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research article

Non-adiabatic coupling vectors within linear response time-dependent density functional theory

Tavernelli, I.  
•
Tapavicza, E.  
•
Rothlisberger, U.  
2009
The Journal of Chemical Physics

A method is developed to compute the nonadiabatic coupling vectors (NACVs) between electronic ground and excited states as well as between any possible pair of excited states within the framework of linear response time-dependent density functional theory (TDDFT) in the adiabatic approximation. The development is an extension to our previous work on surface hopping dynamics [E. Tapavicza , Phys. Rev. Lett. 98, 023001 (2007)] for which we improve the description of the TDDFT approximation of the excited state wavefunctions by means of linear response orbitals. The method is first validated on the H+H-2 system that has a region of strong coupling near the conical intersection at the equilateral geometry. These results confirm the quality and the numerical efficiency of the approach, which has an accuracy comparable to the one achieved with wavefunction-based methods. Finally, we apply the method to the calculation of the NACVs of protonated formaldimine (NH2CH2+) along a surface hopping trajectory initiated in the second excited state.

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Type
research article
DOI
10.1063/1.3097192
Web of Science ID

WOS:000264775200010

Author(s)
Tavernelli, I.  
•
Tapavicza, E.  
•
Rothlisberger, U.  
Date Issued

2009

Published in
The Journal of Chemical Physics
Volume

130

Article Number

124107

Subjects

density functional theory

•

excited states

•

ground states

•

Tamm-Dancoff Approximation

•

Conical Intersections

•

Molecular-Dynamics

•

Excited-States

•

Electronic Excitations

•

Perturbation-Theory

•

Charge-Transfer

•

System

•

Simulations

•

Transitions

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCBC  
Available on Infoscience
April 11, 2009
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/37078
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