| 11. |
- Lin, Na, 1981-
(författare)
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Theoretical Studies on Electronic and Vibrationally Resolved Multi-Photon Absorption and Dichroism
- 2009
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis presents time-dependent density functional theory studies on electronic and vibronically resolved linear and nonlinear optical absorption and dichroism spectra of organic molecules. Special attention has been paid to the influence of solvent environment and molecular vibrations on one-, two- and three-photon absorption and one- and two-photon circular dichroism. It is found that dielectric medium as described by polarizable continuum model can enhance remarkably three-photon absorption cross section of a highly conjugated fluorene derivative, for which the simplified two-state model is shown to be largely inadequate. Origin-invariant density functional calculations on one- and two-photon circular dichroisms of a chiral molecule confirm that the recently developed CAMB3LYP functional performs better than the popular B3LYP functional for Rydberg-states. The first experimental measurement of TPCD spectra is performed on an axial chiral system in tetrahydrofunan, where the double L-scan technique is applied. Theoretical calculations well reproduce the experimental profiles when both the electron correlation and the solvent effect are taken into account. Vibronically resolved one- and two-photon absorption spectra of charge-transfer molecules have been obtained using a Linear Coupling model, where the 'borrowing mechanism' for the so-called Herzberg-Teller contribution is analyzed in detail. It is shown that Herzberg-Teller contribution can introduce a change of sign to the chiral responses of a molecule without the involvement of different electronic states, which has important consequences for the assignment of absolute configurations of chiral molecules. Adiabatic harmonic Franck-Condon model is also applied to simulate vibronically resolved one- and two-photon circular dichroism spectra of the same chiral system, where the sign-inversion and the interference between Franck-Condon and Herzberg-Teller contributions are also observed.
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| 12. |
- Lin, Na, et al.
(författare)
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Theory for Vibrationally Resolved Two-Photon Circular Dichroism Spectra : Application to(R)-(R)-(R)-(+)-3-Methylcyclopentanone
- 2009
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Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 113:16, s. 4198-4207
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Tidskriftsartikel (refereegranskat)abstract
- A harmonic adiabatic approach in combination with density functional response theory for computing twophotonvibronically resolved circular dichroism spectra of chiral molecules is presented. It includes bothFranck-Condon and Herzberg-Teller contributions and it takes fully into account frequency changes andDuschinsky effects. Model calculations have been performed for two dominant conformers of (R)-(+)-3-methylcyclopentanone in the gas phase. It is found that the Herzberg-Teller contribution can introduce asign change in two-photon circular dichroism of a single excited electronic state of a conformer. The changesurvives after Boltzmann averaging, and it might be amenable to experimental verification. Interestinginterference effects between Franck-Condon and Herzberg-Teller contributions are revealed and analyzedin detail. Results obtained within the more approximate and less computationally intensive linear couplingvibronic model are also given for comparison.
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| 13. |
- Lin, Na, et al.
(författare)
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Vibronic induced one- and two-photon absorption in a charge-transfer stilbene derivate
- 2007
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 126:244509
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Tidskriftsartikel (refereegranskat)abstract
- Both the electronic and the vibronic contributions to one- and two-photon absorption of a D-pi-D charge-transfer molecule (4-dimethylamino-4(')-methyl-trans stilbene) are studied by means of density functional response theory combined with a linear coupling model. Vibronic profiles of the first four excited states are fully explored. The dominating vibrational modes for both Franck-Condon and Herzberg-Teller contributions are identified. The Franck-Condon contribution dominates the spectra of first, second, and fourth excited states. The Herzberg-Teller contribution is on the other hand of comparable size for the third excited state, where its inclusion leads to a blueshift with respect to the vertical transition. A similar vibronic coupling behavior is found for both one- and two-photon absorptions
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| 14. |
- Lin, Na, et al.
(författare)
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Vibronically-induced change in the chiral response of molecules revealed by electronic circular dichroism spectroscopy
- 2008
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Ingår i: Chemical Physics Letters. - : Elsevier BV. - 0009-2614 .- 1873-4448. ; 464, s. 144-149
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Tidskriftsartikel (refereegranskat)abstract
- A computational study of the vibronically resolved electronic circular dichroism (ECD) spectra of R-(+)- 3-methyl-cyclopentanone, including both Franck-Condon and Herzberg-Teller contributions, shows how the latter can introduce a change of sign on the chiral response of an electronic excited state. This sign inversion within the vibronically resolved electronic band, which can be interpreted as a change of the chirality of the system, has in principle important consequences in comparisons of theoretical and experimental ECD spectra employed for the assignment of absolute configurations.
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| 15. |
- Tao, Yi, et al.
(författare)
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Rapid synthesis of auxin via a new tryptophan-dependent pathway is required for shade avoidance in plants
- 2008
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Ingår i: Cell. - : Elsevier. - 0092-8674 .- 1097-4172. ; 133:1, s. 164-176
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Tidskriftsartikel (refereegranskat)abstract
- Plants grown at high densities perceive a decrease in the red to far-red (R:FR) ratio of incoming light, resulting from absorption of red light by canopy leaves and reflection of far-red light from neighboring plants. These changes in light quality trigger a series of responses known collectively as the shade avoidance syndrome. During shade avoidance, stems elongate at the expense of leaf and storage organ expansion, branching is inhibited, and flowering is accelerated. We identified several loci in Arabidopsis, mutations in which lead to plants defective in multiple shade avoidance responses. Here we describe TAA1, an aminotransferase, and show that TAA1 catalyzes the formation of indole-3-pyruvic acid (IPA) from L-tryptophan (L-Trp), the first step in a previously proposed, but uncharacterized, auxin biosynthetic pathway. This pathway is rapidly deployed to synthesize auxin at the high levels required to initiate the multiple changes in body plan associated with shade avoidance.
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| 16. |
- Tsai, Dun-Hou, et al.
(författare)
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Stories within and behind the story: A representation of entrepreneurial process
- 2009
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Ingår i: Critical Management Studies, Warwick 2009.
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Konferensbidrag (refereegranskat)abstract
- This paper uses a narrative approach to represent entrepreneurial process. It is a story about a specific process taking place in Yan-shuei, Taiwan, which is built upon a single entrepreneur and the people around him; what they did when they were“ entrepreneuring.” Within the story there are also other stories representing the researchers’ own experiences of entrepreneurial processes. As well, behind the story there is a story about The Moon Port City which relates to ancient times. Theories inspiring a process theory of entrepreneurship mark the beginning of the story. The middle is made up by the three main stories within the story as a whole. At the end the authors explain in what ways the narrative approach has emphasized entrepreneurial process.
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| 17. |
- Yang, Chia-Min, et al.
(författare)
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2D-Rectangular c2mm mesoporous silica nanoparticles with tunable elliptical channels and lattice dimensions
- 2008
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Ingår i: Chemical Communications. - : Royal Society of Chemistry (RSC). - 1359-7345 .- 1364-548X. ; :45, s. 5969-5971
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Tidskriftsartikel (refereegranskat)abstract
- Mesoporous silica nanoparticles with a two-dimensional center-rectangular (plane group c2mm) lattice and coiled elliptical channels have been synthesized; the new synthetic route also allows simple control over the lattice dimensions and the elliptical shape of the channels.
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| 18. |
- Yuesheng, Ning, et al.
(författare)
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Single molecule's conductance depending on its orientation
- 2009
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 113:1, s. 26-30
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Tidskriftsartikel (refereegranskat)abstract
- Single molecules of 1,1,2,3,4,5-hexaphenylsilole adsorbed on Cu(111) have been investigated using low-temperature scanning tunneling microscopy, scanning tunneling spectroscopy, and quantum chemistry calculations. Two adsorption states have been identified, showing distinctive tunneling conductance. The molecules can switch their states under tip influence. Theoretical calculations indicate that the two states are associated with molecules adsorbed at two 90°-rotated orientations, and the tunneling conductance is attributed to molecular orbitals that spatially bridge tip-to-substrate gap. Our findings demonstrate a decisive dependence of single-molecule conductance on the molecular orientation with respect to electrodes.
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