ReactionMechanismGenerator / ReactionMechanismGenerator/ARC

Improper to neglect single-well hindered rotor with a high barrier?

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#400 1 comment 0 reactions 1 assignee View on GitHub

@alongd is already working on this.

Since Jun 3, 2020.

Topic: Rotors Type: Question
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Python
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Description

I am trying to benchmark some of our calculations. Currently, ARC will neglect a single-well hindered rotor with a high barrier. It is reasonable when the PES shape is close to cosine curve, so that RRHO approximation can work okay. But there are many cases where the shapes are much different, like the one below
image
(Around 120 degrees, there is a plateau-like region, but not a well). The barrier height is 50 kJ/mol

Whether or not treat this mode as hindered rotor, can cause a difference, especially at high-T. like below
image
(without [1,2] is not treating the torsional mode above as a hindered rotor which obtained from ARC, and the other curve is by manually add this torsional mode in Arkane calculation)

I think we should still treat it as a hindered rotor. Although this is a single example, but there are plenty of cases like this. If people agree with the idea, I will modify the corresponding part in ARC.

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