A surface hopping algorithm for nonadiabatic minimum energy path calculations. Issue 5 (6th January 2015)

• Record Type: Journal Article
• Authors: Schapiro, Igor; Roca‐Sanjuán, Daniel; Lindh, Roland; Olivucci, Massimo
• Is Part Of: Journal of computational chemistry. Volume 36:Issue 5(2015)
• Page Start: 312
• Page End: 320
• Publication Date: 2015-01-06
• Subjects: Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.23805
• Languages: English
• ISSNs: 0192-8651

Abstract

<abstract abstract-type="main"> <title> <x xml:space="preserve">Abstract</x> </title> <p>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‐<italic>cis</italic>‐retinal protonated Schiff base. © 2015 Wiley Periodicals, Inc.</p> </abstract>