Direct determination of collision rates beyond the Lennard-Jones model through state-resolved measurements of strong and weak collisions.
We describe a new approach for measuring absolute rates for molecular collisions including contributions of both strong and weak collisions. Elastic and inelastic collisions are monitored using high-resolution transient IR spectroscopy by measuring increases in the velocity distributions of individual rotational states of scattered molecules. Weak collisional energy transfer is detected by measuring velocity increases for the low-energy rotational states. This technique is illustrated for the collisional relaxation of highly vibrationally excited pyrazine (108 kcal/mol) with HOD. The observed collision rate is nearly twice the Lennard-Jones collision rate.
Havey
Daniel K
DK
Liu
Qingnan
Q
Li
Ziman
Z
Elioff
Michael
M
Fang
Maosen
M
Neudel
Joshua
J
Mullin
Amy S
AS