Quasiclassical simulations based on cluster models reveal vibration-facilitated roaming in the isomerization of CO adsorbed on NaCl

Abstract

The desire to better understand the quantum nature of isomerization led to recent experimental observations of the vibrationally induced isomerization of OC–NaCl(100) to CO–NaCl(100). To investigate the mechanism of this isomerization, we performed dynamics calculations using finite (CO–NaCl)n cluster models. We constructed new potential energy surfaces for CO–NaCl and CO–CO interactions using high-level ab initio data and report key properties of the bare CO–NaCl potential energy surface, which show much in common with the experiment. We investigated the isomerization dynamics using several cluster models and, in all cases, isomerization was seen for highly excited CO vibrational states, in agreement with experiments. A detailed examination of the reaction trajectories indicates that isomerization occurs when the distance between CO and NaCl is larger than the distance at the conventional isomerization saddle point, which is a strong indicator of ‘roaming’.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Fig. 1: Structures of the C-down and O-down minima from the average CO–NaCl potential.
Fig. 2: Depictions of the central CO for C-down and O-down isomers for the cluster with 13 COs.
Fig. 3: One-dimensional unrelaxed potential cuts for isomerization.
Fig. 4: Contour plots for the large cluster PES of the central CO.
Fig. 5: Histogram of the distribution of z, the distance above the surface, at which isomerization occurs.
Fig. 6: Signature of roaming dynamics.

Data availability

All the data shown here are available in the Supplementary Information. Source data are provided with this paper.

Code availability

The potentials reported in the paper are available in compressed folders as Supplementary Information.

References

  1. 1.

    Bowman, J. M., Gazdy, B., Bentley, J. A., Lee, T. J. & Dateo, C. E. Ab initio calculation of a global potential, vibrational energies, and wave functions for HCN/HNC, and a simulation of the \(\tilde A\)\(\tilde A\) emission spectrum. J. Chem. Phys. 99, 308–323 (1993).

    CAS  Article  Google Scholar 

  2. 2.

    Bowman, J. M. Beyond platonic molecules. Science 290, 724–725 (2000).

    CAS  Article  Google Scholar 

  3. 3.

    Zou, S., Bowman, J. M. & Brown, A. Full-dimensionality quantum calculations of acetylene vinylidene isomerization. J. Chem. Phys. 118, 10012–10023 (2003).

    CAS  Article  Google Scholar 

  4. 4.

    DeVine, J. A. et al. Encoding of vinylidene isomerization in its anion photoelectron spectrum. Science 358, 336–339 (2017).

    CAS  Article  Google Scholar 

  5. 5.

    Lau, J. A. et al. Observation of an isomerizing double-well quantum system in the condensed phase. Science 367, 175–178 (2020).

    CAS  PubMed  Google Scholar 

  6. 6.

    Chen, L. et al. The Sommerfeld ground-wave limit for a molecule adsorbed at a surface. Science 363, 158–161 (2019).

    CAS  Article  Google Scholar 

  7. 7.

    Vogt, J. & Vogt, B. The structure of carbon monoxide adsorbed on the NaCl(100) surface: a combined LEED and DFT-D/vdW-DF study. J. Chem. Phys. 141, 214708 (2014).

    Article  Google Scholar 

  8. 8.

    Chen, J., Li, J., Bowman, J. M. & Guo, H. Energy transfer between vibrationally excited carbon monoxide based on a highly accurate six-dimensional potential energy surface. J. Chem. Phys. 153, 054310 (2020).

    CAS  Article  Google Scholar 

  9. 9.

    Hoang, P. N. M., Picaud, S., Girardet, C. & Meredith, A. W. Structure of CO monolayer adsorbed on NaCl(100) from molecular dynamics. J. Chem. Phys. 105, 8453–8462 (1996).

    CAS  Article  Google Scholar 

  10. 10.

    Meredith, A. W. & Stone, A. J. A perturbation theory study of adlayer CO on NaCl(100). J. Chem. Phys. 104, 3058–3070 (1996).

    CAS  Article  Google Scholar 

  11. 11.

    Corcelli, S. A. & Tully, J. C. Vibrational energy pooling in CO on NaCl(100): methods. J. Chem. Phys. 116, 8079–8092 (2002).

    CAS  Article  Google Scholar 

  12. 12.

    Boney, E. T. D. & Marcus, R. A. On the infrared fluorescence of monolayer 13CO:NaCl(100). J. Chem. Phys. 139, 184712 (2013).

    CAS  Article  Google Scholar 

  13. 13.

    Boese, A. D. & Saalfrank, P. CO molecules on a NaCl(100) surface: structures, energetics, and vibrational Davydov splittings at various coverages. J. Phys. Chem. C 120, 12637–12653 (2016).

    CAS  Article  Google Scholar 

  14. 14.

    Chen, J., Hariharan, S., Meyer, J. & Guo, H. Potential energy landscape of CO adsorbates on NaCl(100) and implications in isomerization of vibrationally excited CO. J. Phys. Chem. C 124, 19146–19156 (2020).

    CAS  Article  Google Scholar 

  15. 15.

    Townsend, D. et al. The roaming atom: straying from the reaction path in formaldehyde decomposition. Science 306, 1158–1161 (2004).

    CAS  Article  Google Scholar 

  16. 16.

    Suits, A. G. Roaming atoms and radicals: a new mechanism in molecular dissociation. Acc. Chem. Res. 41, 873–881 (2008).

    CAS  Article  Google Scholar 

  17. 17.

    Bowman, J. M. & Shepler, B. C. Roaming radicals. Ann. Rev. Phys. Chem. 62, 531–553 (2011).

    CAS  Article  Google Scholar 

  18. 18.

    Homayoon, Z. & Bowman, J. M. Quasiclassical trajectory study of CH3NO2 decomposition via roaming mediated isomerization using a global potential energy surface. J. Phys. Chem. A 117, 11665–11672 (2013).

    CAS  Article  Google Scholar 

  19. 19.

    Zhu, R. & Lin, M. CH3NO2 decomposition/isomerization mechanism and product branching ratios: an ab initio chemical kinetic study. Chem. Phys. Lett. 478, 11–16 (2009).

    CAS  Article  Google Scholar 

  20. 20.

    Dey, A. et al. Photodissociation dynamics of nitromethane and methyl nitrite by infrared multiphoton dissociation imaging with quasiclassical trajectory calculations: signatures of the roaming pathway. J. Chem. Phys. 140, 054305 (2014).

    Article  Google Scholar 

  21. 21.

    Wodtke, A. M., Hintsa, E. J. & Lee, Y. T. Infrared multiphoton dissociation of three nitroalkanes. J. Phys. Chem. 90, 3549–3558 (1986).

    CAS  Article  Google Scholar 

Download references

Acknowledgements

J.M.B. and H.G. thank the Alexander von Humboldt Foundation for Humboldt Research Awards. In addition, J.M.B. thanks NASA (80NSSC20K0360) for financial support and H.G. thanks the National Science Foundation (CHE-1462109 and CHE-1951328) for financial support. We thank J. Lau and A. Wodtke for extensive discussions.

Author information

Affiliations

Authors

Contributions

A.N. performed the dynamics calculations, developed the CO–NaCl potential and cluster potential, refitted the CO–CO potential and helped write the paper and prepared most of the figures. P.Z. performed DFT calculations of energies of the CO–NaCl stationary points. J.C. performed electronic structure calculations of the CO–CO interaction. H.G. helped conceive the research, helped writing the paper and supervised the creation of the CO–CO electronic energy dataset. J.M.B. conceived the research, wrote the paper and supervised the dynamics calculations.

Corresponding author

Correspondence to Joel M. Bowman.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Peer review information Nature Chemistry thanks Jochen Vogt and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–14, and Tables 1–9.

Supplementary Video 1

QCT Trajectory Animation.

Supplementary Software 1

All three PES Software. ‘CO_CO_Int’ folder contains CO-CO interaction PES; ‘CO_MRCI’ folder contains isolated CO PES; and ‘NaCl_CO_Int’ folder contains NaCl-CO interaction PES.

Supplementary Data 1

Source data for the figures within the Supplementary Information file.

Source data

Source Data Fig. 3

Source data for Figure 3.

Source Data Fig. 4

Source data for Figure 4.

Source Data Fig. 5

Source data for Figure 5 .

Source Data Fig. 6

Source data for Figure 6.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Nandi, A., Zhang, P., Chen, J. et al. Quasiclassical simulations based on cluster models reveal vibration-facilitated roaming in the isomerization of CO adsorbed on NaCl. Nat. Chem. (2021). https://doi.org/10.1038/s41557-020-00612-y

Download citation

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