correct macro-states idea

[hamid...@yahoo.com]

Dear Pyxaid users,

I have one question regarding the idea of macrostates when studying the dynamics of charge transfer at the A/B interface. Suppose, the transfer is from structure A to structure B, and HOMO, HOMO-1, LUMO, LUMO+1 belong to the acceptor structure B and HOMO-2 and LUMO+2 and LUMO+3 belong to donor structure A.

When defining multi-electron states (MES) in NAMD simulation step, some MESs containing one electron in LUMO+2 and LUMO+3 of donor structure A and the hole in HOMO, and HOMO+1 of acceptor state can be defined.

Can these MESs be included when describing a macrostate of charge population in the donor structure A?

Thank you

[Alexey Akimov]

Hamid,

The multi-electron states (in the form of Slater determinants) can be defined no matter what. It is the question of how you interpret them. If you have electron and hole localized on different parts of the actual system and these electron and hole are parts of the same determinant, this is a charge-separated state. This is unlike the determinants which have both electron and hole localized on the same part of a system - that would be exciton (localized excitation). All types of states may participate in the dynamics - both excitonic and charge separated states, so it may be better to include them in your basis. 

It makes sense to define macrostates based on the localization properties. E.g. I'd group the configurations with similar energy range and both of the charge-separated character in a one macrostate, localized excitation in another state, etc. 

Hope this helps,

Alexey

[hamid...@yahoo.com]

Really appreciated