Intramolecular Dynamics and Statistical Theories of Chemical Reactions

We are interested in the intramolecular dynamics of small systems and the exact calculation of molecular eigenstates. This gives us valuable material to compare with calculations from more approximate models.

Models for numbers of states and densities of states are of utmost importance in chemistry due to their relevance for statistical theories for rate constants. Usually, these quantities are calculated based on a purely harmonic model which essentially contradicts the underlying physics, in particular the intramolecular vibrational energy redistribution (IVR). Recently, we have published a paper in which we present a new model that accounts for both anharmonicity and intermode coupling in the calculation of vibrational state densities.

Approximate calculation of anharmonic densities of vibrational states for very large molecules,
S. Schmatz,
Chem. Phys. 346, 198 (2008) [special issue in honor of Prof. Dr. P. Botschwina].

Long-range effects in the density of loosely bound states of ion-dipole systems: The S_N2 complex Cl^{- ...} CH₃Cl,
A. Delon, S. Heiliette and S. Schmatz,
Phys. Chem. Chem. Phys. 4, 6006 (2002).

Relaxation dynamics of deuterated formyl and isoformyl cations,
R. Wester, U. Hechtfischer, L. Knoll, M. Lange, J. Levin, M. Scheffel, D. Schwalm, A. Wolf, A. Baer, Z. Vager, D. Zajfman, M. Mladenovic and S. Schmatz,
J. Chem. Phys. , 116, 7000 (2002).

Numbers and densities of states from an efficient approach to phase space integration,
G. Taubmann and S. Schmatz,
Phys. Chem. Chem. Phys. 3 , 2296 (2001).

Theoretical study of the rovibrational energy spectrum and the numbers and densities of bound vibrational states for the system HCO⁺ - HOC⁺,
M. Mladenovic and S. Schmatz,
J. Chem. Phys. 109, 4456 (1998).

Globale Potentialhyperflächen und genaue Schwingungszustandsdichten am Beispiel der Kationen HN₂⁺ und HCO⁺ (Dissertation),
S. Schmatz,
Cuvillier, Göttingen 1997 (ISBN 3-89588-801-X)

Intramolecular dynamics and density of states for HN₂⁺,
S. Schmatz and M. Mladenovic,
Ber. Bunsenges. Phys. Chem.101, 372 (1997) [special issue 'Unimolecular Reaction Dynamics'].