Who ever loved that loved not at first sight? — Shakespeare
Here's the detailed synastry chart for Brad Pitt and Angelina Jolie as viewed in both their natal chart and the 90-degree Cosmobiology (midpoint astrology) chart.
Brad is a fiery Sagittarius sun sign, which maps to a Mutable position on the Cosmobiology wheel. The Mutables are excellent companions because they are beautifully adaptable. Your way is their way. Sagittarians are always on the go with people and their honesty can be very refreshing in a relationship.
Angelina is a Gemini air sun sign, which also maps to a Mutable position on the Cosmobiology wheel. Gemini's are enthusiastic, interesting people. They are never bored and they pass this love of life on to others.
And the rest of their midpoints ... Wow! So where did things go wrong and end in divorce?
Some of the tighter midpoints offer a clue:
Mars □ Mars at 0 °41' is a very close orb and implies a constant exchange of energy between the couple. This might mean great vitality and activity or it could mean stress and fighting.
Similarly, Neptune □ Uranus at 0 °16' represents deep caring feelings but there is the downside of agitation and restlessness (Uranus) and shattered ideals and despondency (Neptune).
Calculations based on: Angelina Jolie, Jun 4 1975, 9:09 AM PDT, Los Angeles CA; Brad Pitt, Dec 18 1963, 6:31AM CST, Shawnee, OK