Proton transfer dynamics in the first excited singlet state of malonaldehyde
J. Chem. Phys. 107, 5617 (1997); doi:10.1063/1.474263
Issue Date: 8 October 1997
You are not logged in to this journal. Log in
The dynamics of proton transfer in the first excited singlet state of malonaldehyde [Ã 1B1(
*n)] have been investigated through the use of high-resolution degenerate four-wave mixing spectroscopy. Observed à 1B1
1A1 (
*
n) rovibronic features are at odds with previous absorption measurements and cannot be explained readily through the accepted description of tunneling behavior within the à 1B1(
*n) potential surface. ©1997 American Institute of Physics.
*n)] have been investigated through the use of high-resolution degenerate four-wave mixing spectroscopy. Observed à 1B1
*
n) rovibronic features are at odds with previous absorption measurements and cannot be explained readily through the accepted description of tunneling behavior within the à 1B1(
*n) potential surface. ©1997 American Institute of Physics.
| History: | Received 26 June 1997; accepted 1 August 1997 |
| Permalink: |
http://link.aip.org/link/?JCPSA6/107/5617/1 |
KEYWORDS and PACS
chemical exchanges,
organic compounds,
excited states,
multiwave mixing,
tunnelling,
rotational-vibrational states,
potential energy surfaces,
isomerisation,
reaction kinetics
- 82.30.Hk
Physical Chemistry Specific chemical reactions; reaction mechanisms Chemical exchanges (substitution, atom transfer, abstraction, disproportionation, and group exchange) - 82.30.Qt
Physical Chemistry Specific chemical reactions; reaction mechanisms Isomerization and rearrangement - 82.20.Kh
Physical Chemistry Chemical kinetics Potential energy surfaces for chemical reactions - YEAR: 1996-97
PUBLICATION DATA
0021-9606 (print)
1089-7690 (online)
REFERENCES (29)
For access to fully linked references, you need to log in.
For access to fully linked references, you need to Log in.
- P. Löwdin,
Rev. Mod. Phys. 35, 724 (1963 ); - D. Devault,
Q. Rev. Biophys. 13, 387 (1980 ); - F. Hibbert,
Adv. Phys. Org. Chem. 22, 113 (1986 ). - W. F. Rowe, R. W. Duerst, and E. B. Wilson,
J. Am. Chem. Soc. 98, 4021 (1976 ); - P. Turner et al.,
ibid. 106, 2265 (1984 ). - S. L. Baughcum et al.,
J. Am. Chem. Soc. 103, 6296 (1981 ); - Z. Smith, E. B. Wilson, and R. W. Duerst,
Spectrochim. Acta. A 39, 1117 (1983 ); - S. L. Baughcum et al.,
J. Am. Chem. Soc. 106, 2260 (1984 ). - M. J. Frisch et al., J. Chem. Phys. 82, 4194 (1985).
- D. W. Firth et al., J. Chem. Phys. 94, 1812 (1991).
- Owing to the pronounced structural nonrigidity that accompanies the large amplitude tunneling motion of malonaldehyde, the most useful description of symmetry properties is provided by the complete nuclear permutation-inversion group of order four: G4. Since G4 is conveniently isomorphic with the C2
molecular symmetry group, it is possible to classify and label the vibronic structure of nonrigid malonaldehyde in terms of the same irreducible representations employed for the rigid planar configuration of the symmetrical (C2
) transition state. - P. R. Bunker, Molecular Symmetry and Spectroscopy (Academic, New York, 1979).
- N. Shida, P. F. Barbara, and J. E. Almlöf, J. Chem. Phys. 91, 4061 (1989).
- P. F. Barbara, P. K. Walsh, and L. E. Brus,
J. Phys. Chem. 93, 29 (1989 ). - H. Ozeki et al., J. Chem. Phys. 99, 56 (1993).
- C. J. Seliskar and R. E. Hoffman,
Chem. Phys. Lett. 43, 481 (1976 ). - C. J. Seliskar and R. E. Hoffman,
J. Am. Chem. Soc. 99, 7072 (1977 ); - D. W. Firth, P. F. Barbara, and H. P. Trommsdorff,
Chem. Phys. 136, 349 (1989 ). - K. Luth and S. Scheiner,
J. Phys. Chem. 98, 3582 (1994 ). - Q. Zhang et al., J. Chem. Phys. 96, 1640 (1992);
- P. H. Vaccaro, in Molecular Dynamics and Spectroscopy by Stimulated Emission Pumping, edited by H. L. Dai and R. W. Field (World Scientific, Singapore, 1995), Chap. 1.
- P. H. Vaccaro, in Nonlinear Spectroscopy for Molecular Structure Determination, edited by E. Hirota, R. W. Field, J. P. Maier, and S. Tsuchiya (Blackwell, London, 1997).
- R. L. Farrow and D. J. Rakestraw,
Science 257, 1894 (1992 ). - T. J. Butenhoff and E. A. Rohlfing, J. Chem. Phys. 97, 1595 (1992);
- E. F. McCormack et al.,
Chem. Phys. Lett. 211, 147 (1993 ); - R. L. Abrams et al., in Optical Phase Conjugation, edited by R. A. Fisher (Academic, San Diego, 1983), p. 211.
- S. Mukamel, Principles of Nonlinear Optical Spectroscopy (Oxford University Press, New York, 1995).
- R. L. Vander Wal, R. L. Farrow, and D. J. Rakestraw, High-Resolution Investigation of Degenerate Four-Wave Mixing in the
(0,0) Band of Nitric Oxide, 24th (International) Symposium on Combustion, 1992, p. 1653;
E. J. Friedman-Hill, L. A. Rahn, and R. L. Farrow, J. Chem. Phys. 100, 4065 (1994). - S. Williams, R. N. Zare, and L. A. Rahn, J. Chem. Phys. 101, 1072, 1093 (1994).
- R. Hüttel, Chem. Ber. 74, 1825 (1941);
- Since the fine structure observed on prominent four-wave mixing features cannot be attributed to isolated rovibronic transitions, the actual lifetime of Ã1B1 malonaldehyde is probably much longer than the 10 ps lower limit established by measured spectral linewidths.
- R. L. Farrow, T. Dreier, and D. J. Rakestraw,
J. Opt. Soc. Am. B 9, 1770 (1992 ). - T. Azumi and K. Matsuzaki,
Photochem. Photobiol. 25, 315 (1977 );
I. Özkan and L. Goodman, - J. A. Pople and J. W. Sidman,
J. Chem. Phys. 26, 1270 (1957 );
J. R. Henderson, ibid. 44, 3496 (1966);
T. A. W. Wasserman et al.,
T. A. W. Wasserman, P. H. Vaccaro, and B. R. Johnson, J. Chem. Phys. 106, 6314 (1997).
J. R. Dunlop and E. A. Rohlfing, ibid. 100, 856 (1993);
J. D. Tobiason, J. R. Dunlop, and E. A. Rohlfing,
E. F. McCormack et al., J. Chem. Phys. 102, 4740 (1995).
G. Fisher, Vibronic Coupling: The Interaction Between the Electronic and Nuclear Motions (Academic, London, 1984).
S. H. Lin,
K. K. Innes,








