The rotationally resolved electronic spectra of the origin bands of 3-cyanoindole, 3-cyanoindole(d1), and the 3-cyanoindole-(H2O)1 cluster have been measured and analyzed using evolutionary algorithms. For the monomer, permanent dipole moments of 5.90 D for the ground state, and of 5.35 D for the lowest excited singlet state have been obtained from electronic Stark spectroscopy. The orientation of the transition dipole moment is that of an 1Lb state for the monomer. The water moiety in the water cluster could be determined to be trans-linearly bound to the NH group of 3-cyanoindole, with an NHO hydrogen bond length of 201.9 pm in the electronic ground state. Like the 3-cyanoindole monomer, the 3-cyanoindole-water cluster also shows an 1Lb-like excited singlet state. The excited state lifetime of isolate 3-cyanoindole in the gas phase has been determined to be 9.8 ns, and that of 3-cyanoindole(d1) has been found to be 14.8 ns, while that of the 1 : 1 water cluster is considerably shorter (3.6 ns). The excited state lifetime of 3-cyanoindole(d1) in D2O solution has been found to be smaller than 20 ps.
The excited state dipole moment of anisole has been determined in the gas phase from electronic Stark spectroscopy and in solution using thermochromic shifts in ethyl acetate. Electronic excitation increases the anisole dipole moment in the gas phase from 1.26 D in the ground state to 2.19 D in the electronically excited singlet state, leaving the orientation of the dipole moment practically unchanged. These values are compared to solution phase dipole moments. From variation of the fluorescence emission and absorption maxima with temperature, an excited state dipole moment of 2.7 D was determined. Several solvent polarity functions have been used in combination with experimentally determined cavity volumes at the respective temperatures. Both gas phase and condensed phase experimental dipole moments are compared to the results of ab initio calculations at the CC2 level of theory, using the cc-pVTZ basis set for the isolated molecule and using the COnductor-like Screening MOdel (COSMO), implemented in Turbomole, for the solvated anisole molecule.
We present the temperature dependent density, fluorescence emission and absorption spectroscopic data, that are needed for an evaluation of the excited state dipole moment of anisole in ethyl acetate via the methods of thermochromic shifts. Furthermore, the rotationally resolved electronic Stark spectrum of anisole in the molecular beam is presented. Finally, the Cartesian coordinates of the CC2/cc-pVTZ optimized structures of anisole are given in bohr units. For details about the evaluation of the dipole moments from the given data, see the connected research article: Lindic et al. (2018) [1].
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