No data available.
Please log in to see this content.
You have no subscription access to this content.
No metrics data to plot.
The attempt to load metrics for this article has failed.
The attempt to plot a graph for these metrics has failed.
The full text of this article is not currently available.
Communication: Smoothing out excited-state dynamics: Analytical gradients for dynamically weighted complete active space self-consistent field
11. R. E. Blankenship, Molecular Mechanisms of Photosynthesis (Blackwell Science, Oxford, 2002).
12. G. S. Engel, T. R. Calhoun, E. L. Read, T.-K. Ahn, T. Mancal, Y.-C. Cheng, R. E. Blankenship, and G. R. Fleming, Nature (London) 446, 782 (2007).
16. M. E. Casida, in Recent Advances in Density Functional Methods, edited by D. P. Chong (World Scientific, Singapore, 1995), p. 155.
29.It should be noted that these issues are not necessarily independent: orbital rotations and symmetry breakings may occur due to an unweighted state crossing.
31.Although the energy expression depends also on N, the total number of states included in the DW averaging, it is recommended this number be increased to convergence whereupon any higher state is introduced with zero weight for all geometries of interest.
33. H.-J. Werner
, P. J. Knowles
, G. Knizia
, F. R. Manby
, M. Schütz et al.
, version 2012.1, a package of ab initio
programs, 2012, see http://www.molpro.net
36.If the adaptive timesteps reached 1 au and the total classical energy was still not conserved to the desired tolerance (as seen in SA-4-CASSCF dynamics), the adaptive timestepping was aborted and propagation was resumed with the original 10-au timestep.
Article metrics loading...
State averaged complete active space self-consistent field (SA-CASSCF) is a workhorse for determining the excited-state electronic structure of molecules, particularly for states with multireference character; however, the method suffers from known issues that have prevented its wider adoption. One issue is the presence of discontinuities in potential energy surfaces when a state that is not included in the state averaging crosses with one that is. In this communication I introduce a new dynamical weight with spline (DWS) scheme that mimics SA-CASSCF while removing energy discontinuities due to unweighted state crossings. In addition, analytical gradients for DWS-CASSCF (and other dynamically weighted schemes) are derived for the first time, enabling energy-conserving excited-state
molecular dynamics in instances where SA-CASSCF fails.
Full text loading...
Most read this month