Two-photon absorption study of 1,3,5-hexatriene by cars and CSRS

Fujii, Toshiyuki; Kamata, Atsushi; Shimizu, Masashi; Adachi, Yukio; Maeda, Shiro

doi:10.1016/0009-2614(85)85150-2

Cited by 59 publications

(31 citation statements)

References 28 publications

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“…CC2 and CC3 in hexatriene deviate [38] by 1.43 and 0.52, respectively, from the experimental two-photon value (5.21 eV). [39] Similar errors are found in other polyenes, also using EOM-CC techniques. [40] In contrast, the CASPT2 vertical result of 5.20 eV [41] can be considered an excellent benchmark.…”

Section: Propagator Approachessupporting

confidence: 78%

Progress and Challenges in the Calculation of Electronic Excited States

2011

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A detailed understanding of the properties of electronic excited states and the reaction mechanisms that molecules undergo after light irradiation is a fundamental ingredient for following light-driven natural processes and for designing novel photonic materials. The aim of this review is to present an overview of the ab initio quantum chemical and time-dependent density functional theory methods that can be used to model spectroscopy and photochemistry in molecular systems. The applicability and limitations of the different methods as well as the main frontiers are discussed. To illustrate the progress achieved by excited-state chemistry in the recent years as well as the main challenges facing computational chemistry, three main applications that reflect the authors' experience are addressed: the UV/Vis spectroscopy of organic molecules, the assignment of absorption and emission bands of organometallic complexes, and finally, the obtainment of non-adiabatic photoinduced pathways mediated by conical intersections. In the latter case, special emphasis is put on the photochemistry of DNA. These applications show that the description of electronically excited states is a rewarding but challenging area of research.

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Section: Propagator Approachessupporting

confidence: 78%

Progress and Challenges in the Calculation of Electronic Excited States

2011

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“…Another triene, 2,4,6-octatriene in a cyclohexane/octane matrix, has also been shown to fluoresce [28], indicating that in this case also the A; origin lies below the B: origin. Very recently the vertical transitions to the A; states of neat cis-and truns-1,3,5-hexatrienes have been shown to lie within 0.5 eV above those of the B: states of these molecules [29]. All three triene results thus provide additional support for the relative transition energy origins indicated in Figure 1.…”

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confidence: 65%

The lower valence states of linear polyenes: Locations and identifications

Diarmid

1986

Int J of Quantum Chemistry

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The experimental transition energy to the valence A, state of butadiene is used to validate a subset of the theoretical calculations that have been carried out on this molecule. The validated calculated A, transition energies of these calculations are then compared with the experimental B, transition energies to determine the relative state ordering in isolated, unsubstituted butadiene, hexatriene, and octatetraene. The A, origins are concluded to lie below the B , origins for all polyenes except butadiene. Experimental confirmation of this conclusion is presented. The extreme breadth of the A, transition, 1 .O eV, is noted. Some possible implications of this breadth are discussed.In this note, all currently available compatable experimental and theoretical information concerning the locations of the lower valence excited states of isolated, unsubstituted, short polyenes are compared, and an assignment is deduced that is consistent with this information and with the accepted major features of condensed phase and substituted polyene spectroscopy [ 11. Several predictions based on this analysis are presented.The experimental transition energies of two valence transitions each are now known for the all trans isomers of butadiene [2,3], hexatriene [4,5], and octatetraene [6,7] in the vapor phase. These are presented as solid symbols in Figure 1. The locations of the lower set of experimental transitions have long been known. They arise from allowed transitions to the B, state in each molecule [ 111. The B, transition energies indicated on the figure are origins. For use in our later analysis, this set is extrapolated to the decapentaene. The locations of the upper set of transitions have been determined by electron impact spectroscopy [ 3,5,7]. From experimental considerations, the upper set of transitions is assigned as arising from forbidden valence transitions. It is assumed, but not proven, that these are transitions to A, states. The transition energies indicated are vertical transitions.The first question that must be answered is whether or not the upper A, state observed in each molecule is the same. The answer is "no" for three reasons. The first is based on a comparison of the singlet A, and B, energy levels. The A,-B, energy gaps observed here in the triene and tetraene, 2.0 and 1.5 eV, respectively, are reasonable extrapolations of those observed in longer polyenes [ 121. The two transitions observed in each of these molecules thus correspond to the traditional B, and "cis" bands. The A,-B, gap observed in the diene, 1.6 eV, is significantly smaller than is 0 1986 John Wiley & Sons, Inc.

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“…In the first column of Table IV, we can see the excitation energies of the 2 1 A g doubly excited state from the ground state of the above molecules. We compare our methodology with CASSCF 13 and experimental values 8,9 given in the next columns. In the last column the results before the orbital optimization are given.…”

Section: Resultsmentioning

confidence: 99%

“…44 For polyenes (1,3-butadiene and trans-1,3,5-hexatriene) comparison was made with experimental results 8,9 and with those obtained by CASSCF. 13 In all cases we found that our results were in satisfactory agreement with those given in the above literature.…”

Section: Discussionmentioning

confidence: 99%

“…Since then, the description of their doubly excited states has become a subject of many theoretical [5][6][7] and experimental works. 8,9 This is due to the fact that these excitations in polyenes can be used for technological applications, such as organic electronics 10 and photonics 11 and play an important role in biological processes such as vision and photosynthesis. 12 Although, multielectron excited states can be modeled using multideterminantal methods such as configuration interaction (CI), 5 Second-Order Perturbation Theory (PT2D), 13 complete active space self-consistent field method (CASSCF), 13,14 its second order perturbation theory (CASPT2), 14,15 and symmetry adapted cluster CI (SAC-CI), 16,17 these kinds of calculations are prohibitively computationally expensive for large molecules.…”

Section: Introductionmentioning

confidence: 99%

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Double excitations from modified Hartree Fock subsequent minimization scheme

Tassi

Θεοφίλου

Thanos

2013

The Journal of Chemical Physics

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Doubly excited states have nowadays become important in technological applications, e.g., in increasing the efficiency of solar cells and therefore, their description using ab initio methods is a great theoretical challenge as double excitations cannot be described by linear response theories based on a single Slater determinant. In the present work we extend our recently developed Hartree-Fock (HF) approximation for calculating singly excited states [M. Tassi, I. Theophilou, and S. Thanos, Int. J. Quantum Chem. 113, 690 (2013)] in order to allow for the calculation of doubly excited states. We describe the double excitation as two holes in the subspace spanned from the occupied HF orbitals and two particles in the subspace of virtual HF orbitals. A subsequent minimization of the energy results to the determination of the spin orbitals of both the holes and the particles in the occupied and virtual subspaces, respectively. We test our method, for various atoms, H 2 and polyene molecules which are known to have excitations presenting a significant double excitation character. Importantly, our approach is computationally inexpensive.

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Two-photon absorption study of 1,3,5-hexatriene by cars and CSRS

Cited by 59 publications

References 28 publications

Progress and Challenges in the Calculation of Electronic Excited States

Progress and Challenges in the Calculation of Electronic Excited States

The lower valence states of linear polyenes: Locations and identifications

Double excitations from modified Hartree Fock subsequent minimization scheme

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