I. Ya. Ogurtsov ◽  
Ion Arsene
Keyword(s):  
Hydrogen Peroxide ◽  
Electronic Structure ◽  
Potential Energy ◽  
Ab Initio Calculations ◽  
Ab Initio ◽  
Adiabatic Potential ◽  
Potential Energy Curves ◽  
High Symmetry ◽  
Analytical Expression ◽  
Peroxide Molecule

The vibronic origin of instability of the symmetrical forms (D¥ h, C2h and C2v) of the hydrogen peroxide molecule H2O2 was revealed using ab initio calculations of the electronic structure and the adiabatic potential energy curves. The vibronic constants in this approach were estimated by fitting of the ab initio calculated adiabatic potential in the vicinity of the high-symmetry nuclear configurations to its analytical expression. It was shown that the equilibrium “skewed” anticline shape of the C2 symmetry can be realized in two ways: D¥h ® C2v® C2 or D¥h ® C2h® C2 with the decreasing of the adiabatic potential energy at every step.

Potential-energy curves, zero-field splittings, and radiative lifetimes for low-lying states of AsH

1987 ◽  
Vol 65 (2) ◽  
pp. 155-164 ◽  
Author(s):  
Toshio Matsushita ◽  
Christel M. Marian ◽  
Rainer Klotz ◽  
Sigrid D. Peyerimhoff
Keyword(s):  
Fine Structure ◽  
Potential Energy ◽  
Ground State ◽  
Zero Order ◽  
Potential Energy Curves ◽  
Basis Set ◽  
Zero Field ◽  
Spin Orbit ◽  
Spin Orbit Interactions ◽  
Π State

Large-scale multireference configuration-interaction (MRD-CI) calculations in an atomic-orbital (AO) basis set containing up to f functions on As and d on hydrogen are employed to study the potential-energy curves of the π2(X3Σ−, a1Δ, b1Σ+), the σ → π, and the π → σ3.1Π states; a large number of σ → σ* states; and the lowest π → s,p Rydberg series. The σ → σ* states are strongly repulsive and exhibit numerous interactions with the Rydberg members causing predissociation. The probabilities for the spin-forbidden transitions from b1Σ+and a1Δ to the X3Σ−ground state as well as the zero-field splittings of theX3Σ−and A3Π states have been evaluated by employing a variational perturbation scheme in which the zero-order wave functions are MRD-CI expansions. The perturber states are determined by their spin-orbit interactions, which are calculated by employing the Breit–Pauli one- and two-electron spin-orbit operator. The radiative lifetime of the b1Σ+ state is predicted to be 0.35 ms, whereby the dominant mechanism is deactivation to the ms = ±1 component.The parallel transition is found to be much weaker. The lifetime of a1Δ is calculated to be 22 ms, whereby the process [Formula: see text] is favored. Both b–X and a–X transitions borrow their intensity primarily from the A3Π–X3Σ− transition and, furthermore, the 1Π–a1Δ and higher 3,1Π state spin-allowed transitions. The probability for the quadrupole b–a transition is evaluated to be three orders of magnitude smaller than the b–X transition. The calculated zero-field splitting of the X3Σ− ground state amounts to 101.4 cm−1, and the fine-structure splitting between the 2, 1, and 0+ components of the A3Π state evaluated to be 544.5 and 674.4 cm−1, respectively, in good accord with experimental results; whereas the calculated Λ doubling of the0+–0− fine-structure levels of the A3Π state (35.2 cm−1 vs. 44.72 cm−1) is too small in the present treatment. The dependence of spin-orbit effects and transition probabilities on AO basis sets and relativistic corrections to the zero-order Hamiltonian are discussed, and it is concluded that lifetime calculations for spin-forbidden processes in first- and second-row molecules can be extended in a fairly straightforward manner to systems with considerable spin-orbit interactions.

Exploring the electronic states of the hydroxyl dication OH2+: thermodynamic (meta)stability, bound-free emission spectra, and charge transfer processes

2021 ◽  
Author(s):  
Gabriel Fernando de Melo ◽  
Klaus Franzreb ◽  
Fernando R. Ornellas
Keyword(s):  
Electronic Structure ◽  
Charge Transfer ◽  
Potential Energy ◽  
Electronic States ◽  
Emission Spectra ◽  
Potential Energy Curves ◽  
Structure Approach ◽  
Transfer Processes ◽  
Stability Bound ◽  
Highly Correlated

Accurate potential energy curves were constructed for a manifold of electronic states of the hydroxyl dication using a highly correlated electronic structure approach (SA-CASSCF/ MRCI+Q/aug-cc-pV5Z). The existence of a bound...

scholarly journals Electronic spectra of ytterbium fluoride from relativistic electronic structure calculations

2021 ◽  
Author(s):  
Johann V. Pototschnig ◽  
Kenneth G. Dyall ◽  
Lucas Visscher ◽  
André Severo Pereira Gomes
Keyword(s):  
Electronic Structure ◽  
Potential Energy ◽  
Electronic Spectra ◽  
Electronic Structure Calculations ◽  
Potential Energy Curves ◽  
Electronic Structure Methods ◽  
Structure Calculations ◽  
Ytterbium Fluoride

Potential energy curves for the YbF obtained by relativistic electronic structure methods are presented. Due to the difficulties of describing this system separate computations for open and closed f-shells were necessary.

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