When do we need to account for the geometric phase in excited state dynamics?
We investigate the role of the geometric phase (GP) in an internal conversion process when the system changes its electronic state by passing through a conical intersection (CI). Local analysis of a two-dimensional linear vibronic coupling (LVC) model Hamiltonian near the CI shows that the role of the GP is twofold. First, it compensates for a repulsion created by the so-called diagonal Born–Oppenheimer correction. Second, the GP enhances the non-adiabatic transition probability for a wave-packet part that experiences a central collision with the CI. To assess the significance of both GP contributions we propose two indicators that can be computed from parameters of electronic surfaces and initial conditions. To generalize our analysis to N-dimensional systems we introduce a reduction of a general N-dimensional LVC model to an effective 2D LVC model using a mode transformation that preserves short-time dynamics of the original N-dimensional model. Using examples of the bis(methylene) adamantyl and butatriene cations, and the pyrazine molecule we have demonstrated that their effective 2D models reproduce the short-time dynamics of the corresponding full dimensional models, and the introduced indicators are very reliable in assessing GP effects.
- Department of Physical and Environmental Sciences, University of Toronto Scarborough, Toronto, Ontario M1C 1A4 (Canada)
- Publication Date:
- OSTI Identifier:
- Resource Type:
- Journal Article
- Resource Relation:
- Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 21; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
- Country of Publication:
- United States
- 74 ATOMIC AND MOLECULAR PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BORN-OPPENHEIMER APPROXIMATION; CATIONS; EXCITED STATES; HAMILTONIANS; INTERNAL CONVERSION; TWO-DIMENSIONAL CALCULATIONS; WAVE PACKETS