Open AccessInfrared Stark and Zeeman spectroscopy of OH–CO: The entrance channel complex along the OH + CO → trans-HOCO reaction pathway
Author(s) -
Joseph T. Brice,
Tao Liang,
Paul L. Raston,
Anne B. McCoy,
Gary E. Douberly
Publication year - 2016
Publication title -
journal of chemical physics online/the journal of chemical physics/journal of chemical physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.071
H-Index - 357
eISSN - 1089-7690
pISSN - 0021-9606
DOI - 10.1063/1.4963226
Subject(s) - zeeman effect , chemistry , spectroscopy , infrared , infrared spectroscopy , photochemistry , physics , organic chemistry , magnetic field , astronomy , quantum mechanics
Sequential capture of OH and CO by superfluid helium droplets leads exclusively to the formation of the linear, entrance-channel complex, OH–CO. This species is characterized by infrared laser Stark and Zeeman spectroscopy via measurements of the fundamental OH stretching vibration. Experimental dipole moments are in disagreement with ab initio calculations at the equilibrium geometry, indicating large-amplitude motion on the ground state potential energy surface. Vibrational averaging along the hydroxyl bending coordinate recovers 80% of the observed deviation from the equilibrium dipole moment. Inhomogeneous line broadening in the zero-field spectrum is modeled with an effective Hamiltonian approach that aims to account for the anisotropic molecule-helium interaction potential that arises as the OH–CO complex is displaced from the center of the droplet.Joseph T. Brice, Tao Liang, Paul L. Raston, Anne B. McCoy and Gary E. Douberl