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ramess101 / JCED_FOMMS_Manuscript

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Physical explanation of Keff in vapor and liquid phases #21

Open ramess101 opened 5 years ago

ramess101 commented 5 years ago

@mrshirts

You mentioned that it would be helpful to have a physical explanation for why the overlap is worse in the liquid phase. I have added a paragraph to explain this more clearly. Let me know if you would like to modify this explanation at all.

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mrshirts commented 5 years ago

I would probably say, to provide a bit more context, that "First, the vapor phase has fewer molecules overall. If each individual molecule has fixed energy difference \Delta E when changing parameters, resulting in a change of probability proportional to exp(-Beta \Delta E), then if the system has N molecules, this results in a probability change of exp(-Beta N\Delta E). This means that smaller systems will be more similar , which leads to greater overlap". That's my first pass - could be improved to be clearer.

Also "varying lambda greatly impacts the non-bonded energy for those close range interactions" -> "varying lambda significantly changes the slope and location of the repulsive wall, greatly impacting the non-bonded energy" . . .

ramess101 commented 5 years ago

@mrshirts

I tried to modify your explanation of "First, the vapor phase has fewer molecules overall..." so that it fit the rest of the manuscript. Let me know if the meaning was changed or lost in this version:

image

mrshirts commented 5 years ago

Maybe just a bit of connections to the Boltzmann factor/probability. For example, maybe "is similar for theta_rr and theta_ref, through the ratio of the Boltzmann factors for two ensembles"

ramess101 commented 5 years ago

@mrshirts

OK, I added: "similar for theta_rr and theta_ref, such that the ratio of Boltzmann factors is close to unity."

Is that good?