Optical Properties from Density-Functional Theory

Casida, Mark E.; Jamorski, Christine; Bohr, Frédéric; Guan, Jingang; Salahub, Dennis R.

doi:10.1021/bk-1996-0628.ch008

Cited by 76 publications

(75 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The conductorlike polarizable continuum model method (CPCM) 26−28 with n-hexane as solvent was used to calculate the electronic structure and the excited states of the molecule in solution. Time-dependent density functional theory (TD-DFT) 29 calculations have provided excitation energies of the compound that agree with experimental results. TD-DFT calculation does not provide the electronic structures of the excited states; 30 however, the electronic distribution and the localization of the singlet excited states may be visualized using electron density difference maps (EDDMs).…”

Section: ■ Experimental Sectionsupporting

confidence: 58%

Ultrafast Dynamical Study of Pyrene-N,N-dimethylaniline (PyDMA) as an Organic Molecular Diode in Solid State

et al. 2014

View full text Add to dashboard Cite

Femtosecond optical pump−probe spectroscopy has been employed for studying the directly linked electron donor−acceptor system pyrene-N,N-dimethylaniline (PyDMA) in solid state. This DMA-pyrene derivative discussed is being applied as a molecular diode system switching on an ultrafast time scale. Our ultrafast solid-state studies reveal a complex photochemistry of this molecular crystal system. Strong couplings of the optically induced charge-transfer state with the radical ion pair state allow a femtosecond transition of the latter. One could see on the highest occupied molecular orbital−lowest unoccupied molecular orbital (HOMO−LUMO) description that a pure optical transition switches the system from a conducting to a blocked system because the molecular orbitals (MOs) of DMA moiety lie in a node plane of the LUMO. Within 800 fs the system relaxes back to the ground state and/or forms a radical ion pair, which is the surprising result of our study; when the system was probed further, the system underwent vibrational cooling and enhanced population inversion of the radical ion pair.

show abstract

Section: ■ Experimental Sectionsupporting

confidence: 58%

Ultrafast Dynamical Study of Pyrene-N,N-dimethylaniline (PyDMA) as an Organic Molecular Diode in Solid State

et al. 2014

View full text Add to dashboard Cite

show abstract

“…In the final stages of this work, the work of Casida and co-workers 5,65,66 came to our attention. They also have an implementation capable of calculating molecular frequencydependent linear response within DFT.…”

Section: Discussionmentioning

confidence: 99%

Improved density functional theory results for frequency-dependent polarizabilities, by the use of an exchange-correlation potential with correct asymptotic behavior

Gisbergen

Osinga

Gritsenko

et al. 1996

The Journal of Chemical Physics

195

111

View full text Add to dashboard Cite

The exchange-correlation potentials v xc which are currently fashionable in density functional theory ͑DFT͒, such as those obtained from the local density approximation ͑LDA͒ or generalized gradient approximations ͑GGAs͒, all suffer from incorrect asymptotic behavior. In atomic calculations, this leads to substantial overestimations of both the static polarizability and the frequency dependence of this property. In the present paper, it is shown that the errors in atomic static dipole and quadrupole polarizabilities are reduced by almost an order of magnitude, if a recently proposed model potential with correct Coulombic long-range behavior is used. The frequency dependence is improved similarly. The model potential also removes the overestimation in molecular polarizabilities, leading to slight improvements for average molecular polarizabilities and their frequency dependence. For the polarizability anisotropy we find that the model potential results do not improve over the LDA and GGA results. Our method for calculating frequency-dependent molecular response properties within time-dependent DFT, which we described in more detail elsewhere, is summarized.

show abstract

“…[36][37][38][39] Our TD-DFRT calculations were performed using version 2 of our program deMon-DynaRho ͑for ''dynamic response of ''͒. 40 This program follows the methodology described in Ref. 5, but differs from version 1 41 ͑used in Ref.…”

Section: Computational Detailsmentioning

confidence: 99%

Molecular excitation energies to high-lying bound states from time-dependent density-functional response theory: Characterization and correction of the time-dependent local density approximation ionization threshold

Casida

Jamorski

Casida

et al. 1998

The Journal of Chemical Physics

Self Cite

4,780

2,672

View full text Add to dashboard Cite

This paper presents an evaluation of the performance of time-dependent density-functional response theory ͑TD-DFRT͒ for the calculation of high-lying bound electronic excitation energies of molecules. TD-DFRT excitation energies are reported for a large number of states for each of four molecules: N 2 , CO, CH 2 O, and C 2 H 4 . In contrast to the good results obtained for low-lying states within the time-dependent local density approximation ͑TDLDA͒, there is a marked deterioration of the results for high-lying bound states. This is manifested as a collapse of the states above the TDLDA ionization threshold, which is at Ϫ⑀ HOMO LDA ͑the negative of the highest occupied molecular orbital energy in the LDA͒. The Ϫ⑀ HOMO LDA is much lower than the true ionization potential because the LDA exchange-correlation potential has the wrong asymptotic behavior. For this reason, the excitation energies were also calculated using the asymptotically correct potential of van Leeuwen and Baerends ͑LB94͒ in the self-consistent field step. This was found to correct the collapse of the high-lying states that was observed with the LDA. Nevertheless, further improvement of the functional is desirable. For low-lying states the asymptotic behavior of the exchange-correlation potential is not critical and the LDA potential does remarkably well. We propose criteria delineating for which states the TDLDA can be expected to be used without serious impact from the incorrect asymptotic behavior of the LDA potential.

show abstract

Optical Properties from Density-Functional Theory

Cited by 76 publications

References 0 publications

Ultrafast Dynamical Study of Pyrene-N,N-dimethylaniline (PyDMA) as an Organic Molecular Diode in Solid State

Ultrafast Dynamical Study of Pyrene-N,N-dimethylaniline (PyDMA) as an Organic Molecular Diode in Solid State

Improved density functional theory results for frequency-dependent polarizabilities, by the use of an exchange-correlation potential with correct asymptotic behavior

Molecular excitation energies to high-lying bound states from time-dependent density-functional response theory: Characterization and correction of the time-dependent local density approximation ionization threshold

Contact Info

Product

Resources

About