Geometric phase effects in low-energy dynamics near conical intersections: A study of the multidimensional linear vibronic coupling model

Journal Article · Sat Dec 21 04:00:00 EST 2013 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4844095· OSTI ID:22253758

Joubert-Doriol, Loïc; Ryabinkin, Ilya G.; Izmaylov, Artur F. ^[1]

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1. Department of Physical and Environmental Sciences, University of Toronto Scarborough, Toronto, Ontario M1C 1A4 (Canada)

In molecular systems containing conical intersections (CIs), a nontrivial geometric phase (GP) appears in the nuclear and electronic wave functions in the adiabatic representation. We study GP effects in nuclear dynamics of an N-dimensional linear vibronic coupling (LVC) model. The main impact of GP on low-energy nuclear dynamics is reduction of population transfer between the local minima of the LVC lower energy surface. For the LVC model, we proposed an isometric coordinate transformation that confines non-adiabatic effects within a two-dimensional subsystem interacting with an N − 2 dimensional environment. Since environmental modes do not couple electronic states, all GP effects originate from nuclear dynamics within the subsystem. We explored when the GP affects nuclear dynamics of the isolated subsystem, and how the subsystem-environment interaction can interfere with GP effects. Comparing quantum dynamics with and without GP allowed us to devise simple rules to determine significance of the GP for nuclear dynamics in this model.

• OSTI ID: 22253758
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 23 Vol. 139; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
COUPLING
INTERACTIONS
WAVE FUNCTIONS