The article introduces a robust algorithm for the computation of minimum energy paths transiting along regions of near-to or degeneracy of adiabatic states. The method facilitates studies of excited state reactivity involving weakly avoided crossings and conical intersections. Based on the analysis of the change in the multiconfigurational wave function the algorithm takes the decision whether the optimization should continue following the same electronic state or switch to a different state. This algorithm helps to overcome convergence difficulties near degeneracies. The implementation in the MOLCAS quantum chemistry package is discussed. To demonstrate the utility of the proposed procedure four examples of application are provided: thymine, asulam, 1,2-dioxetane, and a three-double-bond model of the 11-cis-retinal protonated Schiff base.

Schapiro, I., Roca Sanjuán, D., Lindh, R., Olivucci, M. (2015). A surface hopping algorithm for nonadiabatic minimum energy path calculations. JOURNAL OF COMPUTATIONAL CHEMISTRY, 36(5), 312-20-320 [10.1002/jcc.23805].

A surface hopping algorithm for nonadiabatic minimum energy path calculations

OLIVUCCI, MASSIMO
2015-01-01

Abstract

The article introduces a robust algorithm for the computation of minimum energy paths transiting along regions of near-to or degeneracy of adiabatic states. The method facilitates studies of excited state reactivity involving weakly avoided crossings and conical intersections. Based on the analysis of the change in the multiconfigurational wave function the algorithm takes the decision whether the optimization should continue following the same electronic state or switch to a different state. This algorithm helps to overcome convergence difficulties near degeneracies. The implementation in the MOLCAS quantum chemistry package is discussed. To demonstrate the utility of the proposed procedure four examples of application are provided: thymine, asulam, 1,2-dioxetane, and a three-double-bond model of the 11-cis-retinal protonated Schiff base.
2015
Schapiro, I., Roca Sanjuán, D., Lindh, R., Olivucci, M. (2015). A surface hopping algorithm for nonadiabatic minimum energy path calculations. JOURNAL OF COMPUTATIONAL CHEMISTRY, 36(5), 312-20-320 [10.1002/jcc.23805].
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11365/977031
 Attenzione

Attenzione! I dati visualizzati non sono stati sottoposti a validazione da parte dell'ateneo