Non-intuitive rotational reorientation in collisions of NO(A 2Σ+) with Ne from direct measurement of a four-vector correlation

• Published in: Nature chemistry 2018-11, Vol.10 (11), p.1148-1153
• Main Authors: Sharples, Thomas R., Leng, Joseph G., Luxford, Thomas F. M., McKendrick, Kenneth. G., Jambrina, Pablo G., Aoiz, F. Javier, Chandler, David W., Costen, Matthew L.
• Format: Article
• Language: English
• Subjects: 639/638/440/94; 639/638/440/948; 639/638/440/949; 639/638/440/950; Analytical Chemistry; Angular velocity; Biochemistry; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Collision dynamics; Correlation analysis; Electronic structure; Energy measurement; Handedness; Inorganic Chemistry; Intermolecular forces; Mathematical analysis; Molecular collisions; Molecular interactions; Molecular structure; Organic Chemistry; Physical Chemistry; Potential energy; Scattering angle
• ISSN: 1755-4330; 1755-4349
• DOI: 10.1038/s41557-018-0121-9

Stereodynamic descriptions of molecular collisions concern the angular correlations that exist between vector properties of the motion of the participating species, including their velocities and rotational angular momenta. Measurements of vector correlations provide a unique view of the forces acting during collisions, and are a stringent test of electronic-structure calculations of molecular interactions. Here, we present direct measurement of the four-vector correlation between initial and final relative velocities and rotational angular momenta in a molecular collision. This property, which quantifies the extent to which a molecule retains a memory of its initial sense of rotation, or handedness, as a function of scattering angle, yields insight into the dynamics of a molecular collision. We report non-intuitive changes in the handedness for specific states and scattering angles, reproduced by classical and quantum scattering calculations. Comparison to calculations on different ab initio potential energy surfaces demonstrates this measurement’s exquisite sensitivity to the underlying intermolecular forces. Measurements of vector correlations provide insight into the forces acting during molecular collisions, and are a stringent test of electronic-structure calculations. Now, non-intuitive dynamics of molecular collisions have been revealed by measuring the correlation between the relative velocities of the colliders and the molecular rotational angular momentum—before and after the collision—for NO(A 2 Σ + ) + Ne.