English
 
User Manual Privacy Policy Disclaimer Contact us
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
 
 
DownloadE-Mail
  TD-DFT and DFT/MRCI study of electronic excitations in Violaxanthin and Zeaxanthin

Götze, J. P., & Thiel, W. (2013). TD-DFT and DFT/MRCI study of electronic excitations in Violaxanthin and Zeaxanthin. Chemical Physics, 415, 247-255. doi:10.1016/j.chemphys.2013.01.030.

Item is

Basic

show hide
Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0014-A3E0-6 Version Permalink: http://hdl.handle.net/11858/00-001M-0000-0014-A3E1-4
Genre: Journal Article

Files

show Files
hide Files
:
mmc1.pdf (Supplementary material), 65KB
Name:
mmc1.pdf
Description:
Supporting information
Visibility:
Public
MIME-Type / Checksum:
application/pdf / [MD5]
Technical Metadata:
Copyright Date:
-
Copyright Info:
-
License:
-

Locators

show

Creators

show
hide
 Creators:
Götze, J. P.1, Author              
Thiel, Walter1, Author              
Affiliations:
1Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445590              

Content

show
hide
Free keywords: Time-dependent density functional theory TD-DFT Xanthophyll Vibrational broadening Bond length alternation DFT configuration interaction DFT-CI DFT/MRCI Violaxanthin Zeaxanthin Solvent effect
 Abstract: We report vibrationally broadened Franck–Condon (FC) spectra of Violaxanthin (Vx) and Zeaxanthin (Zx) for the lowest-energy 1Ag → 1Bu band that arises from the bright HOMO → LUMO single-electron excitation. Geometries were optimized using standard (1Ag) and time-dependent (1Bu) density functional theory (DFT) at the (TD-)CAM-B3LYP/6-31G(d) level, both in the gas phase and in acetone using a polarizable continuum model (PCM). DFT/MRCI multireference calculations were performed at the optimized (TD)-CAM-B3LYP structures to evaluate the energies of doubly excited states that are not accessible to linear response TD-DFT theory. The FC spectra were calculated using the time-independent (TI) scheme. The calculated spectra of Vx and Zx are very similar, with a red shift of about 0.1 eV for Zx relative to Vx, which is in agreement with the experimental data. The predicted spectral peaks of Vx and Zx deviate from experiment by less than 0.1 eV when performing the calculations in the gas phase. In the presence of acetone (PCM model), there are larger deviations so that a state specific correction scheme needs to be applied, which accounts for non-equilibrium solvent relaxation. The 1Ag → 1Bu vertical absorption energies and the corresponding vertical fluorescence energies from TD-CAM-B3LYP and DFT/MRCI agree reasonably well. The DFT/MRCI absorption and fluorescence energies for the doubly excited 2Ag and 2Bu states are found to be rather sensitive to the underlying geometry, in particular to the bond length alternation in the polyene chain. In acetone (PCM), Vx and Zx show little bond alternation, and thus the doubly excited Bu state becomes the lowest excited Bu state. (TD)-CAM-B3LYP appears to be suitable for generating realistic geometries for higher-level calculations in such molecules.

Details

show
hide
Language(s): eng - English
 Dates: 2012-10-152013-01-222013-01-312013-03-29
 Publication Status: Published in print
 Pages: 9
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1016/j.chemphys.2013.01.030
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Chemical Physics
  Abbreviation : Chem. Phys.
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: Amsterdam : North-Holland
Pages: 9 Volume / Issue: 415 Sequence Number: - Start / End Page: 247 - 255 Identifier: ISSN: 0301-0104
CoNE: https://pure.mpg.de/cone/journals/resource/954925509371