Intrinsic-reaction-coordinate calculations: Difference between revisions
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The potential energy profiles along intrinsic reaction coordinate (IRC) can be computed via d method of Hratchian and Schlegel<ref>[https://pubs.acs.org/doi/abs/10.1021/jp012125b H. P. Hratchian and H. B. Schlegel, J. Phys. Chem. A 106, 165 (2002).] </ref>. The algorithm starts from transition state and propagates the system via damped velocity Verlet algorithm. The damping is realized via rescaling the velocity vector to a constant value (<math>v_0</math>) after each propagation step. At the same time, the time step is adaptively changed so as to ensure that the trajectory generated by the algorithm does not differ from true IRC by more that the predefined tolerance factor <math>\Delta_0</math>. As an input, the structure of well relaxed transition state and the direction of unstable vibration mode must be provided. To obtain a complete energy profile along IRC connecting two stable states, two independent calculations with positive and negative initial displacement along the direction of unstable mode must be performed. | The potential energy profiles along intrinsic reaction coordinate (IRC) can be computed via d method of Hratchian and Schlegel<ref>[https://pubs.acs.org/doi/abs/10.1021/jp012125b H. P. Hratchian and H. B. Schlegel, J. Phys. Chem. A 106, 165 (2002).] </ref>. The algorithm starts from transition state and propagates the system via damped velocity Verlet algorithm. The damping is realized via rescaling the velocity vector to a constant value (<math>v_0</math>) after each propagation step. At the same time, the time step is adaptively changed so as to ensure that the trajectory generated by the algorithm does not differ from true IRC by more that the predefined tolerance factor <math>\Delta_0</math>. As an input, the structure of well relaxed transition state and the direction of unstable vibration mode must be provided. For that purpose, a CONTCAR file from the To obtain a complete energy profile along IRC connecting two stable states, two independent calculations with positive and negative initial displacement along the direction of unstable mode must be performed. | ||
*{{TAG|IRC_DIRECTION }} direction of the initial displacement (-1|1 – negative|positive) | *{{TAG|IRC_DIRECTION }} direction of the initial displacement (-1|1 – negative|positive) | ||
*{{TAG|IRC_STOP}} = 20 the number of steps the energy must monotonously increase before the algorithm terminates. In order to avoid a premature terminations, especially close to transition states., e.g., due to a numerical noise, {{TAG|IRC_STOP}} should always be greater than 1. | *{{TAG|IRC_STOP}} = 20 the number of steps the energy must monotonously increase before the algorithm terminates. In order to avoid a premature terminations, especially close to transition states., e.g., due to a numerical noise, {{TAG|IRC_STOP}} should always be greater than 1. | ||
*{{TAG|IRC_DELTA0}} = 0.0015 the tolerance factor <math>\Delta_0</math> in Å – the smaller value, the closer the computed trajectory follows the true IRC (but the more DFT steps is needed) | *{{TAG|IRC_DELTA0}} = 0.0015 the tolerance factor <math>\Delta_0</math> in Å – the smaller value, the closer the computed trajectory follows the true IRC (but the more DFT steps is needed) | ||
*{{TAG|IRC_MINSTEP}} = 0.0250 | *{{TAG|IRC_MINSTEP}} = 0.0250 | ||
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{{NB|mind|2=This method is presently available only for fixed cell shape (i.e., {{TAG|ISIF}} = 2) simulations.}} | {{NB|mind|2=This method is presently available only for fixed cell shape (i.e., {{TAG|ISIF}} = 2) simulations.}} | ||
{{NB|mind|2=The calculation must be initialized from a very well relaxed transition state ({{TAG|EDIFFG}} = -0.005 or less in absolute value).}} | {{NB|mind|2=The calculation must be initialized from a very well relaxed transition state ({{TAG|EDIFFG}} = -0.005 or less in absolute value).}} | ||
<references /> | <references /> | ||
Revision as of 16:06, 11 February 2023
The potential energy profiles along intrinsic reaction coordinate (IRC) can be computed via d method of Hratchian and Schlegel[1]. The algorithm starts from transition state and propagates the system via damped velocity Verlet algorithm. The damping is realized via rescaling the velocity vector to a constant value () after each propagation step. At the same time, the time step is adaptively changed so as to ensure that the trajectory generated by the algorithm does not differ from true IRC by more that the predefined tolerance factor . As an input, the structure of well relaxed transition state and the direction of unstable vibration mode must be provided. For that purpose, a CONTCAR file from the To obtain a complete energy profile along IRC connecting two stable states, two independent calculations with positive and negative initial displacement along the direction of unstable mode must be performed.
- IRC_DIRECTION direction of the initial displacement (-1|1 – negative|positive)
- IRC_STOP = 20 the number of steps the energy must monotonously increase before the algorithm terminates. In order to avoid a premature terminations, especially close to transition states., e.g., due to a numerical noise, IRC_STOP should always be greater than 1.
- IRC_DELTA0 = 0.0015 the tolerance factor in Å – the smaller value, the closer the computed trajectory follows the true IRC (but the more DFT steps is needed)
- IRC_MINSTEP = 0.0250
- IRC_MAXSTEP = 3.0000
- IRC_VNORM0 = 0.0020 the value of in Å/fs
| Mind: This method is presently available only for fixed cell shape (i.e., ISIF = 2) simulations. |
| Mind: The calculation must be initialized from a very well relaxed transition state (EDIFFG = -0.005 or less in absolute value). |