** Reference to paper:

https://doi.org/10.1021/acs.jpclett.1c02093

** DOI:

10.1021/acs.jpclett.1c02093

** Title:

Highly Efficient Activation of HCl Dissociation on Au(111) via Rotational Preexcitation

** Authors:

Gerrits, Nick; Geweke, Jan; Auerbach, Daniel J.; Beck, Rainer D.; Kroes, Geert-Jan

** Contact e-mail:

n.gerrits@lic.leidenuniv.nl
g.j.kroes@chem.leidenuniv.nl

** Abstract:

The probability for dissociation of molecules on metal surfaces, which often controls the rate of industrially important catalytic processes, can depend strongly on how energy is partitioned in the incident molecule.
There are many example systems where the addition of vibrational energy promotes reaction more effectively than the addition of translational energy, but for rotational pre-excitation similar examples have not yet been discovered.
Here, we make an experimentally testable theoretical prediction that adding energy to the rotation of HCl can promote its dissociation on Au(111) 20 times more effectively than increasing its translational energy.
In the underlying mechanism, the molecule’s initial rotational motion allows it to pass through a critical region of the reaction path, where this path shows a strong and nonmonotonic dependence on the molecular orientation.

** Description per file:

Most of the files necessary to reproduce this work have already been provided in ../2020_jpcc_HCl_Au111/.
One important caveat is that the original initial conditions code made by Gernot Fuechsel contained a bug in the mJ sampling (mJ=0 was counted twice), which has been remedied in this work.

** Folder Figure01:
plotsticking_rotationalefficacy.py - Generates the plot. Can also be used to compute efficacies (see the commented code).
reactionprobability_rotationalefficacy.pdf
sticking_data.py - Contains the new sticking data with the correct mJ sampling

** Folder Figure02:
plotsticking_laseron.py - Generates the plot; also used to generate Figure S03
reactionprobability_laser.pdf

** Folder Figure03:
explanation_rotational_mechanism.pdf
explanation_rotational_mechanism.py - Generates the plot. Some parts requires MD data to generate the subplot

** Folder Figure04:
draw_elbow.py - Generates the plot
energy_*.dat - Contains the data
TS_elbow_theta.pdf

** Folder Figure05:
plotsticking_DS1DS2_jpcl.py - Generates the plot
reactionprobability_DS1DS2_jpcl.pdf

** Folder FigureS01:
reactionprobability_exp_fits.pdf
plotsticking_exp_fits.py - Generates the plot

** Folder FigureS02:
vjpopulation.pdf
plotvjpopulation.py - Generates the plot

** Folder FigureS03:
reactionprobability_laser_SI.pdf - Generated by Figure02/plotsticking_laseron.py

** Folder FigureS04:
reactionprobability_DS1DS2.pdf
plotsticking_DS1DS2.py - Generates the plot

** Folder FigureS05:
Analysis_angle_r_snapshot.py - Generates the plot; requires MD data
angles_r_snapshot.pdf

** Folder FigureS06:
Analysis_angle_reactionpath.py - Generates the plot; requires MD data
angles_reactionpath.pdf

** Folder FigureS07:
Analysis_theta_sticking.py - Obtains the results from the MD data
plotsticking_theta.py - Generates the plot
reactionprobability_theta.pdf

** Folder FigureS08:
Analysis_momentum_theta_relative.py - Generates the plot; requires MD data
momentum_theta_relative_v0.pdf

** Folder FigureS09:
momentum_theta_relative_v1.pdf - Generated by FigureS08/Analysis_momentum_theta_relative.py

** Folder FigureS10:
momentum_theta_relative_v2.pdf - Generated by FigureS08/Analysis_momentum_theta_relative.py

** Folder FigureS11:
plotrotationalstate.py - Generates the plot
rotationalstate.pdf

** Folder FigureS12:
momentum_theta_analytical_v0.pdf
Analysis_momentum_theta_analytical.py - Generates the plot

** Folder FigureS13:
sticking_theta_analytical.pdf - Generated by FigureS12/Analysis_momentum_theta_analytical.py

** Folder FigureS14:
MEP_theta_MD.pdf
MEP_theta_MD.py - Generates the plot; requires MD trajectories (analysis_rcom.dat)

** Folder FigureS15:
plottheta_mep_pbe.py - Generates the plot
theta_mep_PBE.pdf

** Folder FigureS16:
TS_theta.pdf
plotTS_theta.py - Generates the plot

** Folder hcl_initialconditions
Contains the initial conditions code for HCl (with the mJ sampling bugfix).
It can be compiled by running './compile' in SOURCE.
Original code is by Gernot Fuechsel, with modifications by Nick Gerrits.
'source_static' and 'MAKE_ONLY_ROVIB' are unaltered versions from Gernot.
'gasphase.dat' contains the vibrational potential of HCl obtained with the MS-RPBEl DF.
One should ask Gernot for permission to use this code and reference 10.1021/acs.jpcc.6b07453 (also contains some details about the initial conditions).
No documentation for the code exists: The source code is your documentation.