Abstract
We introduce the two-particle probability density X(x) of x=r 12· p12=(r1 - r2) ·(p1 - p2). The fundamental equations involved in the derivation of this new intracule X(x), which we call the Posmom intracule, are derived and we show how to derive X(x) from the many-particle wave-function. We contrast it with the Dot intracule [Y.A. Bernard, D.L. Crittenden, and P.M.W. Gill, Phys. Chem. Chem. Phys. 10, 3447 (2008)] which can be derived from the Wigner distribution and show the relationships between the Posmom intracule and the one-particle Posmom density [Y.A. Bernard, D.L. Crittenden, and P.M.W. Gill, J. Phys. Chem. A 114, 11984 (2010)]. To illustrate the information provided by the Posmom intracule, we apply this new formalism to various two-electron systems: the three-dimensional parabolic quantum dot, the helium-like ions and the ground and excited states of the helium atom.
| Original language | English |
|---|---|
| Pages (from-to) | 2414-2426 |
| Number of pages | 13 |
| Journal | Molecular Physics |
| Volume | 111 |
| Issue number | 16-17 |
| DOIs | |
| Publication status | Published - 1 Sept 2013 |
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