Both FreezeArrow and ImmoArrow have only one synergy for each of their effects (AoE Damage, fire dps, or freeze length). Because of that, one of those branches can be built up pretty well with just 40 skill points.
If you choose FrozenArrow, then the AoE Damage synergy (ColdArrow) is worth maxing because the freeze duration on FrozenArrow is long enough without a boost from IceArrow, even in Hell Difficulty where durations are reduced to 1/4 (the duration is enough for another arrow).
If you choose ImmoArrow, then the decision is slightly harder, since both synergies have a noticeable effect. I usually choose to max the fire dps (FlameArrow) instead of the explosion damage. You could max both, the explosions do only slightly less damage than FreezingArrow's explosions. Their radius is about 1/2 the radius of FreezingArrow, which can mean much lower damage.
Points to consider: 1) +FireDmg to attack (e.g. DwarfStar, Facets) is added to fire explosions while +IceDmg to attack (e.g. RavenFrost, Facets) is added to ice explosions. This makes the leveling of the skills slightly less important, since you can get charms or other sources to help out with the explosion damage.
2) As mentioned, FreezingArrow's ability ot stop trash from moving is really nice when you want to maximize your damage. You can freeze a group as they form a line of battle, and then walk to a point where you can fire an arrow that pierces all critters in the line (pretty much no trash monsters survive one of these well placed arrows). Battles that take place in crowded corridors can be particularly amusing.
3) The radius of FreezingArrow (6 yards I think) is about double that of ImmoArrow (3 yards). I once noticed the text files for FreezeArrow showed a radius of 6 yards, so I think any display stating otherwise is just a bug. It's been a long time since I looked into this, but it matches my play experience. This doubling of radius will double the damage of FreezeArrow when it strikes a mob because every explosion will hit more creatures, so more explosions will strike previously hit creatures.
4) With either cold or fire branch of the Bow tree, your arrows can do just as much phys damage as Zons built for the PhysDmg bow skills (provided you're built with a lot of dex like them). This means that 1 point into Multi, GA, and Strafe can be very effective. I often keep a massive-damage bow on switch just so I can use Strafe to deal with cold immunes (my regular bow is gemmed for -%ColdRes and +IceDmg to attack). It's worth noting that both Strafe and Multi only do 3/4 of your regular attack damage (skill description may be incorrect if it states otherwise), this was recently tested and verified.
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