skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Excited-state studies of polyacenes: A comparative picture using EOMCCSD, CR-EOMCCSD(T), range-separated (LR/RT)-TDDFT, TD-PM3 and TD-ZINDO

Abstract

The low-lying excited states (L{sub a} and L{sub b}) of polyacenes from naphthalene to heptacene (N = 2-7) are studied using various time-dependent computational approaches. We perform high-level excited-state calculations using equation of motion coupled cluster with singles and doubles (EOMCCSD) and completely renormalized equation of motion coupled cluster with singles, doubles, and perturbative triples (CR-EOMCCSD(T)) and use these results to evaluate the performance of various range-separated exchange-correlation functionals within linearresponse (LR) and real-time (RT) time-dependent density functional theories (TDDFT). As has been reported recently, we find that the range-separated family of functionals address the well-documented TDDFT failures in describing these low-lying singlet excited states to a large extent and are as about as accurate as results from EOMCCSD on average. Real-time TDDFT visualization shows that the excited state charged densities are consistent with the predictions of the perimeter free electron orbital (PFEO) model. This corresponds to particle-on-a-ring confinement, which leads to the well-known red-shift of the excitations with acene length. We also use time-dependent semi-empirical methods like TD-PM3 and TD-ZINDO, which are capable of handling very large systems. Once re-parametrized to match the CR-EOMCCSD(T) results, TD-ZINDO becomes roughly as accurate as range-separated TDDFT, which opens the door to modelingmore » systems such as large molecular assemblies.« less

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1031420
Report Number(s):
PNNL-SA-81719
Journal ID: ISSN 1549-9618; 42591; KP1704020; TRN: US201201%%595
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 7; Journal Issue: 11; Journal ID: ISSN 1549-9618
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CONFINEMENT; DOORS; ELECTRONS; EXCITED STATES; FUNCTIONALS; NAPHTHALENE; PERFORMANCE; RED SHIFT; SIMULATION; equation of motion coupled cluster; time-dependent density functional theories; naphthalene; heptacene; coupled-cluster methods; thin-film transistors; light-emitting-diodes; organic semiconductors; excitation-energies; anthracene; molecules; Environmental Molecular Sciences Laboratory

Citation Formats

Lopata, Kenneth A, Reslan, Randa, Kowalska, Malgorzata I, Neuhauser, Daniel, Govind, Niranjan, and Kowalski, Karol. Excited-state studies of polyacenes: A comparative picture using EOMCCSD, CR-EOMCCSD(T), range-separated (LR/RT)-TDDFT, TD-PM3 and TD-ZINDO. United States: N. p., 2011. Web. doi:10.1021/ct2005165.
Lopata, Kenneth A, Reslan, Randa, Kowalska, Malgorzata I, Neuhauser, Daniel, Govind, Niranjan, & Kowalski, Karol. Excited-state studies of polyacenes: A comparative picture using EOMCCSD, CR-EOMCCSD(T), range-separated (LR/RT)-TDDFT, TD-PM3 and TD-ZINDO. United States. https://doi.org/10.1021/ct2005165
Lopata, Kenneth A, Reslan, Randa, Kowalska, Malgorzata I, Neuhauser, Daniel, Govind, Niranjan, and Kowalski, Karol. 2011. "Excited-state studies of polyacenes: A comparative picture using EOMCCSD, CR-EOMCCSD(T), range-separated (LR/RT)-TDDFT, TD-PM3 and TD-ZINDO". United States. https://doi.org/10.1021/ct2005165.
@article{osti_1031420,
title = {Excited-state studies of polyacenes: A comparative picture using EOMCCSD, CR-EOMCCSD(T), range-separated (LR/RT)-TDDFT, TD-PM3 and TD-ZINDO},
author = {Lopata, Kenneth A and Reslan, Randa and Kowalska, Malgorzata I and Neuhauser, Daniel and Govind, Niranjan and Kowalski, Karol},
abstractNote = {The low-lying excited states (L{sub a} and L{sub b}) of polyacenes from naphthalene to heptacene (N = 2-7) are studied using various time-dependent computational approaches. We perform high-level excited-state calculations using equation of motion coupled cluster with singles and doubles (EOMCCSD) and completely renormalized equation of motion coupled cluster with singles, doubles, and perturbative triples (CR-EOMCCSD(T)) and use these results to evaluate the performance of various range-separated exchange-correlation functionals within linearresponse (LR) and real-time (RT) time-dependent density functional theories (TDDFT). As has been reported recently, we find that the range-separated family of functionals address the well-documented TDDFT failures in describing these low-lying singlet excited states to a large extent and are as about as accurate as results from EOMCCSD on average. Real-time TDDFT visualization shows that the excited state charged densities are consistent with the predictions of the perimeter free electron orbital (PFEO) model. This corresponds to particle-on-a-ring confinement, which leads to the well-known red-shift of the excitations with acene length. We also use time-dependent semi-empirical methods like TD-PM3 and TD-ZINDO, which are capable of handling very large systems. Once re-parametrized to match the CR-EOMCCSD(T) results, TD-ZINDO becomes roughly as accurate as range-separated TDDFT, which opens the door to modeling systems such as large molecular assemblies.},
doi = {10.1021/ct2005165},
url = {https://www.osti.gov/biblio/1031420}, journal = {Journal of Chemical Theory and Computation},
issn = {1549-9618},
number = 11,
volume = 7,
place = {United States},
year = {Tue Nov 08 00:00:00 EST 2011},
month = {Tue Nov 08 00:00:00 EST 2011}
}