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Role of non-Condon vibronic coupling and conformation change on two-photon absorption spectra of green fluorescent protein
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0002-3915-300X
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0003-0007-0394
2013 (English)In: Molecular Physics, ISSN 0026-8976, E-ISSN 1362-3028, Vol. 111, no 9-11, 1316-1321 p.Article in journal (Refereed) Published
Abstract [en]

Two-photon absorption spectra of green fluorescent proteins (GFPs) often show a blue-shift band compared to their conventional one-photon absorption spectra, which is an intriguing feature that has not been well understood. We present here a systematic study on one- and two-photon spectra of GFP chromophore by means of the density functional response theory and complete active space self-consistent field (CASSCF) methods. It shows that the popular density functional fails to provide correct vibrational progression for the spectra. The non-Condon vibronic coupling, through the localised intrinsic vibrational modes of the chromophore, is responsible for the blue-shift in the TPA spectra. The cis to trans isomerisation can be identified in high-resolution TPA spectra. Our calculations demonstrate that the high level ab initio multiconfigurational CASSCF method, rather than the conventional density functional theory is required for investigating the essential excited-state properties of the GFP chromophore.

Place, publisher, year, edition, pages
2013. Vol. 111, no 9-11, 1316-1321 p.
Keyword [en]
non-Condon vibronic coupling, two-photon absorption spectra, green fluorescent proteins (GFP)
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-122173DOI: 10.1080/00268976.2013.771800ISI: 000323409600026Scopus ID: 2-s2.0-84882453867OAI: oai:DiVA.org:kth-122173DiVA: diva2:621179
Note

QC 20130930

Available from: 2013-05-14 Created: 2013-05-14 Last updated: 2017-12-06Bibliographically approved
In thesis
1. Electron-vibration coupling and its effects on optical and electronic properties of single molecules
Open this publication in new window or tab >>Electron-vibration coupling and its effects on optical and electronic properties of single molecules
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The thesis is devoted to theoretical investigations of electron-vibration coupling and its effects on optical and electronic properties of single molecules, especially for molecules confined between metallic electrodes.

A density-matrix approach has been developed to describe the photon emission of single molecules confined in the scanning tunneling microscope (STM). With this new method electronic excitations induced by both the tunneling electron and the localized surface plasmon (LSP) can be treated on an equal footing. Model calculations for porphyrin derivatives have successfully reproduced and explained the experimentally observed unusual variation of the photon emission spectra. The method has also been extended to study the STM induced fluorescence and phosphorescence of C60 molecules in combination with the first principles calculations. In particularly, the non-Condon vibronic couplings have been exclusively included in the calculations. The experimental spectra have been nicely reproduced by our calculations, which also enable us to identify the unique spectral fingerprint and origin of the measured spectra. The observed rich spectral features have been finally correctly assigned.

The electron transport properties of molecular junctions with bipyridine isomers have been studied in the sequential tunneling (SET) regime by assuming that the molecules are weakly coupled to metallic electrodes. It is shown that the strong electron-vibration coupling in the 2, 2’-bipyridine molecule and the 4,4’-bipyridine molecule can lead to observable Franck-Condon blockade. Taking advantage of such novel effect, a gate-controlled conductance switch with ideal on-off ratio has been proposed for a molecular junction with the 4, 4’-bipyridine molecule.

The effect of the electron-vibration coupling on one-photon and two-photon absorption spectra of green fluorescent protein (GFP) has been systematically examined. The hydroxybenzylidene-2, 3-dimethylimidazolinone molecule in the deprotonated anion state (HBDI) is used to model the fluorescence chromophore of the GFP. Both Condon and non-Condon vibronic couplings have been considered in the calculations. The calculated spectra are in good agreement with the available experimental spectra. It confirms the notion that the observed blue-shift of the two-photon absorption spectrum with respect to its one-photon absorption counterpart is caused by the non-Condon vibronic coupling.

All the calculations are carried out with our own software package, DynaVib. It is capable of modeling a variety of vibrational-resolved spectroscopies, such as absorption, emission, and resonant Raman scattering (RRS) spectra. In our package, the Duschinsky rotation and non-Condon effect have been fully taken into account. Both time-independent and time-dependent approaches have been implemented, allowing to simulate the spectra of very large molecules.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2013. xiv, 66 p.
Series
Trita-BIO-Report, ISSN 1654-2312 ; 2013:10
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-122180 (URN)978-91-7501-773-0 (ISBN)
Public defence
2013-06-07, FA32, AlbaNova University Center, Roslagstullsbacken 21, Stockholm, 14:00 (English)
Opponent
Supervisors
Note

QC 20130520

Available from: 2013-05-20 Created: 2013-05-14 Last updated: 2013-05-20Bibliographically approved

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