Response theory calculations of the vibronically induced 1A1g−1B2u two-photon spectrum of benzene

Luo, Yi; Ågren, Hans; Knuts, Sören; Minaev, B. F.; Jørgensen, Poul

doi:10.1016/0009-2614(93)80126-a

Cited by 32 publications

(20 citation statements)

References 21 publications

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“…Within the FranckCondon approximation, both spectra should have exactly the same profile. Such a difference in spectra could thus come from a non-Condon contribution, such as HerzbergTeller coupling as demonstrated in the first ab initio studies on TPA of polyatomic molecules [7]. Two recent studies have examined the effect of non-Condon effects and obtained similar general conclusions [5,6].…”

Section: Introductionmentioning

confidence: 88%

Role of non-Condon vibronic coupling and conformation change on two-photon absorption spectra of green fluorescent protein

Tian

Luo

2013

Molecular Physics

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Two-photon absorption spectra of green fluorescent proteins (GFPs) often show a blue-shift band compared to their conventional one-photon absorption spectra, which is an intriguing feature that has not been well understood. We present here a systematic study on one-and two-photon spectra of GFP chromophore by means of the density functional response theory and complete active space self-consistent field (CASSCF) methods. It shows that the popular density functional fails to provide correct vibrational progression for the spectra. The non-Condon vibronic coupling, through the localised intrinsic vibrational modes of the chromophore, is responsible for the blue-shift in the TPA spectra. The cis to trans isomerisation can be identified in high-resolution TPA spectra. Our calculations demonstrate that the high level ab initio multiconfigurational CASSCF method, rather than the conventional density functional theory is required for investigating the essential excited-state properties of the GFP chromophore.

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Section: Introductionmentioning

confidence: 88%

Role of non-Condon vibronic coupling and conformation change on two-photon absorption spectra of green fluorescent protein

Tian

Luo

2013

Molecular Physics

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“…[12][13][14][15][16][17] The effects of electronic, vibronic, and solvent contributions on the TPA cross sections have been analyzed in some detail, with spe-cial attention paid to the understanding of the role of the conjugation length, 12,13 dimensionality of charge-transfer networks, 14,16 the polarity of solutions, 15 and vibronic coupling. [16][17][18][19] In general, solvent effects on TPA cross sections are quite moderate, e.g., much smaller than those for the first hyperpolarizability ␤. We have shown that the effects of the vibronic coupling on the TPA cross sections can be large for the multibranched molecules, but that they tend to be very small for one-dimensional conjugated systems.…”

Section: Introductionmentioning

confidence: 99%

Effects of π centers and symmetry on two-photon absorption cross sections of organic chromophores

Wang

Macák

Luo

et al. 2001

The Journal of Chemical Physics

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“…[14][15][16][17] However, in the present work a more elaborate and accurate description of the vibrational wave function and the geometry dependence of the transition dipole moment is used.…”

Section: Introductionmentioning

confidence: 99%

A theoretical study of the 1B2u and 1B1u vibronic bands in benzene

Bernhardsson

Forsberg

Malmqvist

et al. 2000

The Journal of Chemical Physics

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The two lowest bands, 1 B 2u and 1 B 1u , of the electronic spectrum of the benzene molecule have been studied theoretically using a new method to compute vibronic excitation energies and intensities. The complete active space ͑CAS͒ self-contained field ͑SCF͒ method ͑with six active -orbitals͒ was used to compute harmonic force field for the ground state and the 1 B 2u and 1 B 1u electronic states. A linear approximation has been used for the transition dipole as a function of the nuclear displacement coordinates. Derivatives of the transition dipole were computed using a variant of the CASSCF state interaction method. Multiconfigurational second-order perturbation theory ͑CASPT2͒ was used to obtain absolute excitation energies ͑12 active -orbitals͒. The results show that the approach works well. Vibrational progressions are well described in both bands and intensities, and energies are in agreement with experiment, in particular when CASPT2 derived geometries are used. One interesting result is that computed vertical energies fall about 0.1 eV on the high energy side of the band maximum.

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Response theory calculations of the vibronically induced 1A1g−1B2u two-photon spectrum of benzene

Cited by 32 publications

References 21 publications

Role of non-Condon vibronic coupling and conformation change on two-photon absorption spectra of green fluorescent protein

Role of non-Condon vibronic coupling and conformation change on two-photon absorption spectra of green fluorescent protein

Effects of π centers and symmetry on two-photon absorption cross sections of organic chromophores

A theoretical study of the 1B2u and 1B1u vibronic bands in benzene

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