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      Two-photon absorption spectroscopy of stilbene and phenanthrene: Excited-state analysis and comparison with ethylene and toluene.

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          Abstract

          Two-photon absorption (2PA) spectra of several prototypical molecules (ethylene, toluene, trans- and cis-stilbene, and phenanthrene) are computed using the equation-of-motion coupled-cluster method with single and double substitutions. The states giving rise to the largest 2PA cross sections are analyzed in terms of their orbital character and symmetry-based selection rules. The brightest 2PA transitions correspond to Rydberg-like states from fully symmetric irreducible representations. Symmetry selection rules dictate that totally symmetric transitions typically have the largest 2PA cross sections for an orientationally averaged sample when there is no resonance enhancement via one-photon accessible intermediate states. Transition dipole arguments suggest that the strongest transitions also involve the most delocalized orbitals, including Rydberg states, for which the relative transition intensities can be rationalized in terms of atomic selection rules. Analysis of the 2PA transitions provides a foundation for predicting relative 2PA cross sections of conjugated molecules based on simple symmetry and molecular orbital arguments.

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          Most cited references72

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          Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

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            Über Elementarakte mit zwei Quantensprüngen

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              Photochromism of diarylethene molecules and crystals: memories, switches, and actuators.

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                Author and article information

                Journal
                J Chem Phys
                The Journal of chemical physics
                AIP Publishing
                1089-7690
                0021-9606
                May 07 2017
                : 146
                : 17
                Affiliations
                [1 ] Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482, USA.
                [2 ] Department of Chemistry, University of Kansas, Lawrence, Kansas 66045-7582, USA.
                Article
                10.1063/1.4982045
                28477598
                bb4c934e-849a-4d4d-945a-d6539d89817f
                History

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