Title :
Performance of DFT Methods in the Calculation of Optical Spectra of Chromophores
Author :
Andzelm, J. ; Rawlett, A. ; Dougherty, John ; Govind, N. ; Baer, R.
Author_Institution :
Res. Lab., Weapons & Mater. Directorate, US Army, Aberdeen, MD
Abstract :
We present electronic structure calculations on the ultraviolet/visible (UV-Vis) spectra of highly active pushpull chromophores. In particular, we have implemented and applied the recently developed long-range corrected Baer-Neuhauser-Livshits (BNL) exchange-correlation functional. We have implemented this functional in the NWChem program package. The UV-Vis spectra obtained with the BNL functional are found to be superior compared with other density functional theory (DFT) functionals. The method captures the charge-transfer states particularly well while the pi-pi* excitations are less accurate. Consideration of the chromophore conformations also improves the strength of the pi-pi* excitations.
Keywords :
charge transfer states; density functional theory; molecular configurations; molecular electronic states; organic compounds; ultraviolet spectra; visible spectra; DFT methods; NWChem program package; UV spectra; charge-transfer states; density functional theory functionals; electronic structure calculations; highly active pushpull chromophore conformations; long-range corrected Baer-Neuhauser-Livshits exchange-correlation functional; optical spectra; pi-pi* excitations; ultraviolet spectra; visible spectra; Chemistry; Computational Intelligence Society; Density functional theory; Hafnium; Nonlinear optics; Optical fiber networks; Optical materials; Packaging; Raw materials; Weapons;
Conference_Titel :
DoD HPCMP Users Group Conference, 2008. DOD HPCMP UGC
Conference_Location :
Seattle, WA
Print_ISBN :
978-1-4244-3323-0
DOI :
10.1109/DoD.HPCMP.UGC.2008.80
