Excited-state studies of polyacenes: A comparative picture using EOMCCSD, CR-EOMCCSD(T), range-separated (LR/RT)-TDDFT, TD-PM3 and TD-ZINDO
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.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1031420
- Report Number(s):
- PNNL-SA-81719; 42591; KP1704020; TRN: US201201%%595
- Journal Information:
- Journal of Chemical Theory and Computation, Vol. 7, Issue 11; ISSN 1549-9618
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
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