Excited state geometry of photoactive yellow protein chromophore

A combined conductorlike polarizable continuum model and time-dependent density functional study

Yali Wang, Hui Li

Research output: Contribution to journalArticle

59 Citations (Scopus)

Abstract

Analytic gradient of the combined conductorlike polarizable continuum model (CPCM) and time-dependent density functional theory method is derived and implemented. Due to the use of the fixed points with variable areas tessellation scheme, the excited state potential energy surfaces (PESs) are rigorously continuous and smooth. The CPCM/TD-B3LYP method is used to study an analog of the photoactive yellow protein chromophore, anionic thiomethyl p -coumaric acid (TMpCA-). Although CPCM/TD-B3LYP method may not be accurate in predicting solvent effect on vertical excitation of TMpCA-, it may be used to predict redshiftings of emission maxima relative to absorption maxima with an accuracy of ∼0.1 eV. We also found that the excited trans- TMpCA- tends to form a single bond twisted structure in the gas phase but a double bond twisted structure in aqueous solution. The TD-B3LYP minimum energy isomerization pathway shows a barrier of 3.6 kcal/mol in aqueous solution and 5.2 kcal/mol in the gas phase. The gas phase double bond twisted structure is trapped in a well of the excited state PES, with a depth of ∼20 kcal/mol (0.88 eV), in good agreement with an experimental value of ∼1 eV.

Original languageEnglish (US)
Article number034108
JournalJournal of Chemical Physics
Volume133
Issue number3
DOIs
StatePublished - Jul 21 2010

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Chromophores
Excited states
chromophores
Potential energy surfaces
Gases
vapor phases
continuums
proteins
Geometry
geometry
potential energy
aqueous solutions
excitation
Proteins
Isomerization
isomerization
Density functional theory
analogs
density functional theory
gradients

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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title = "Excited state geometry of photoactive yellow protein chromophore: A combined conductorlike polarizable continuum model and time-dependent density functional study",
abstract = "Analytic gradient of the combined conductorlike polarizable continuum model (CPCM) and time-dependent density functional theory method is derived and implemented. Due to the use of the fixed points with variable areas tessellation scheme, the excited state potential energy surfaces (PESs) are rigorously continuous and smooth. The CPCM/TD-B3LYP method is used to study an analog of the photoactive yellow protein chromophore, anionic thiomethyl p -coumaric acid (TMpCA-). Although CPCM/TD-B3LYP method may not be accurate in predicting solvent effect on vertical excitation of TMpCA-, it may be used to predict redshiftings of emission maxima relative to absorption maxima with an accuracy of ∼0.1 eV. We also found that the excited trans- TMpCA- tends to form a single bond twisted structure in the gas phase but a double bond twisted structure in aqueous solution. The TD-B3LYP minimum energy isomerization pathway shows a barrier of 3.6 kcal/mol in aqueous solution and 5.2 kcal/mol in the gas phase. The gas phase double bond twisted structure is trapped in a well of the excited state PES, with a depth of ∼20 kcal/mol (0.88 eV), in good agreement with an experimental value of ∼1 eV.",
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