Abstract
We derive reduced equations of motion (REM) which describe the dynamics of polyatomic molecules in the presence of strong infrared lasers. The derivation is made starting from the complete molecular Liouville equation and making use of the Zwanzig-Mori projection operator formalism. The complete molecular information relevant for the dynamics of molecular multiphoton processes (MMP) is expressed in terms of a hierarchy of intramolecular dipole correlation functions. We show how by invoking simple statistical assumptions (the random phase approximation and separation of time scales) this information is considerably reduced to essentially four quantities per transition: An integrated Rabi frequency\(\overline \Omega \) nm, a dephasing rate Γnm, a detuning \(\overline \omega \) nm and ratios of statistical weights of the levels dn/dm. Depending on our choice of reduction scheme we may obtain either generalized Bloch equations or simple rate equations. The interrelation between the two and their limits of validity are precisely specified. The present formulation enables us to describe the dynamics of MMP all the way from “region I” via the quasicontinuum and up to the dissociation. Finally we present novel spectroscopic results done in supersonic beams which provide us directly with the intramolecular dephasing rates which are the key dynamical quantities in MMP.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
R. Bray and M.J. Berry, J. Chem. Phys. 71, 4909 (1979).
D.F. Heller and S. Mukamel, J. Chem. Phys. 70, 463 (1979).
D.H. Levy, L. Wharton and R.E. Smalley, in C-Fiemical and Biochemical Applications of Lasers, Vol. II, ed. C.B. Moore (Academic Press,1977).
J.B. Hopkins, D.E. Powers and R.E. Smalley, J. Chem. Phys. (in press).
J.B. Hopkins, D.E. Powers, S. Mukamel and R.E. Smalley, J. Chem. Phys. (in press).
S. Mukamel and R.E. Smalley, J. Chem. Phys. (in press).
A. Laubereau and W. Kaiser,in Chemical and Biochemical Applications of Lasers, Vol. II, ed. C.B. Moore (Academic Press, 1977 ).
See papers in: (a) Tunable Lasers and Applications, ed. A. Mooradian, T. Jaeger and P. Stokseth ( Springer, New York, 1976 ).
Multiphoton Processes, ed. J.H. Eberly and P. Lambropolous ( Wiley, New York, 1978 ).
Adv. Chem. Phys. (1980). ( Proceedings of the Laser Chemistry Conference, Israel 1978 ).
For recent reviews see: R.L. Woodin, D.S. Bomse and J.L. Beauchamp,in Chemical and Biochemical Applications of Lasers, Vol. IV, ed. C.B. Moore (Academic Press, 1979 );
N. Bloembergen and E. Yablonovitch, Phys. Today, May, p. 23 (1978).
S.A. Rice,in Excited States, Vol. 2, ed. E.C. Lim (Academic Press, 1975 ).
S. Mukamel, Phys. Rev. Lett. 42, 168 (1979);
S. Mukamel, J. Chem. Phys. 70, 5834 (1979)
S. Mukamel, J. Chem. Phys. 71, 2012 (1979)
R. Zwanzig, Physica 30, 1109 (1964)
H. Mori, Prog. TÏeoret. Phys. 33, 423 (1965)
M. Tokuyama and H. Mori, ibid 55, 411 (1976).
S. Mukamel, Chem. Phys. 37, 33 (1979).
W.H. Louisell, Quantum Statistical Properties of Radiation( Wiley, New York, 1973 ).
R. Kubo, in Fluctuation, Relaxation and Resonance in Magnetic Systems, ed. D. Ter Haar ( Oliver & Boyd, Edinburgh, 1962 ).
R. Kubo, in Adv. Chem. Phys. X V (1969).
R.G. Brewer and R.L. Shoemaker, Phys. Rev. Lett. 27, 631 (1971).
T.J. Aartsma, J. Morsink and D.A. Wiersma, Chem. Phys. Lett. 42, 520 (1976); 47, 425 (1977); 49, 34 (1977).
J. Fiutak and J. Van Kranëndonk, Can. J. Phys. 40, 1085 (1962).
V. Hizhnyakov and I. Tehver, Phys. Stat. Sol. 21, 755 (1967).
P.W. Anderson, Phys. Rev. 80, 511 (1950).
W.H. Miller, Adv. Chem. Phys. Vol. 30, p. 77, ed. H.P. Lawley (Wiley, 1975 ).
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1980 Springer-Verlag Berlin Heidelberg
About this paper
Cite this paper
Mukamel, S. (1980). Theory of Collisionless Molecular Multiphoton Processes. In: Kubo, R., Hanamura, E. (eds) Relaxation of Elementary Excitations. Springer Series in Solid-State Sciences, vol 18. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-81482-2_16
Download citation
DOI: https://doi.org/10.1007/978-3-642-81482-2_16
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-642-81484-6
Online ISBN: 978-3-642-81482-2
eBook Packages: Springer Book Archive