The role of high-level calculations in the assignment of the Q-band spectra of chlorophyll

Jeffrey R. Reimers, Zheng Li Cai, Rika Kobayashi, Margus Rätsep, Arvi Freiberg, Elmars Krausz

    Research output: Chapter in Book/Report/Conference proceedingConference contributionpeer-review

    2 Citations (Scopus)

    Abstract

    We recently established a novel assignment of the visible absorption spectrum of chlorophyll-a that sees the two components Qx and Qy of the low-energy Q band as being intrinsically mixed by non-adiabatic coupling. This ended 50 years debate as to the nature of the Q bands, with prior discussion poised only in the language of the Born-Oppenheimer and Condon approximations. The new assignment presents significant ramifications for exciton transport and quantum coherence effects in photosystems. Results from state of the art electronic structure calculations have always been used to justify assignments, but quantitative inaccuracies and systematic failures have historically limited usefulness. We examine the role of CAM-B3LYP time-dependent density-functional theory (TD-DFT) and Symmetry Adapted Cluster-Configuration Interaction (SAC-CI) calculations in first showing that all previous assignments were untenable, in justifying the new assignment, in making some extraordinary predictions that were vindicated by the new assignment, and in then identifying small but significant anomalies in the extensive experimental data record.

    Original languageEnglish
    Title of host publicationInternational Conference of Computational Methods in Sciences and Engineering 2014, ICCMSE 2014
    EditorsTheodore E. Simos, Theodore E. Simos, Theodore E. Simos, Theodore E. Simos, Theodore E. Simos, Zacharoula Kalogiratou, Theodore Monovasilis
    PublisherAmerican Institute of Physics Inc.
    Pages18-22
    Number of pages5
    ISBN (Electronic)9780735412552
    DOIs
    Publication statusPublished - 6 Oct 2014
    EventInternational Conference of Computational Methods in Sciences and Engineering 2014, ICCMSE 2014 - Athens, Greece
    Duration: 4 Apr 20147 Apr 2014

    Publication series

    NameAIP Conference Proceedings
    Volume1618
    ISSN (Print)0094-243X
    ISSN (Electronic)1551-7616

    Conference

    ConferenceInternational Conference of Computational Methods in Sciences and Engineering 2014, ICCMSE 2014
    Country/TerritoryGreece
    CityAthens
    Period4/04/147/04/14

    Fingerprint

    Dive into the research topics of 'The role of high-level calculations in the assignment of the Q-band spectra of chlorophyll'. Together they form a unique fingerprint.

    Cite this