期刊
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
卷 8, 期 11, 页码 4434-4440出版社
AMER CHEMICAL SOC
DOI: 10.1021/ct300372x
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资金
- NSERC
- Humboldt foundation
We present the results of calculations on the vertical singlet L-1(a) and L-1(b) excitation energies in acenes within time dependent density functional theory (TDDFT), second order constricted variational DFT (CV(2)-DFT), and all order constricted variational DFT (CV(infinity)-DFT) using the local density approximation LDA(VWN). For the linear acenes it is shown that the application of the Tamm-Dancoff (TD) approximation to TDDFT (TDDFT-TD) substantially improves the agreement with experiment compared to pure TDDFT. This improvement leads to the correct ordering of the L-1(a) and L-1(b) excitation energies in naphthalene. As TDDFT-TD is equivalent to the second order CV(2)-TD method one might hope for further improvements by going to all orders in CV(infinity)-TD. Indeed, for linear acenes the application of the CV(infinity)-TD method brings the agreement with experiment to within 0.1 eV for both types of excitations using the simple LDA functional. The CV(infinity)-TD method based on LDA is also shown to be accurate for 15 nonlinear acenes with root-mean-square deviations of 0.24 eV for L-1(a) and 0.17 eV for L-1(b).
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