Laser Induced Fluorescence and Ultraviolet Absorption Spectra, DFT Calculations, and Structure of 1,3-Benzodioxan

ORAL

Abstract

The laser induced fluorescence spectra, both excitation and dispersed, of jet-cooled 1,3-benzodioxan along with ultraviolet absorption spectra of the ambient temperature vapors have been recorded and analyzed. The focus of the study was on the low-frequency out-of-plane vibrational modes which are useful for determining the potential energy surface which governs the molecular structure. In the S$_{0}$ electronic ground state these have vibrational frequencies of 107.6 cm$^{-1}$ (ring-bending), 157.3 cm$^{-1}$ (ring-twisting), 275.1 cm$^{-1}$ (ring-flapping), and 350.2 cm$^{-1}$ (ring-twisting at the benzene ring). The corresponding values for the S$_{1}(\pi $,$\pi $*) excited state are 96.3, 102.2, 194.6, and 255.8 cm$^{-1}$ with the lower values reflecting a less rigid ring structure. DFT calculations predict a twisted structure and a barrier to planarity of 3475 cm$^{-1}$ for the S$_{0}$ ground state and this is consistent with the experimental data.

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Authors

  • Kathleen McCann

    Texas A\&M University, College Station, Texas

  • Edward Fry

    Institute for Astronomy, ETH, National Optical Astronomy Observatory, Department of Physics, ETH, Texas A&M University, LANL, American Physical Society, Society of Physics Students National Office, Texas Tech University, University of Texas, Universite d'Orleans, Steward Observatory, University of Arizona, Texas A\&M University-Commerce, Texas A\&M University, Institute for Quantum Electronics, ETH Zurich, Department of Engineering and Applied Science, Harvard University, Rice University, University of Houston, Bucknell University, Department of Physics, Texas A\&M University, Air Force Research Laboratory, Department of Physics, Texas A\&M University, College Station, TX 77843, Department of Physics and MIC, Texas A\&M University, University of Texas at Arlington, Changwon National University, University of North Texas, Southwestern University, The Pennsylvania State University, University of Dallas, UT Southwestern Medical Center, Naval Air Systems Command, Institute for Quantum Studies and Department of Physics, Texas A\&M University, College Station, TX 77843, The University of Texas at Arlington, TCU, ELTE, National Institute of Chemistry, Ljubljana, Slovenia, Texas Christian University, Fort Worth, TX, Dept. of Physics, Texas A\&M University-Commerce, Univ. of North Texas, Los Alamos National Laboratory, Oswego State University of New York, Lee College, University of Texas at San Antonio, UTSA-Professor, UNT, Sam Houston State University, Sewanee: The University of the South, Director of Education for NSF, Center for Nonlinear Dynamics and Department of Physics, The University of Texas at Austin, Sackler School of Chemistry, Tel-Aviv University, Rice University, Department of Physics and Astronomy, Houston, TX 77005, Center for Nonlinear Dynamics, University of Texas at Austin

  • Edward Fry

    Institute for Astronomy, ETH, National Optical Astronomy Observatory, Department of Physics, ETH, Texas A&M University, LANL, American Physical Society, Society of Physics Students National Office, Texas Tech University, University of Texas, Universite d'Orleans, Steward Observatory, University of Arizona, Texas A\&M University-Commerce, Texas A\&M University, Institute for Quantum Electronics, ETH Zurich, Department of Engineering and Applied Science, Harvard University, Rice University, University of Houston, Bucknell University, Department of Physics, Texas A\&M University, Air Force Research Laboratory, Department of Physics, Texas A\&M University, College Station, TX 77843, Department of Physics and MIC, Texas A\&M University, University of Texas at Arlington, Changwon National University, University of North Texas, Southwestern University, The Pennsylvania State University, University of Dallas, UT Southwestern Medical Center, Naval Air Systems Command, Institute for Quantum Studies and Department of Physics, Texas A\&M University, College Station, TX 77843, The University of Texas at Arlington, TCU, ELTE, National Institute of Chemistry, Ljubljana, Slovenia, Texas Christian University, Fort Worth, TX, Dept. of Physics, Texas A\&M University-Commerce, Univ. of North Texas, Los Alamos National Laboratory, Oswego State University of New York, Lee College, University of Texas at San Antonio, UTSA-Professor, UNT, Sam Houston State University, Sewanee: The University of the South, Director of Education for NSF, Center for Nonlinear Dynamics and Department of Physics, The University of Texas at Austin, Sackler School of Chemistry, Tel-Aviv University, Rice University, Department of Physics and Astronomy, Houston, TX 77005, Center for Nonlinear Dynamics, University of Texas at Austin

  • Jaan Laane

    Department of Chemistry, Texas A\&M University, Texas A\&M University, College Station, Texas, Texas A&M University