Solvent effects on molecular spectra. III. Absorption to and emission from the lowest singlet (n,Ï€*) state of dilute pyrimidine in water

Zeng, J.; Hush, N. S.; Reimers, J. R.
August 1993
Journal of Chemical Physics;8/1/1993, Vol. 99 Issue 3, p1508
Academic Journal
A model is developed for the solvent shift of the center of an electronic absorption or emission band and is applied to the interpretation of the spectra of dilute pyrimidine in water. It is based on the use of standard simulation techniques such as molecular dynamics and Monte Carlo to calculate the liquid structure around the chromophore in its initial electronic state; the solvent shift is then deduced by considering the changes in the electrostatic distribution of the chromophore on vertical Franck–Condon excitation. During the solvent-shift evaluation only, spherical boundary conditions are used and the sample, containing both the solute and a large number of explicitly polarizable solvent molecules, is placed inside a dielectric continuum. The results show that the solvent shifts of both the absorption and fluorescence spectra of pyrimidine in water are comprised of approximately equal contributions from specific hydrogen-bonding interactions and long-range–plus–nonspecific dipole solvation effects. The solvent shift is shown to be very sensitive to the structure of the liquid. A specific aim of our approach is to develop a method applicable to molecular electronic devices, and to inorganic complexes.


Related Articles

  • Observation of the à 1A″ state of isocyanogen. Lynch, W. Bryan; Bechtel, Hans A.; Steeves, Adam H.; Curley, John J.; Field, Robert W. // Journal of Chemical Physics;6/28/2007, Vol. 126 Issue 24, p244307 

    The à 1A″ state of isocyanogen, CNCN, is observed using photofragment fluorescence excitation spectroscopy in a room temperature cell and in a molecular beam. The spectra are highly congested, but progressions that correspond to the Franck-Condon active C–N–C bending...

  • Three-dimensional analytical model for the photodissociation of symmetric triatomics. Absorption and fluorescence spectra of ozone. Atabek, O.; Bourgeois, M. T.; Jacon, M. // Journal of Chemical Physics;6/15/1986, Vol. 84 Issue 12, p6699 

    A full three-dimensional analytical Franck–Condon analysis is presented for dissociative spectroscopies of a symmetric triatomic system. Formulas derived for harmonic potential surfaces are applied to the theoretical calculation of ozone absorption spectrum in the Hartley continuum as...

  • Rotationally resolved dicopper (Cu2) laser-induced fluorescence spectra. Page, Ralph H.; Gudeman, Christopher S. // Journal of Chemical Physics;1/1/1991, Vol. 94 Issue 1, p39 

    We have used an RF sputter source to produce gas-phase copper dimer molecules for study with laser-induced fluorescence spectroscopy. Rotationally resolved spectra of transitions from the electronic ground (X) state to the A, B, C, G, and J states have been obtained. Previous rotational analyses...

  • Photodissociation study of CS[sub 2] at 193 nm using slice imaging. Kitsopoulos, Theofanis N.; Gebhardt, Christoph R.; Rakitzis, T. Peter // Journal of Chemical Physics;12/1/2001, Vol. 115 Issue 21, p9727 

    The photodissociation of CS[sub 2] at 193 nm (51 700) cm[sup -1]) is studied using the slice imaging technique, and velocity distributions for state selected S([sup 3]P[sub 2,1,0]) and S([sup 1]D[sub 2]) photofragments are measured. From the analysis of the speed distributions we determine the...

  • Analysis of vibronic mode coupling in pentacene by fully resonant coherent four-wave mixing. Carlson, Roger J.; Nguyen, Dinh C.; Wright, John C. // Journal of Chemical Physics;2/1/1990, Vol. 92 Issue 3, p1538 

    This paper develops the theoretical framework for the analysis of relative peak intensities in fully resonant, three laser, coherent four-wave mixing spectra of molecular vibrational and vibronic levels. For a Franck–Condon system, the relative vibronic peak intensities are shown to scale...

  • Combined experimental-theoretical study of the lower excited singlet states of paravinyl phenol, an analog of the paracoumaric acid chromophore. de Groot, Mattijs; Buma, Wybren Jan; Gromov, Evgeniy V.; Burghardt, Irene; Köppel, Horst; Cederbaum, Lorenz S. // Journal of Chemical Physics;11/28/2006, Vol. 125 Issue 20, p204303 

    The low-lying excited singlet states of paravinyl phenol (pVP) are investigated experimentally and theoretically paying attention to their similarity to excited states of paracoumaric acid, the chromophore of the photoactive yellow protein (PYP). Resonance enhanced multiphoton ionization and...

  • Geometry change of simple aromatics upon electronic excitation obtained from Franck-Condon fits of dispersed fluorescence spectra. Imhof, Petra; Krügler, Daniel; Brause, Robert; Kleinermanns, Karl // Journal of Chemical Physics;8/8/2004, Vol. 121 Issue 6, p2598 

    The S1 state geometries of benzonitrile, p-cyanophenol, o-cyanophenol, chlorobenzene, and p-chlorophenol were determined by Franck-Condon simulations and a fit of the geometry to the vibronic intensities and effective rotational constants in the harmonic limit based on ab initio force constants....

  • Low-frequency vibrations specific for conformers of 1-aminoindan studied by UV-UV hole-burning spectroscopy. Isozaki, Tasuku; Iga, Hiroshi; Suzuki, Tadashi; Ichimura, Teijiro // Journal of Chemical Physics;6/7/2007, Vol. 126 Issue 21, p214304 

    The UV-UV hole-burning spectra of the jet-cooled 1-aminoindan were measured for the first time. Complicated spectral features observed in the laser-induced fluorescence excitation spectrum due to two conformers, R and B, were firmly separated. On the basis of fluorescence measurements and...

  • Manifestation of the vibronic analogue of the Fermi resonance in quasi-line spectra of porphyrins: Experiment and theoretical analysis. Arabei, S. M.; Kuzmitsky, V. A.; Solovyov, K. N. // Optics & Spectroscopy;May2007, Vol. 102 Issue 5, p692 

    The quasi-line low-temperature (4.2 K) fluorescence excitation spectra of two porphyrins, meso-tetraazaporphin and meso-tetrapropylporphin introduced into an n-octane matrix are measured in the range of the S 0 → S 2 electronic transition. A characteristic feature of these spectra is that...


Read the Article


Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics