Nonadiabatic transition-state theory: A Monte Carlo study of competing bond fission processes in bromoacetyl chloride

2001 ◽  
Vol 114 (4) ◽  
pp. 1700-1708 ◽  
Author(s):  
Alison J. Marks
Keyword(s):  
Monte Carlo ◽  
Transition State ◽  
Transition State Theory ◽  
Monte Carlo Study ◽  
State Theory ◽  
Nonadiabatic Transition

scholarly journals Simulations of long time scale dynamics using the dimer method

2001 ◽  
Vol 677 ◽  
Author(s):  
Graeme Henkelman ◽  
Hannes Jónsson
Keyword(s):  
Monte Carlo ◽  
Monte Carlo Method ◽  
Transition State ◽  
Time Scale ◽  
Transition State Theory ◽  
Kinetic Monte Carlo ◽  
Chem Phys ◽  
State Theory ◽  
Kinetic Monte Carlo Method ◽  
Long Time

We have carried out long time scale simulations where the “dimer method” [G. Henkelman and H. Jónsson, J. Chem. Phys. 111, 7010 (1999)] is used to find the mechanism and estimate the rate of transitions within harmonic transition state theory and time is evolved by using the kinetic Monte Carlo method. Unlike traditional applications of kinetic Monte Carlo, the atoms are not assigned to lattice sites and a list of all possible transitions does not need to be specified beforehand. Rather, the relevant transitions are found on the y during the simulation. An application to the diffusion and island formation of Al adatoms on an Al(100) surface is presented.

ELECTRON TRANSFER RATE UNIFORMLY VALID FROM NONADIABATIC TO ADIABATIC REGIME BASED ON THE ZHU–NAKAMURA THEORY

2006 ◽  
Vol 05 (spec01) ◽  
pp. 299-306 ◽  
Author(s):  
YI ZHAO ◽  
HIROKI NAKAMURA
Keyword(s):  
Electron Transfer ◽  
Transition State ◽  
Transfer Rate ◽  
Transition State Theory ◽  
Numerical Solutions ◽  
Present Theory ◽  
State Theory ◽  
Electron Transfer Rate ◽  
Nonadiabatic Transition ◽  
Potential Applicability

On the basis of the generalized nonadiabatic transition state theory recently introduced to remedy the crucial deficiencies of the conventional transition state theory, we have presented a new formula for electron transfer rate, which can cover the whole range from adiabatic to nonadiabatic regime in the absence of solvent dynamics control. The rate is expressed as a product of the well-known Marcus theory and a new coefficient that represents the effects of nonadiabatic transition at the crossing seam surface. The numerical comparisons are performed with different approaches and the present approach shows an excellent agreement with the quantum mechanical numerical solutions from weak to strong electronic coupling. The explanation of the experimental data of Nelsen et al. manifests the potential applicability of the present theory.

Intersystem crossing in tunneling regime: T1 → S0 relaxation in thiophosgene

2020 ◽  
Vol 22 (10) ◽  
pp. 5500-5508 ◽  
Author(s):  
Aleksandr O. Lykhin ◽  
Sergey A. Varganov
Keyword(s):  
Transition State ◽  
Quantum Tunneling ◽  
Transition State Theory ◽  
Electronic States ◽  
State Theory ◽  
Intersystem Crossing ◽  
Nonadiabatic Transition ◽  
Insight Into

The nonadiabatic transition state theory provides insight into the T1 → S0 intersystem crossing in thiophosgene driven by quantum tunneling through the barrier formed by the crossing T1 and S0 electronic states.

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