Block-diagonalization as a tool for the robust diabatization of high-dimensional potential energy surfaces

Venghaus F, Eisfeld W (2016)
JOURNAL OF CHEMICAL PHYSICS 144(11): 114110.

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Zeitschriftenaufsatz | Veröffentlicht | Englisch
Abstract / Bemerkung
Robust diabatization techniques are key for the development of high-dimensional coupled potential energy surfaces (PESs) to be used in multi-state quantum dynamics simulations. In the present study we demonstrate that, besides the actual diabatization technique, common problems with the underlying electronic structure calculations can be the reason why a diabatization fails. After giving a short review of the theoretical background of diabatization, we propose a method based on the block-diagonalization to analyse the electronic structure data. This analysis tool can be used in three different ways: First, it allows to detect issues with the ab initio reference data and is used to optimize the setup of the electronic structure calculations. Second, the data from the block-diagonalization are utilized for the development of optimal parametrized diabatic model matrices by identifying the most significant couplings. Third, the block-diagonalization data are used to fit the parameters of the diabatic model, which yields an optimal initial guess for the non-linear fitting required by standard or more advanced energy based diabatization methods. The new approach is demonstrated by the diabatization of 9 electronic states of the propargyl radical, yielding fully coupled full-dimensional (12D) PESs in closed form. (C) 2016 AIP Publishing LLC.
Erscheinungsjahr
Zeitschriftentitel
JOURNAL OF CHEMICAL PHYSICS
Band
144
Zeitschriftennummer
11
Artikelnummer
114110
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eISSN
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Venghaus F, Eisfeld W. Block-diagonalization as a tool for the robust diabatization of high-dimensional potential energy surfaces. JOURNAL OF CHEMICAL PHYSICS. 2016;144(11): 114110.
Venghaus, F., & Eisfeld, W. (2016). Block-diagonalization as a tool for the robust diabatization of high-dimensional potential energy surfaces. JOURNAL OF CHEMICAL PHYSICS, 144(11), 114110. doi:10.1063/1.4943869
Venghaus, F., and Eisfeld, W. (2016). Block-diagonalization as a tool for the robust diabatization of high-dimensional potential energy surfaces. JOURNAL OF CHEMICAL PHYSICS 144:114110.
Venghaus, F., & Eisfeld, W., 2016. Block-diagonalization as a tool for the robust diabatization of high-dimensional potential energy surfaces. JOURNAL OF CHEMICAL PHYSICS, 144(11): 114110.
F. Venghaus and W. Eisfeld, “Block-diagonalization as a tool for the robust diabatization of high-dimensional potential energy surfaces”, JOURNAL OF CHEMICAL PHYSICS, vol. 144, 2016, : 114110.
Venghaus, F., Eisfeld, W.: Block-diagonalization as a tool for the robust diabatization of high-dimensional potential energy surfaces. JOURNAL OF CHEMICAL PHYSICS. 144, : 114110 (2016).
Venghaus, Florian, and Eisfeld, Wolfgang. “Block-diagonalization as a tool for the robust diabatization of high-dimensional potential energy surfaces”. JOURNAL OF CHEMICAL PHYSICS 144.11 (2016): 114110.

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