Abstract
In the realm of molecular collision dynamics, stereochemistry refers to the dependence of the collision outcome on the mutual orientation of the colliding partners. This may involve directed end-on collisions along a molecular bond axis or encounters in which the partner approaches the bond of an oriented molecule from the side. Using both experiment and theory, we show here that in the simplest case of an inelastic collision between an atom and a nearly homonuclear diatom, in which the two atoms have almost the same mass, the scattering dynamics are very distinct for impacts on either side of the molecule. By recording the direction of the scattered particles after the collision, we demonstrate that the intensity of products scattered in the forward direction, near parallel to the initial motion, can be substantially controlled and even maximized by altering the side-on orientation of the quantum state selected NO molecules that collide with Ar atoms. In addition, our findings provide valuable information about the preferred collision mechanism and reveal interesting quantum interference effects.
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Data availability
Experimental and computational data that support the findings of this study are available from the Oxford Research Archive (https://doi.org/10.5287/bodleian:j0eYa9r6g).
Code availability
The Hibridon set of programs used for the QM calculations can be downloaded from www2.chem.umd.edu/groups/alexander/hibridon/hib43/index.html. The computer codes used for the data analysis are available from the corresponding author upon reasonable request.
References
Trautz, M. Das Gesetz der Reaktionsgeschwindigkeit und der Gleichgewichte in Gasen. Bestätigung der Additivität von C v−3/2R. Neue Bestimmung der Integrationskonstanten und der Moleküldurchmesser (The law of reaction rates and equilibria in gases. Confirmation of the additivity of C v−3/2R: New determination of the integration constants and the molecular diameters). Z. Anorg. Allg. Chem. 96, 1–28 (1916).
Levine, R. D. & Bernstein, R. B. Molecular Reaction Dynamics and Chemical Reactivity (Oxford Univ. Press, 1987).
Parker, D. H. & Bernstein, R. B. Oriented molecule beams via the electrostatic hexapole: preparation, characterization, and reactive scattering. Ann. Rev. Phys. Chem. 40, 561–595 (1989).
Loesch, H. J. Orientation and alignment in reactive beam collisions: recent progress. Ann. Rev. Phys. Chem. 46, 555–594 (1995).
Paterson, G., Costen, M. L. & McKendrick, K. G. Collisional depolarisation of rotational angular momentum: influence of the potential energy surface on the collision dynamics? Int. Rev. Phys. Chem. 31, 69–109 (2012).
Brouard, M. & Vallance, C. Tutorials in Molecular Reaction Dynamics (Royal Society of Chemistry, 2012).
Aoiz, F. J. et al. A new perspective: imaging the stereochemistry of molecular collisions. Phys. Chem. Chem. Phys. 17, 30210–30228 (2015).
Sharples, T. R. et al. Non-intuitive rotational reorientation in collisions of NO(A2Σ+) with Ne from direct measurement of a four-vector correlation. Nat. Chem. 10, 1148–1153 (2018).
Wang, F., Lin, J.-S. & Liu, K. Steric control of the reaction of CH stretch-excited CHD3 with chlorine atom. Science 331, 900–903 (2011).
Wang, F., Liu, K. & Rakitzis, T. P. Revealing the stereospecific chemistry of the reaction of Cl with aligned CHD3 (ν 1 = 1). Nat. Chem. 4, 636–641 (2012).
Perreault, W. E., Mukherjee, N. & Zare, R. N. Quantum control of molecular collisions at 1 kelvin. Science 358, 356–359 (2017).
Van Leuken, J. J., Bulthuis, J., Stolte, S. & Snijders, J. G. Steric asymmetry in rotationally inelastic state-resolved NO + Ar collisions. Chem. Phys. Lett. 260, 595–603 (1996).
Alexander, M. H. & Stolte, S. Investigation of steric effects in inelastic collisions of NO(X) with Ar. J. Chem. Phys. 112, 8017–8026 (2000).
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 (2006).
de Miranda, M. H. G. et al. Controlling the quantum stereodynamics of ultracold bimolecular reactions. Nat. Phys. 7, 502–507 (2011).
Onvlee, J. et al. Imaging quantum stereodynamics through Fraunhofer scattering of NO radicals with rare-gas atoms. Nat. Chem. 9, 226–233 (2016).
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).
Kohguchi, H., Suzuki, T. & Alexander, M. H. Fully state-resolved differential cross section for the inelastic scattering of the open-shell NO molecule by Ar. Science 294, 832–834 (2001).
Lorenz, K. T. et al. Direct measurement of the preferred sense of NO rotation after collision with argon. Science 293, 2063–2066 (2001).
Gijsbertsen, A. et al. Differential cross sections for collisions of hexapole state-selected NO with He. J. Chem. Phys. 123, 224305 (2005).
Eyles, C. J. et al. Interference structures in the differential cross-sections for inelastic scattering of NO by Ar. Nat. Chem. 3, 597–602 (2011).
von Zastrow, A. et al. State-resolved diffraction oscillations imaged for inelastic collisions of NO radicals with He, Ne and Ar. Nat. Chem. 6, 216–221 (2014).
Vogels, S. N. et al. Imaging resonances in low-energy NO–He inelastic collisions. Science 350, 787–790 (2015).
Nichols, B. et al. Steric effects and quantum interference in the inelastic scattering of NO(X) + Ar. Chem. Sci. 6, 2202–2210 (2015).
Brouard, M. et al. Stereodynamics in NO(X) + Ar inelastic collisions. J. Chem. Phys. 144, 224301 (2016).
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).
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).
Eyles, C. J. et al. The effect of parity conservation on the spin–orbit conserving and spin–orbit changing differential cross sections for the inelastic scattering of NO(X) by Ar. Phys. Chem. Chem. Phys. 14, 5420–5439 (2012).
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).
Eyles, C. J. et al. Fully Λ-doublet resolved state-to-state differential cross-sections for the inelastic scattering of NO(X) with Ar. Phys. Chem. Chem. Phys. 14, 5403–5419 (2012).
McCurdy, C. W. & Miller, W. H. Interference effects in rotational state distributions: propensity and inverse propensity. J. Chem. Phys. 67, 463–468 (1977).
Brouard, M. et al. Integral steric asymmetry in the inelastic scattering of NO(X2Π). J. Chem. Phys. 146, 014302 (2017).
Khare, V., Kouri, D. J. & Hoffman, D. K. On j z-preserving propensities in molecular collisions. I. Quantal coupled states and classical impulsive approximations. J. Chem. Phys. 74, 2275–2286 (1981).
Acknowledgements
The support of the UK EPSRC (to M.B. via Programme Grant EP/L005913/1), and the Spanish Ministry of Science and Innovation (Grant No. CTQ2015-65033-P to F.J.A.) is acknowledged. P.G.J. acknowledges funding by the Fundación Salamanca city of culture and knowledge (programme for attracting scientific talent to Salamanca). We thank S. Stolte for many stimulating discussions throughout the course of some of the research described here.
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The research project was conceived by M.B., C.G.H. and F.J.A. The experiments were performed by V.W. and C.G.H., and the data analysis was carried out by V.W. The theory was developed by M.B., V.W., P.G.J. and F.J.A., with the calculations performed by V.W. and P.G.J. The paper was written by M.B. and F.J.A., with all the authors contributing to discussions about the content of the paper.
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Supplementary Methods, Supplementary analysis and Supplementary Figs. 1–8.
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Heid, C.G., Walpole, V., Brouard, M. et al. Side-impact collisions of Ar with NO. Nat. Chem. 11, 662–668 (2019). https://doi.org/10.1038/s41557-019-0272-3
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DOI: https://doi.org/10.1038/s41557-019-0272-3