Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 131, Issue 2, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.3158990
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Funding
- Academy of Finland [118195, 126905]
- Deutsche Forschungsgemeinschaft (DFG) [C3.9]
- Lundbeck Foundation
- NordForsk [070253]
- Academy of Finland (AKA) [126905, 118195, 126905, 118195] Funding Source: Academy of Finland (AKA)
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The electronic excitation spectra of trans-1,3-butadiene (CH2=CH-CH=CH2) and trans-2-propeniminium (CH2=CH-CH=NH2+) have been studied at several coupled-cluster and time-dependent density functional theory levels using the linear response approach. Systematic studies employing large correlation-consistent basis sets show that approximate singles and doubles coupled-cluster calculations yield excitation energies in good agreement with experiment for all states except for the two lowest excited A(g) states of trans-1,3-butadiene which have significant multiconfigurational character. Time-dependent density functional theory calculations employing the generalized gradient approximation and hybrid functionals yield too low excitation energies in the basis set limit. In trans-1,3-butadiene, increasing the basis set size by augmenting multiple diffuse functions is observed to reduce the high-lying excitation energies with most density functionals. The decrease in the energies is connected to the incorrect asymptotic behavior of the exchange-correlation potential. The results also demonstrate that standard density functionals are not capable of providing excitation energies of sufficient accuracy for experimental assignments. (C) 2009 American Institute of Physics. [DOI: 10.1063/1.3158990]
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