Multiquantum Vibrational Excitation of NO Scattered from Au(111): Quantitative Comparison of Benchmark Data to Ab Initio Theories of Nonadiabatic Molecule–Surface Interactions

Cooper, Russell; Bartels, Christof; Kandratsenka, Alexander; Rahinov, Igor; Shenvi, Neil; Golibrzuch, Kai; Li, Zhisheng; Auerbach, Daniel J.; Tully, John C.; Wodtke, Alec M.

doi:10.1002/anie.201201168

Cited by 41 publications

(62 citation statements)

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“…26 This approach, which is an extension to the original surface hopping scheme, 19 is explained in detail in Refs. 20 and 21.…”

Section: B Theorymentioning

confidence: 99%

“…20 We used the same potential energy surfaces and nonadiabatic couplings as in previous IESH studies for NO/Au(111). 22,25,26 For comparison, analogous simulations were performed using an adiabatic model, employing the same code as for the IESH simulations but suppressing the electronic surface hopping. We also made comparison to an implementation of EF theory, 33 using the same potential energy surface as for the IESH calculations.…”

Section: B Theorymentioning

confidence: 99%

“…11,15 A detailed comparison of experimental results to IESH-based simulations showed good semi-quantitative agreement over the entire range of experimental conditions, whereas electronic friction based simulations failed completely. 26 Despite this unprecedented success, the IESH-based simulations deviated from experiment in a systematic way: they predicted a dependence of vibrational excitation on incidence energy of translation that was somewhat weaker than that seen experimentally. Subsequent work at a single incidence energy also showed the IESH-based simulations underestimated the amount of NO(v = 0 → 3) excitation.…”

Section: Introductionmentioning

confidence: 99%

“…Finally, it was argued that the IESH theory unifies our picture of energy transfer for NO/Au(111) scattering for vibrational excitation of v = 0 and vibrational relaxation of v = 15. 26 The application of the same model to NO(v = 3 → 3, 2, 1) relaxation is an obvious additional test.…”

Section: Introductionmentioning

confidence: 99%

“…The experimental data are compared to state-to-state scattering probabilities derived from electronically adiabatic MD simulations as well as two approaches to electronically nonadiabatic molecular dynamics (IESH 22,26 and EF 26 ). We find significant disagreement between observation and all three theoretical models.…”

Section: Introductionmentioning

confidence: 99%

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The importance of accurate adiabatic interaction potentials for the correct description of electronically nonadiabatic vibrational energy transfer: A combined experimental and theoretical study of NO(v = 3) collisions with a Au(111) surface

Golibrzuch

Shirhatti

Rahinov

et al. 2014

The Journal of Chemical Physics

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We present a combined experimental and theoretical study of NO(v = 3 → 3, 2, 1) scattering from a Au(111) surface at incidence translational energies ranging from 0.1 to 1.2 eV. Experimentally, molecular beam-surface scattering is combined with vibrational overtone pumping and quantumstate selective detection of the recoiling molecules. Theoretically, we employ a recently developed first-principles approach, which employs an Independent Electron Surface Hopping (IESH) algorithm to model the nonadiabatic dynamics on a Newns-Anderson Hamiltonian derived from density functional theory. This approach has been successful when compared to previously reported NO/Au scattering data. The experiments presented here show that vibrational relaxation probabilities increase with incidence energy of translation. The theoretical simulations incorrectly predict high relaxation probabilities at low incidence translational energy. We show that this behavior originates from trajectories exhibiting multiple bounces at the surface, associated with deeper penetration and favored (N-down) molecular orientation, resulting in a higher average number of electronic hops and thus stronger vibrational relaxation. The experimentally observed narrow angular distributions suggest that mainly single-bounce collisions are important. Restricting the simulations by selecting only single-bounce trajectories improves agreement with experiment. The multiple bounce artifacts discovered in this work are also present in simulations employing electronic friction and even for electronically adiabatic simulations, meaning they are not a direct result of the IESH algorithm. This work demonstrates how even subtle errors in the adiabatic interaction potential, especially those that influence the interaction time of the molecule with the surface, can lead to an incorrect description of electronically nonadiabatic vibrational energy transfer in molecule-surface collisions. © 2014 AIP Publishing LLC. [http://dx

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“…26 This approach, which is an extension to the original surface hopping scheme, 19 is explained in detail in Refs. 20 and 21.…”

Section: B Theorymentioning

confidence: 99%