6533b86efe1ef96bd12cbeb2
RESEARCH PRODUCT
A surface hopping algorithm for nonadiabatic minimum energy path calculations
Roland LindhMassimo OlivucciMassimo OlivucciDaniel Roca-sanjuánIgor Schapirosubject
Surface PropertiesComputationSurface hoppingCASSCFretinalHeterocyclic Compounds 1-RingHeterocyclic CompoundsasulamConvergence (routing)dioxetaneAdiabatic processWave functionSchiff BasesChemistrysurface hopping algorithmGeneral ChemistryKineticsComputational MathematicsExcited statePath (graph theory)RetinaldehydeQuantum TheoryThermodynamicsCarbamatesCASSCF; asulam; dioxetane; minimum energy path; retinal; surface hopping algorithm; thymineProtonsDegeneracy (mathematics)Algorithmminimum energy pathAlgorithmsThyminedescription
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.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2015-01-06 | Journal of Computational Chemistry |