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Spectroscopic investigations of the vibrational potential energy surfaces in electronic ground and excited states

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Title: Spectroscopic investigations of the vibrational potential energy surfaces in electronic ground and excited states
Author: Yang, Juan
Abstract: The vibrational potential energy surfaces in electronic ground and excited states of several ring molecules were investigated using several different spectroscopic methods, including far-infrared (IR), Raman, ultraviolet (UV) absorption, fluorescence excitation (FES), and single vibronic level fluorescence (SVLF) spectroscopies. Based on new information obtained from SVLF and millimeter wave spectra, the far-IR spectra of coumaran were reassigned and the one-dimensional ring-puckering potential energy functions for several vibrational states in the S0 ground state were determined. The barrier was found to be 154 cm-1 and the puckering angles to be ± 25°, in good agreement with the millimeter wave barrier of 152 cm-1 and puckering angles of ± 23°. Moreover, the UV absorption and FES spectra of coumaran allowed the one-dimensional ring-puckering potential energy functions in the S1 excited state to be determined. The puckering barrier is 34 cm-1 for the excited state and the puckering angles are ± 14°. Several calculations with different basis sets have been carried out to better understand the unusual vibrational frequencies of cyclopropenone. It was shown that there is strong interaction between the C=O and symmetric C-C stretching vibrations. These results differ quantitatively from a previous normal coordinate calculation and interpretation. The vapor-phase Raman spectrum of 3,7-dioxabicyclo[3.3.0]oct-1,5-ene was analyzed and compared to the predicted spectrum from DFT calculations. The spectrum further shows it has D2h symmetry, in which the skeletons of both rings are planar. The infrared and Raman spectra of vapor-phase and liquid-phase 1,4-benzodioxan and 1,2,3,4-tetrahydronaphthalene were collected and the complete vibrational assignments for both molecules were made. Theoretical calculations predicted the barriers to planarity to be 4809 cm-1 for 1,2,3,4-tetrahydonaphthalene and 4095 cm-1 for 1,4-benzodioxan. The UV absorption, FES, and SVLF spectra of both molecules were recorded and assigned. Both one and two-dimensional potential energy functions of 1,4-benzodioxan for the ring-twisting and ring-bending vibrations were carried out for the S0 and S1(π,π*) states, and these were consistent with the high barriers calculated for both states. The low-frequency spectra of 1,2,3,4-tetrahydronaphthalene in both S0 and S1(π,π*) states were also analyzed.
Publisher: Texas A&M University
Subject: potential energy surface
spectroscopy
vibrational spectra
excited state
molecular structure
fluorescence
ultraviolet
infrared
URI: http://hdl.handle.net/1969.1/5900
Date: 2003-05

Citation

Yang, Juan (2003). Spectroscopic investigations of the vibrational potential energy surfaces in electronic ground and excited states. Doctoral dissertation, Texas A&M University. Texas A&M University. Available electronically from http : / /hdl .handle .net /1969 .1 /5900.

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