Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Interference structures in the differential cross-sections for inelastic scattering of NO by Ar

Nature Chemistry volume 3, pages 597–602 (2011)Cite this article

Subjects

Abstract

Inelastic scattering is a fundamental collisional process that plays an important role in many areas of chemistry, and its detailed study can provide valuable insight into more complex chemical systems. Here, we report the measurement of differential cross-sections for the rotationally inelastic scattering of NO(X2Π1/2, v = 0, j = 0.5, f) by Ar at a collision energy of 530 cm−1 in unprecedented detail, with full Λ-doublet (hence total NO parity) resolution in both the initial and final rotational quantum states. The observed differential cross-sections depend sensitively on the change in total NO parity on collision. Differential cross-sections for total parity-conserving and changing collisions have distinct, novel quantum-mechanical interference structures, reflecting different sensitivities to specific homonuclear and heteronuclear terms in the interaction potential. The experimental data agree remarkably well with rigorous quantum-mechanical scattering calculations, and reveal the role played by total parity in acting as a potential energy landscape filter.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Rent or buy this article

Get just this article for as long as you need it

$39.95

Learn more

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Experimental and fitted ion images.
Figure 2: Experimental versus quantum-mechanically calculated DCSs.
Figure 3: An illustration of the blurring effect of averaging over the initial NO Λ-doublet states.
Figure 4: Illustration of the four limiting paths used in the hard shell calculations.
Figure 5: Comparison of DCSs from the hard shell model with those from CC QM and QQT theory.

References

  1. Ottinger, C., Velasco, R. & Zare, R. N. Some propensity rules in collision-induced rotational quantum jumps. J. Chem. Phys. 52, 1636–1643 (1970).

    Article  CAS  Google Scholar 

  2. Levine, R. D. Molecular Reaction Dynamics (Cambridge Univ. Press, 2005).

    Book  Google Scholar 

  3. Chandler, D. W. & Stolte, S. in Tutorials in Molecular Reaction Dynamics (eds Brouard, M. & Vallance, C.) Ch. 5, 116–166 (Royal Society of Chemistry, 2010).

    Google Scholar 

  4. Elioff, M. S., Valentini, J. J. & Chandler, D. W. Subkelvin cooling NO molecules via ‘billiard-like’ collisions with argon. Science 302, 1940–1943 (2003).

    Article  CAS  Google Scholar 

  5. Gilijamse, J. J., Hoekstra, S., van de Meerakker, S. Y. T., Groenenboom, G. C. & Meijer, G. Near-threshold inelastic collisions using molecular beams with a tunable velocity. Science 313, 1617–1620 (2006).

    Article  CAS  Google Scholar 

  6. Gijsbertsen, A. et al. Differential cross sections for collisions of hexapole state-selected NO with He. J. Chem. Phys. 123, 224305–224318 (2005).

    Article  CAS  Google Scholar 

  7. Sudbo, A. S. & Loy, M. M. T. Measurement of absolute state-to-state rate constants for collision-induced transitions between spin–orbit and rotational states of NO(X2Π, v = 2). J. Chem. Phys. 76, 3646–3654 (1981).

    Article  Google Scholar 

  8. Andresen, P., Joswig, H., Pauly, H. & Schinke, R. Resolution of interference effects in the rotational excitation of NO(N = O) by Ar. J. Chem. Phys. 77, 2204–2205 (1982).

    Article  CAS  Google Scholar 

  9. Suits, A. G., Bontuyan, L. S., Houston, P. L. & Whitaker, B. J. Differential cross sections for state-selected products by direct imaging: Ar+NO. J. Chem. Phys. 96, 8618–8620 (1992).

    Article  CAS  Google Scholar 

  10. Alexander, M. H. A new, fully ab initio investigation of the NO(X2Π)Ar system. I. Potential energy surfaces and inelastic scattering. J. Chem. Phys. 111, 7426–7434 (1999).

    Article  CAS  Google Scholar 

  11. Kohguichi, H., Suzuki, T. & Alexander, M. H. Fully state-resolved differential cross sections for the inelastic scattering of the open-shell NO molecule by Ar. Science 294, 832–834 (2001).

    Article  Google Scholar 

  12. Lorenz, K. T. et al. Direct measurement of the preferred sense of NO rotation after collision with argon. Science 293, 2063–2066 (2001).

    Article  CAS  Google Scholar 

  13. Elioff, M. S. & Chandler, D. W. State-to-state differential cross sections for spinmultiplet-changing collisions of NO(X2Π1/2) with argon. J. Chem. Phys. 117, 6455–6462 (2002).

    Article  CAS  Google Scholar 

  14. Aoiz, F. J., Verdasco, J. E., Herrero, V. J., Rábanos, V. S. & Alexander, M. H. Attractive and repulsive interactions in the inelastic scattering of NO by Ar: a comparison between classical trajectory and close-coupling quantum mechanical results. J. Chem. Phys. 119, 5860–5866 (2003).

    Article  CAS  Google Scholar 

  15. Alexander, M. H. Rotationally inleastic collisions between a diatomic molecule in a 2Π electronic state and a structureless target. J. Chem. Phys. 76, 5974–5988 (1982).

    Article  CAS  Google Scholar 

  16. Alexander, M. H. Quantum treatment of rotationally inelastic collisions involving molecules in Π electronic states: new derivation of the coupling potential. Chem. Phys. 92, 337–344 (1985).

    Article  CAS  Google Scholar 

  17. Zare, R. N. Angular Momentum, Understanding Spatial Aspects in Chemistry and Physics (John Wiley & Sons, 1988).

    Google Scholar 

  18. McCurdy, C. W. & Miller, W. H. Interference effects in rotational state distributions: propensity and inverse propensity. J. Chem. Phys. 67, 463–468 (1977).

    Article  CAS  Google Scholar 

  19. Korsch, H. J. & Schinke, R. A uniform semiclassical sudden approximation for rotationally inelastic scattering. J. Chem. Phys. 73, 1222–1232 (1980).

    Article  CAS  Google Scholar 

  20. Korsch, H. J. & Schinke, R. Rotational rainbows: an IOS study of rotational excitation of hard shell molecules. J. Chem. Phys. 75, 3850–3859 (1981).

    Article  CAS  Google Scholar 

  21. Bowman, J. M. Rotational rainbows in inelastic atommolecule differential cross sections. Chem. Phys. Lett. 62, 309–311 (1979).

    Article  CAS  Google Scholar 

  22. Gijsbertsen, A., Linnartz, H., Taatjes, C. A. & Stolte, S. Quantum interference as the source of steric asymmetry and parity propensity rules in NO–rare gas inelastic scattering. J. Am. Chem. Soc. 128, 8777–8789 (2005).

    Article  Google Scholar 

  23. Kłos, J. et al. Fully quantum state-resolved inelastic scattering between He and NO(X2Π). J. Chem. Phys. 127, 031102 (2007).

    Article  Google Scholar 

  24. Aoiz, F. J. et al. Inelastic scattering of He Atoms and NO(X2Π) molecules: The role of parity on the differential cross section. J. Phys. Chem. A 113, 14636–14649 (2009).

    Article  CAS  Google Scholar 

  25. Manolopoulos, D. E. An improved log derivative method for inelastic scattering. J. Chem. Phys. 85, 6425–6429 (1986).

    Article  CAS  Google Scholar 

  26. Alexander, M. H. & Manolopoulos, D. E. A stable linear reference potential algorithm for solution of the quantum close-coupled equations in molecular scattering theory. J. Chem. Phys. 86, 2044–2050 (1987).

    Article  CAS  Google Scholar 

  27. Bennewitz, H. G., Paul, W. & Schlier, C. Fokussierung polarer molekule. Z. Phys. 141, 6–15 (1955).

    Article  Google Scholar 

  28. Eppink, A. T. J. B. & Parker, D. H. Velocity map imaging of ions and electrons using electrostatic lenses: application in photoelectron and photofragment ion imaging of molecular oxygen. Rev. Sci. Instrum. 68, 3477–3484 (1997).

    Article  CAS  Google Scholar 

  29. Chandler, D. W. & Houston, P. L. Two-dimensional imaging of state-selected photodissociation products detected by multiphoton ionization. J. Chem. Phys. 87, 1445–1447 (1987).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

Support was provided by the UK EPSRC (to M.B. via programme grant no. EP/G00224X/1), the EU (to M.B. via FP7 EU People ITN project 238671), Consolider Ingenio 2010 (grant CSD2009-00038) and the Spanish Ministry of Science and Innovation (grant CTQ2008-02578/BQU). J.K. acknowledges financial support from the US National Science Foundation (grant no. CHE-0848110 to M.H. Alexander (Department of Chemistry and Biochemistry, University of Maryland, USA)) and the University Complutense de Madrid/Grupo Santander (under the ‘Movilidad de Investigadores Extranjeros’ programme). The support of the LASERLAB EUROPE is also gratefully acknowledged. Finally, the authors thank D.H. Parker and G. McBane for valuable discussions, and A. Ballast for help with collecting some of the data reported here.

Author information

Authors and Affiliations

  1. The Department of Chemistry, University of Oxford, The Physical and Theoretical Chemistry Laboratory, South Parks Road, Oxford, OX1 3QZ, UK

    C. J. Eyles & M. Brouard

  2. Institute for Molecules and Materials, Radboud University Nijmegen, Heijendaalseweg 135, 6525 ED Nijmegen, The Netherlands

    C.-H. Yang

  3. Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland, 20742, USA

    J. Kłos

  4. Departamento de Química Física, Facultad de Química, Universidad Complutense, Madrid, 28040, Spain

    F. J. Aoiz

  5. Laser Centre and Department of Physical Chemistry, Vrije Universiteit, Amsterdam, De Boelelaan 1083, Amsterdam, 1081 HV, The Netherlands

    A. Gijsbertsen, A. E. Wiskerke & S. Stolte

  6. FOM Institute AMOLF, Science Park 104, Amsterdam, 1098 XG, The Netherlands

    A. Gijsbertsen

  7. Atomic and Molecular Physics Institute, Jilin University, Changchun, 130012, China

    S. Stolte

  8. Laboratoire Francis Perrin, Bâtiment 522, DRECEM/SPAM/CEA Saclay, Gif sur Yvette, 91191, France

    S. Stolte

Authors
  1. C. J. Eyles
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. M. Brouard
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. C.-H. Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. J. Kłos
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. F. J. Aoiz
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. A. Gijsbertsen
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. A. E. Wiskerke
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. S. Stolte
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

The research project was conceived by M.B., F.J.A. and S.S., and the experiments were performed by C.J.E., C.-H.Y., A.G., A.E.W. and S.S. Calculations were performed by C.J.E., A.G., J.K., F.J.A. and S.S., and the paper was written by M.B. and C.J.E. All authors contributed to discussions about the content of the paper.

Corresponding author

Correspondence to M. Brouard.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 771 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Eyles, C., Brouard, M., Yang, CH. et al. Interference structures in the differential cross-sections for inelastic scattering of NO by Ar. Nature Chem 3, 597–602 (2011). https://doi.org/10.1038/nchem.1071

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nchem.1071

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing