Activation of C2H6by Gas-Phase Ta+: Potential Energy Surfaces, Spin−Orbit Coupling, Spin-Inversion Probabilities, and Reaction Mechanisms

2009 ◽  
Vol 28 (21) ◽  
pp. 6160-6170 ◽  
Author(s):  
Ling-Ling Lv ◽  
Yong-Cheng Wang ◽  
Zhi-Yuan Geng ◽  
Yu-Bing Si ◽  
Qiang Wang ◽  
...  
Keyword(s):  
Potential Energy ◽  
Gas Phase ◽  
Reaction Mechanisms ◽  
Potential Energy Surfaces ◽  
Orbit Coupling ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Energy Surfaces ◽  
Spin Inversion

Spin-orbit coupling and the intersection of potential energy surfaces in polyatomic molecules

1976 ◽  
Vol 351 (1664) ◽  
pp. 141-150 ◽  
Keyword(s):  
Potential Energy ◽  
Configuration Space ◽  
Potential Energy Surfaces ◽  
Polyatomic Molecules ◽  
Orbit Coupling ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Lower Symmetry ◽  
Symmetry Species ◽  
Energy Surfaces

Longuet-Higgins’ theorem, which shows that the existence of intersections between potential energy surfaces may be deduced from the behaviour of the wavefunction at points remote from the intersection, is generalized to cover cases where the Hamiltonian is complex. It is concluded that an intersection due to symmetry in one region of nuclear configuration space may imply that the same surfaces intersect over a region of higher dimen­sion and lower symmetry where their wavefunctions belong to the same symmetry species. It is shown that this behaviour occurs in d 1 octahedral complexes in the presence of spin-orbit coupling.

Refined potential-energy surfaces for the 2A" and à 2A' electronic states of the HO2 molecule

2001 ◽  
Vol 79 (2-3) ◽  
pp. 641-652 ◽  
Author(s):  
P Jensen ◽  
R J Buenker ◽  
J -P Gu ◽  
G Osmann ◽  
P R Bunker
Keyword(s):  
Dipole Moment ◽  
Potential Energy ◽  
Electric Dipole ◽  
Potential Energy Surfaces ◽  
Electronic States ◽  
Spin Component ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Vibronic State ◽  
Energy Surfaces

In a previous paper (G. Osmann et al. J. Mol. Spectrosc. 197, 262 (1999)) we calculated ab initio the potential-energy surfaces of the ground [Formula: see text]2A" and excited Ã2A' electronic states of the HO2 molecule; these two states correlate with a 2Π state at linearity and participate in a Renner effect interaction. In that paper, we also calculated the electric- and magnetic-dipole moment and transition-moment surfaces, and the spin-orbit coupling constant; we then simulated the à ® [Formula: see text] emission band system including both electric-dipole and magnetic-dipole transitions. We now calculate more points on the surfaces to cover a wider range of bending geometries, and then refine the surfaces by fitting to rovibronic term values for both electronic states simultaneously. In the fitting we include levels having J values up to 9/2 and term values up to about 8000 cm–1. In our calculation of the energy levels we allow for the Renner effect and spin-orbit coupling by using our variational computer program RENNER. A good fitting to the data is obtained and as a result we obtain an accurate representation of these two potential surfaces over an energy range of more than 1 eV. We tabulate the vibronic energies up to 1 eV for both HO2 and DO2. We can explain the origin of a perturbation observed in the F1 spin component levels of the Ã(0, 0, 0) vibronic state for J values around 51/2; this is caused by a spin-orbit interaction satisfying Δ N = ± 1 with the F2 spin component levels of the [Formula: see text](1,1,2) vibronic state. Using the new rovibronic energies and wave functions, with our ab initio electric dipole moment and transition moment surfaces, we calculate Stark coefficients and compare them with experiment for some ground vibronic state levels. PACS Nos.: 31.20D, 31.50, 33.10, 33.20E, 35.20D, 35.20J

scholarly journals Reduced-Dimensionality Quantum Dynamics Study of the 3Fe(CO)4 + H2 → 1FeH2(CO)4 Spin-inversion Reaction

Molecules ◽  
2020 ◽  
Vol 25 (4) ◽  
pp. 882 ◽  
Author(s):  
Toshiyuki Takayanagi ◽  
Yuya Watabe ◽  
Takaaki Miyazaki
Keyword(s):  
Potential Energy ◽  
Potential Energy Surfaces ◽  
Quantum Dynamics ◽  
Reaction Probability ◽  
Spin Orbit ◽  
Inversion Point ◽  
Nonadiabatic Transition ◽  
Metal Compounds ◽  
Energy Surfaces ◽  
Spin Inversion

Many chemical reactions of transition metal compounds involve a change in spin state via spin inversion, which is induced by relativistic spin-orbit coupling. In this work, we theoretically study the efficiency of a typical spin-inversion reaction, 3Fe(CO)4 + H2 → 1FeH2(CO)4. Structural and vibrational information on the spin-inversion point, obtained through the spin-coupled Hamiltonian approach, is used to construct three degree-of-freedom potential energy surfaces and to obtain singlet-triplet spin-orbit couplings. Using the developed spin-diabatic potential energy surfaces in reduced dimensions, we perform quantum nonadiabatic transition state wave packet calculations to obtain the cumulative reaction probability. The calculated cumulative reaction probability is found to be significantly larger than that estimated from the one-dimensional surface-hopping probability. This indicates the importance of both multidimensional and nuclear quantum effects in spin inversion for polyatomic chemical reaction systems.

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