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.

Download
Es wurde kein Volltext hochgeladen. Nur Publikationsnachweis!
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
Ausgabe
11
Art.-Nr.
114110
ISSN
eISSN
PUB-ID

Zitieren

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.

95 References

Daten bereitgestellt von Europe PubMed Central.


AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0
Ab initio potential-energy surfaces for complex, multichannel systems using modified novelty sampling and feedforward neural networks.
Raff LM, Malshe M, Hagan M, Doughan DI, Rockley MG, Komanduri R., J Chem Phys 122(8), 2005
PMID: 15836017

AUTHOR UNKNOWN, 0
A nested molecule-independent neural network approach for high-quality potential fits.
Manzhos S, Wang X, Dawes R, Carrington T Jr., J Phys Chem A 110(16), 2006
PMID: 16623455
Using neural networks to represent potential surfaces as sums of products.
Manzhos S, Carrington T Jr., J Chem Phys 125(19), 2006
PMID: 17129087
Generalized neural-network representation of high-dimensional potential-energy surfaces.
Behler J, Parrinello M., Phys. Rev. Lett. 98(14), 2007
PMID: 17501293
Parametrization of analytic interatomic potential functions using neural networks.
Malshe M, Narulkar R, Raff LM, Hagan M, Bukkapatnam S, Komanduri R., J Chem Phys 129(4), 2008
PMID: 18681638

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0
Effects of higher order Jahn-Teller coupling on the nuclear dynamics.
Viel A, Eisfeld W., J Chem Phys 120(10), 2004
PMID: 15267319
Higher order (A+E) multiply sign in circle e pseudo-Jahn-Teller coupling.
Eisfeld W, Viel A., J Chem Phys 122(20), 2005
PMID: 15945734

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0
Interpolation of diabatic potential energy surfaces.
Evenhuis CR, Collins MA., J Chem Phys 121(6), 2004
PMID: 15281848
Interpolation of diabatic potential-energy surfaces: quantum dynamics on ab initio surfaces.
Evenhuis CR, Lin X, Zhang DH, Yarkony D, Collins MA., J Chem Phys 123(13), 2005
PMID: 16223278
Interpolation of multidimensional diabatic potential energy matrices.
Godsi O, Evenhuis CR, Collins MA., J Chem Phys 125(10), 2006
PMID: 16999513
Full-Dimensional Quantum State-to-State Nonadiabatic Dynamics for Photodissociation of Ammonia in its A-Band.
Xie C, Ma J, Zhu X, Zhang DH, Yarkony DR, Xie D, Guo H., J Phys Chem Lett 5(7), 2014
PMID: 26274448

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0
Material in PUB:
Dissertation, die diesen PUB Eintrag enthält

Export

Markieren/ Markierung löschen
Markierte Publikationen

Open Data PUB

Web of Science

Dieser Datensatz im Web of Science®

Quellen

PMID: 27004865
PubMed | Europe PMC

Suchen in

Google Scholar