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Document specifying the PCM solvent by name - #193

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Document specifying the PCM solvent by name#193
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JustinKyleKirkland:pcm-solvent-name-docs

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Documentation for pyscf/pyscf#3416, as requested by @jeanwsr in that PR.

That change lets the PCM family take a solvent name, which assigns both the static dielectric constant eps and the optical one eps_optical. The user guide previously described only assigning eps by hand, and never mentioned eps_optical at all, even though it is what the non-equilibrium solvation of excited states actually uses.

Changes to source/user/solvent.rst

The PCM Solvent parameters section is rewritten around the name-based API and now covers:

  • the three places a name can be given: the PCM constructor, the .PCM() method of a mean-field object, and assignment to with_solvent.solvent at any point;
  • case-insensitive matching that ignores spaces and hyphens, and the recognized abbreviations (h2o, dmso, dmf, dma, thf, dcm, ccl4, chcl3, mecn, acn, meoh, etoh, et2o, ether);
  • what the two dielectric constants each control, and that eps_optical matters only for excited states;
  • that without a name, eps_optical falls back to water and a warning is issued when eps indicates a different solvent.

The manual eps route is kept, since it still works and still overrides the database value.

The Solvent for excited states section gains a short pointer noting that the slow solvent uses eps_optical, so specifying the solvent by name is the right way to set up those calculations.

The attribution of the parameters is also brought in line with the merged database: they come from the Minnesota Solvent Descriptor Database, except for the dielectric constant of water, which is the 78.3553 value from gaussian.com/scrf.

Checks

The two new internal cross references resolve against unique section titles, and docutils reports no warnings for the file beyond the pre-existing note about the _user_solvent label being referenced from other pages.

This should be merged after pyscf/pyscf#3416, since it documents behaviour that only exists there.

pyscf/pyscf#3416 lets the PCM family take a solvent name, which sets both
the static dielectric constant and the optical one. The user guide still
only described assigning eps by hand, and never mentioned eps_optical at
all, even though it is what the non-equilibrium solvation of excited states
uses.

Rewrite the PCM "Solvent parameters" section around the name-based API,
covering the three places a name can be given, the case-insensitive
matching and the recognized abbreviations, and what the two dielectric
constants each control. Keep the manual eps route, which still works and
still overrides the database.

Also note in "Solvent for excited states" that the slow solvent uses
eps_optical, so a solvent name is the right way to set those calculations
up. Without one, eps_optical falls back to the value for water.
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