The Non-Ergodic Nature of Internal Conversion

• Published in: Chemphyschem Vol. 15; no. 2; pp. 249 - 259
• Main Authors: Sølling, Theis I., Kuhlman, Thomas S., Stephansen, Anne B., Klein, Liv B., Møller, Klaus B.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 03.02.2014; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Subjects: Atomic and molecular physics; electronic structure; Electronic structure of atoms, molecules and their ions: theory; energy localization; Exact sciences and technology; internal conversion; molecular dynamics; Molecular properties and interactions with photons; Photoelectron spectra; Physics; Potential energy surfaces; Photoelectron spectra; Peptides; energy localization; Electronically excited state; Molecular dynamics; Vibronic interaction; Momentum; Chemical reactions; Excited states; Electronic structure; Transition energy; Potential energy surfaces; Internal conversion; Phase space; Organic compounds; Ultrafast process; potential energy surfaces; molecular dynamics; internal conversion; electronic structure
• ISSN: 1439-4235; 1439-7641
• DOI: 10.1002/cphc.201300926

The absorption of light by molecules can induce ultrafast dynamics and coupling of electronic and nuclear vibrational motion. The ultrafast nature in many cases rests on the importance of several potential energy surfaces in guiding the nuclear motion—a concept of central importance in many aspects of chemical reaction dynamics. This Minireview focuses on the non‐ergodic nature of internal conversion, that is, on the concept that the nuclear dynamics only sample a reduced phase space, potentially resulting in localization of the dynamics in real space. A series of results that highlight the nonstatistical nature of the excited‐state deactivation process is presented. The examples are categorized into four groups. 1) Localization of the energy in one degree of freedom in S2→S1 transitions, in which the transition is either determined by the time spent in the S2→S1 coupling region or by the time it takes to reach it. 2) Localization of energy into a single reactive mode, which is dictated by the internal conversion process. 3) Initiation of the internal conversion by activation of a single complex motion, which then specifically couples to a reactive mode. 4) Nonstatistical internal conversion as a tool to accomplish biomolecular stability. Herein, the discussion on nonstatistical internal conversion in DNA as a mechanism to eliminate electronic excitation energy is extended to include molecules with an SS bond as a model of the disulfide bridge in peptides. All of these examples are summed up in Kasha’s rule. For systems with multiple degrees of freedom it will be possible to locate an appropriate motion somewhere in phase space that will take the wavepacket to the coupling region and facilitate an ultrafast transition to S1. Once at S1, the momentum of the wavepacket is lost and the only options left are the statistical processes of reaction or light emission. Spotlight on energy localization: Coupling of electronic states by specific vibrational degrees of freedom leads to ultrafast internal conversion in a range of different molecular systems. The electronic structure defines the potential energy surfaces, but it is the nuclear dynamics that restricts and determines what parts of the surfaces will be visited during the transition processes (see picture).