Martin Quack
Laboratorium fuer Physikalische Chemie, ETH Zurich (Zentrum), CH-8092 Zurich, SWITZERLAND
In the early 80ies my research group embarked on a project to derive the primary processes of intramolecular kinetics in highly excited polyatomic molecules from their high resolution rovibrational spectra. The key steps in the new methods developed in this context by us are : 1. Development of the new experimental techniques allowing for obtaining complete analysis and assignments of complex spectra. 2. Description of the spectra in terms of adequate effective hamiltonians containing a limited number of parameters. 3. Deriving new descriptions of the full molecular hamiltonian including also new developments for accurate analytical representations of multidimensional potential hypersurfaces as well as new, often very small terms in the hamiltonian. 4. Solving multidimensional rovibrational Schroedinger equations with finite basis or discrete variable representations as well as Quantum Monte Carlo methods. 5. Deriving the time dependent quantum wavepacket motion for highly excited states for individual molecules in isolation as well as under intense coherent infrared radiation. 6. Obtaining quantum statistical approximations. The combination of experimental and theoretical methods is essential in this project. As is well but perhaps not widely known, this approach has led to the first multidimensional femtosecond wavepackets from experiments on polyatomic molecules and has also been the basis for a proposal of the most sensitive experimental test of CPT symmetry. The earlier work has been reviewed [1-6]. In the lecture, we will briefly discuss our current experimental and theoretical methods and then present our most recent results on the spectroscopy and quantum dynamics of chiral molecules [7] in the low and the high barrier limit [8,9,10], including the new theory of parity violation in polyatomic molecules [7-13]. Depending on the time available, we will discuss also the symmetry and rovibrational quantum dynamics of the absolute molecular clock [14].
[1] M. Quack, Adv. Chem. Phys. 50, 395-473 (1982)
[2] M. Quack, Annual Rev. Phys. Chem. 41, 839-874 (1990)
[3] M. Quack, J. Mol. Struct. 347, 245-266 (1995)
[4] M. Quack, chapter 27 in : `Femtosecond Chemistry', J. Manz
and L. Woeste eds., Proc. Berlin Conf. Femtosecond Chemistry, Berlin
(March 1993), Verlag Chemie, Weinheim (1994), p. 781-818
[5] M. Quack and M.A. Suhm, in `Advances in Molecular Vibrations
and Collision Dynamics, Vol. III, Molecular Clusters', p. 205-248,
Z. Bacic & J. Bowman eds., JAI Press, Stamford, Conn. (1998)
[6] M. Quack. Multiphoton Excitation in `Encyclopedia of Computational
Chemistry', Vol. 3, p. 1775-1791, P. von Rague Schleyer,
et al
eds., John Willey and Sons 1998
[7] M.Quack, Angewandte Chemie 101, 588-604 (1989); Angewandte
Chemie (Intl. Ed.) 28, 571-586 (1989)
[8] B. Fehrensen, M. Hippler and M. Quack, Chem. Phys. Lett.
298, 320-328 (1998)
[9] B. Fehrensen, D. Luckhaus and M. Quack, Chem. Phys. Lett.300,
547-557 (1999)
[10] J. Pochert and M. Quack, Mol. Phys. 95, 1055-1075
(1998)
[11] A. Bakasov and M. Quack, Chem. Phys. Lett. 303,
547-557 (1999)
[12] R. Berger and M. Quack, J. Chem. Phys. 112, 3148-3158
(2000); (cf. R. Berger and M. Quack, Proc. 37th IUPAC Congress
Vol. 2, p. 518 Berlin (1999))
[13] M. Quack and J. Stohner, Phys. Rev. Lett. 84, 3807-3810
(2000); M. Quack and J. Stohner, Z. Phys. Chem. 214, 5, 675-703
(2000)
[14] M. Quack, Nova Acta Leopoldina 81, Neue Folge (No.
314) 137-173 (1999)