10th Congress of the World Association o f Theor etical and Comp utational C hem ists

WATOC 2014, 5 -10 October 2014, Santiago, Chile

Ab initio Calculation of Collisional And Spectroscopic

Molecular Properties for Astrochemical And Atmospheric Applications
Gerrit C. Groenenboom, Lei Song, Dennis Grimminck, Boy Lankhaar, and Ad
van der Avoird
Theoretical Chemistry, Institute for Molecules and Materials, Radboud Univeristy
Nijmegen, Heyendaalse weg 135, 6525 AJ Nijmegen, The Netherlands; e-mail:
gerritg@theochem.ru.nl

Abstract
Infrared radiation from ro-vibrationally excited carbon monoxide (CO) is observed in
protoplanetary disks and star-forming regions. Extracting information on densities and
temperatures from the observed intensities requires knowledge of Einstein A coefficients.
When the environments are not in local thermal equilibrium collision rates of
CO(v,J)+H2/H/He are also required. There are still large uncertainties in the H+CO(v,J) rates,
despite years of research. We will present results based on a new high level ab initio
interaction potential [1], coupled channel quantum scattering calculations, and using more
approximate modeling methods to cover the full range of rotational and vibrational states that
is required.
Circularly polarized radiation of methanol masers carries information on magnetic field
strengths, which play a crucial role in models that try to explain how stars much heavier than
our sun can be formed. Spectroscopic determination of the rotational g-tensor, which relates
Zeeman splittings of rotational transitions to the magnetic field strength, first attempted in
the early seventies, has not yet been achieved for methanol. We present theoretical results
based on coupled cluster calculations of the required electronic property, and a proper
treatment of overall and internal rotation.
The oxygen (O 2) b-X transition is used extensively for the calibration of satellite instruments
that study the atmosphere. Because of the high oxygen concentration and the long path-length
only the wings of this spin-orbit coupling induced magnetic dipole transition can be used. This
far wing region cannot be described with a simple Lorentzian line shape and line-mixing
effects are important. As a first step we have studied the pressure broadening of this
transition by helium. This work required He-O 2 interaction potentials for both the electronic
ground and excited state of O 2, and coupled channels scattering calculations on both surfaces.
We demonstrate good agreement with cavity ring down experiments in a joint theoretical experimental study [2].
Acknowledgments: We acknowledge the NWO Dutch Astrochemistry Network for financial
support. The H+CO work is a collaboration with N. Balakrishnan (University of Nevada Las
Vegas) and P. Stancil (University of Georgia) et al. The work on methanol is a collaboration
with H. J. van Langevelde (JIVE, Leiden University) et al.
[1] L. Song, A. van der Avoird, G. C. Groenenboom, J. Phys. Chem. 117 (2013) 7571.
[2] L. A. G. Grimminck, F. R. Spiering, L. M. C. Janssen, A. van der Avoird, W. J. van der Zande,
and G. C. Groenenboom, J. Chem. Phys. 140 (2014) 204314.

WATOC 2014 10 th Congress of the World Association of Theoretical and Computational Chemist s