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What psychical discipline makes the most sense for a librarian accompanying an honor guard squad?

Psychic?

I'd say Biomancy or Divination, with a preference to Biomancy. It offers the chance to either buff your Librarian's CC potential or your HGs survivability, with a small chance of fluking and ending up with hemorrhage.

Divination if you can get the 4++ power. Prescience is always good too. That would be assuming you're taking Tiggy or the FW character that has access to it.

As mentioned Biomancy wouldn't be bad if you can get the FNP power.

Telepathy for Invisibility is a no-brainer.

Divination is better to buff a shooting squad with Presience. Of course the 4++ helps as well.
Other than that, it's Biomancy. It has couple of flops, but still worth it at it's best. Warp Speed and Iron Arm are both good and Endurance is just pure win!

I prefer Biomancy for the witchfire power and added grunt in assault but Divination is equally as good.

Just give them invisibility to get them into close combat for all those amazing power weapon attacks. Throw in the banner and prescience and you have a mean cheap assault unit that can pretty much kill anything in assault. Don't grab biomancy, if you're gonna grab from anything else other then div and telep go sanctic for hammerhand, gate, or sanctuary

Sanctic risks massive perils feedback. Telepathy is good, but just as with divination, you're fishing for 1-2 spells. Biomancy is largely good for cc, sans hemorrhage.

What about life leech? Not that great for close combat, also since the "melee" powers only affect just the psyker it isn't worth it most of the time. The only useful one is smash, warp speed isn't good on a psyker who is still only str 4. Sure you will nuke weaker units, but against monstrous creatures and daemons you're going to have a rough time. By the way you are still only fishing for 1-2 powers on biomancy. I'd rather have the chance at unit wide buffs to make the honor guard better.

Question for the OP, which librarian is it going to be in the first place? Named character, or just an average Joe?

another question for the OP: where's your chapter master? is he rolling with the HG squad as well or off doing his own thing? if he's in the squad, does that change what discipline(s) you want to use?

Lord Asterion Moloc will be accompanying his HG in a Stormhawk.

If you just play vanilla marines you don't even get the choice to use divination unless you take Tigurius. I like telepathy though, and Psychic Shriek is awesome with the 18'' range.