If I had to suggest a benzo to use to mellow out a trip and quell some of the nervousness and restlessness, if you want to take one off the bat from the beginning, with regard to avoiding too much dulling of the experience, I'd probably say Valium (diazepam), Librium (chlordiazepoxide), or Serax (oxazepam) would be the best, but most other benzo's would be able to be used for this purpose. Assuming you have no or very little benzo tolerance, I would suggest maybe 2.5 mg to 5 mg diazepam, equipotent to 6.25 mg to 12.5 mg chlordiazepoxide or 5 mg to 10 mg oxazepam, taken an hour prior to taking the psychedelic. I am writing this, if you want the whole trip to be a bit mellowed out - if you were to take them at the same time, I would guess there would be more dulling of the experience, even if the psychedelic took some time to take effect. If you were using Ativan (lorazepam) or Klonopin (clonazepam), I would try 0.5 mg Ativan or 0.125 mg to 0.25 mg Klonopin; the Klonopin dose I suggest might seem very low, but it is very potent in its anti-panic and anti-anxiety properties. If you were to use Xanax (alprazolam) for this purpose, I would suggest the same dose of 0.125 mg to 0.25 mg, and give the same reasoning and rationale.
If you want a benzo to calm you down during a trip, while still keeping the trip well-alive, that might be very hard to do, because a benzo will just fade it out in a certain way and the whole remainder or the trip will not be as intense. But, if you want a benzo to have just in case the trip is too anxious, and you are willing to sacrifice it, I'd say 10 mg Valium, 0.5 mg Xanax, 1 mg Ativan, or 0.5 mg Klonopin would do the job in wiping away nearly all of the anxiety, but then a good deal of the trip, too. That would be to, really, kill the trip. And, those are solid therapeutic doses for someone with no benzo tolerance.