This is a build I've been working on the past few days just for giggles. It turned out to be both interesting and surprisingly effective, so I figured I may as well share it.
I must admit, I shamelessly based this build on a character from an anime. Namely, this one:
This is Misaka Mikoto, main character of A Certain Scientific Railgun. She uses her potent psionic ability to generate and manipulate electromagnetic forces to shoot coins with tremendous force, a distinctive signature move for which she's given the nickname "Railgun".
So...anyone care to guess how much punch we can pack into as few shuriken as possible with the restriction of using an electricity-focused psionic build? The answer may surprise you!
No, it's not exactly up to par with your typical high-optimization damage-dealing builds, but it's certainly enough to obliterate most level-appropriate enemies, or at least take out a very significant chunk of their health.
Let's build us a Railgun.
Assembling a Railgun
First and foremost, what ability scores does the Railgun need?
Dex is by far the most important stat for the Railgun, providing accuracy and (at short range) power for the railgun attack itself as well as helping her other electricity-based attacks hit. And the extra AC and initiative certainly don't hurt either!
Wis is good to have as much as you can, as it benefits the Railgun's AC, power points, and Will save (her weakest save). It's a distant second in priority to Dex, though.
Con is always good to have as high as you can get for any character, and since all of the Railgun's classes have d8 HD, a high score is definitely helpful. It's probably not quite as high-priority as Dex or Wis, though, since hp is about all it's really needed for.
Str needs to be at least 13 by level 18, but doesn't really need to be any higher than that.
Int is good to keep at least out of the negatives to maintain a decent amount of skill points, but otherwise is unnecessary.
Cha is entirely dispensable for the Railgun. And really, even from a flavor perspective of trying to emulate the anime character as closely as possible, it wouldn't be all that inappropriate to have this a bit below average (a certain teleporter's opinion notwithstanding).
Using a 32-point buy, I'd personally build the Railgun as a human with starting stats of 12 Str, 16 Dex, 14 Con, 10 Int, 16 Wis, and 8 Cha. Stat increases will go to Dex at every level except 16, where it will go to Str instead. Unless the DM rules that item-based ability score increases count for meeting feat prereqs, in which case it all goes to Dex and you just pick up a +2 Str item at some point before level 18. (While this is the ruling favored by the FAQ, the FAQ is not strictly RAW and I know many groups disagree with this point.)
You could also go strongheart halfling, for the Dex bonus and size bonuses to hit and AC, though the Str hit would make getting that 13 Str a little trickier (particularly if the DM doesn't allow items to count). Personally, I prefer the human skill point bonus regardless.
Any other race wouldn't really work unless flaws are allowed, as you really need that extra feat at level 1. Unless you can talk your DM into houseruling Point Blank Shot to be a default part of the ranged weapon rules rather than a feat, and thereby strike it from all places where it appears as a prerequisite -- which, frankly, is probably easier to do than getting permission to take flaws.
Now that we have our base attributes, let's look at the Railgun's build.
[TABLE="width: 90%, align: center"] [TR] [TD="align: center"]Level[/TD] [TD="align: center"]BAB[/TD] [TD="align: center"]Saves (F/R/W)[/TD] [TD="align: center"]Feats[/TD] [TD="align: center"]Special[/TD] [/TR] [TR] [TD]1-Monk1[/TD] [TD="align: center"]+0[/TD] [TD="align: center"]2/2/2[/TD] [TD]Point Blank Shot, Precise Shot, Power Attack[/TD] [TD]AC bonus, Decisive strike (-2), Unarmed strike 1d6[/TD] [/TR] [TR] [TD]2-Monk2[/TD] [TD="align: center"]+1[/TD] [TD="align: center"]3/3/3[/TD] [TD]Monastic Training (Electromaster)[/TD] [TD]Evasion[/TD] [/TR] [TR] [TD]3-Monk3[/TD] [TD="align: center"]+2[/TD] [TD="align: center"]3/3/3[/TD] [TD]Weapon Focus (Shuriken)[/TD] [TD]Fast movement +10 ft, Still mind[/TD] [/TR] [TR] [TD]4-Psychic Warrior 1[/TD] [TD="align: center"]+2[/TD] [TD="align: center"]5/3/3[/TD] [TD]Dead Eye[/TD] [TD]
[/TD] [/TR] [TR] [TD]5-Psychic Warrior 2[/TD] [TD="align: center"]+3[/TD] [TD="align: center"]6/3/3[/TD] [TD]Psionic Shot[/TD] [TD]
[/TD] [/TR] [TR] [TD]6-Electromaster 1[/TD] [TD="align: center"]+3[/TD] [TD="align: center"]8/5/3[/TD] [TD]Tashalatora[/TD] [TD]Electricity lash, Unarmed strike 1d8[/TD] [/TR] [TR] [TD]7-Electromaster 2[/TD] [TD="align: center"]+4[/TD] [TD="align: center"]9/6/3[/TD] [TD]
[/TD] [TD]AC +1, Decisive strike (-1), Electricity adaptation, Hand electrified[/TD] [/TR] [TR] [TD]8-Electromaster 3[/TD] [TD="align: center"]+5[/TD] [TD="align: center"]9/6/4[/TD] [TD]
[/TD] [TD]Bolt of electricity[/TD] [/TR] [TR] [TD]9-Electromaster 4[/TD] [TD="align: center"]+6[/TD] [TD="align: center"]10/7/4[/TD] [TD]Greater Psionic Shot[/TD] [TD]Weapon electrified[/TD] [/TR] [TR] [TD]10-Master Thrower 1[/TD] [TD="align: center"]+7[/TD] [TD="align: center"]10/9/4[/TD] [TD]Quick Draw[/TD] [TD]Palm Throw[/TD] [/TR] [TR] [TD]11-Electromaster 5[/TD] [TD="align: center"]+7[/TD] [TD="align: center"]10/9/4[/TD] [TD]
[/TD] [TD]Nimbus, Unarmed strike 1d10[/TD] [/TR] [TR] [TD]12-Electromaster 6[/TD] [TD="align: center"]+8[/TD] [TD="align: center"]11/10/5[/TD] [TD]Psionic Meditation[/TD] [TD]Decisive strike (+0), Lightning walk[/TD] [/TR] [TR] [TD]13-Electromaster 7[/TD] [TD="align: center"]+9[/TD] [TD="align: center"]11/10/5[/TD] [TD]
[/TD] [TD]AC +2, Fear no lightning[/TD] [/TR] [TR] [TD]14-Electromaster 8[/TD] [TD="align: center"]+10[/TD] [TD="align: center"]12/11/5[/TD] [TD]
[/TD] [TD]Decisive strike (2 attacks), Greater weapon electrified[/TD] [/TR] [TR] [TD]15-Master Thrower 2[/TD] [TD="align: center"]+11[/TD] [TD="align: center"]12/12/5[/TD] [TD]Brutal Throw[/TD] [TD]Improved evasion[/TD] [/TR] [TR] [TD]16-Master Thrower 3[/TD] [TD="align: center"]+12[/TD] [TD="align: center"]13/12/6[/TD] [TD]
[/TD] [TD]Defensive throw[/TD] [/TR] [TR] [TD]17-Master Thrower 4[/TD] [TD="align: center"]+13[/TD] [TD="align: center"]13/13/6[/TD] [TD]Snatch Arrows[/TD] [TD]
[/TD] [/TR] [TR] [TD]18-Master Thrower 5[/TD] [TD="align: center"]+14[/TD] [TD="align: center"]13/13/6[/TD] [TD]Power Throw[/TD] [TD]Weak spot[/TD] [/TR] [TR] [TD]19-Swordsage1[/TD] [TD="align: center"]+14[/TD] [TD="align: center"]13/15/8[/TD] [TD]
[/TD] [TD]Discipline focus (Weapon Focus), Quick to act +1[/TD] [/TR] [TR] [TD]20-Swordsage2[/TD] [TD="align: center"]+15[/TD] [TD="align: center"]13/16/9[/TD] [TD]
[/TD] [TD]AC bonus[/TD] [/TR] [/TABLE]
How the Railgun Works
Essentially, the Railgun tries to stack loads of static damage bonuses onto shuriken attacks to be doubled with Decisive Strike, along with a little extra from Greater Psionic Shot and Weapon Electrified (for flavor as much as anything). With the Tashalatora feat, her electromaster levels advance her decisive strike all the way to the point of making two attacks at no penalty to hit (at least assuming the DM is reasonable enough to allow the feat to apply to decisive strike rather than flurry of blows, which DS replaces). The Railgun takes advantage of the fact that shuriken, being considered ammunition, are dirt cheap to get in small quantities even with very extensive enchantment. Granted, shuriken are technically destroyed when used, but most DMs would presumably not apply this rule for adamantine shuriken, given that the whole point of adamantine is that it's nigh-indestructible. Thus, you simply carry around a handful of +N Collision Returning adamantine shuriken. At higher levels, when you have more gold to throw around, you can have a sizable collection of shuriken consisting of a number of different Bane varieties keyed to different enemy types. If you were to invest as much in your shuriken collection as you would in a primary weapon, you could easily have enough different types to have a set of +N Collision Returning XBane shuriken on hand for most any X you come across that you'd really want to pull the railgun on. Maybe throw Distance on them too, because shuriken have piddly range normally.
A large chunk of the Railgun's damage comes from the Dead Eye feat (from Dragon Compendium), allowing her to add her Dex bonus to damage against crit-susceptible targets within 30 ft. While this does mean the Railgun suffers from many of the same restrictions as sneak-attack-based damage dealers for peak effectiveness, the amount of other, unconditional bonuses that can be accrued make the attack retain a reasonable degree of effectiveness even against targets immune to or too far away to be affected by Dead Eye's bonus. The targetteer variant fighter from Dragon Magazine #310 could allow Dex to damage without range restrictions, but since this feature replaces your Str bonus to damage it would not be applicable in conjunction with the tricks from Master Thrower (which do not allow you to apply your Str bonus to damage). Dead Eye, rather than replacing your Str bonus, adds Dex as an extra bonus, and thus should be valid with the Master Thrower's tricks.
Those tricks, by the way, are what really bump the Railgun up from "passable" to "shockingly potent" (pun 100% effective). Palm Throw doubles the damage of each attack in your decisive strike (and this is a real-math doubling, not a D&D-math stacking multiplier, as it actually has you resolve damage twice for each attack), while Weak Spot lets you dump all of your BAB into Power Throw while making ranged touch attacks. Technically. A lot of DMs might take issue with using Power Throw on an attack that doesn't allow Str to damage, in which case you'll probably want to cut Master Thrower off at a one-level dip for Palm Throw and instead take four levels of fighter to get Weapon Specialization and Ranged Weapon Mastery by level 18. It's not as good as ranged-touch Power Throws, but it's still not too shabby.
Finishing off the build with two levels of swordsage loses you a point of BAB, but shore up the Railgun's weak Will save, provides a variety of useful maneuvers, and most importantly, gives access to Giant Killing Style. This stance is one of the few Tome of Battle tricks that can apply to ranged attacks, and while it only applies to enemies that are bigger than you, most things that have huge pools of hp you'd want to railgun through are bigger. And for those that aren't, the Railgun's psychic warrior levels allow her to use a dorje of Compression to make sure the bonus applies.
And speaking of dorjes, with a dorje of Hustle the Railgun can significantly improve the efficacy of her signature attack. At higher levels, she can make two attacks in a round with decisive strike, using Hustle to regain psionic focus as a swift action between attacks thanks to Psionic Meditation and thus apply Greater Psionic Shot to both shots rather than just one. If sustained fire is needed, the Railgun can Hustle to re-electrify the shuriken at the start of each turn after the first. She won't be able to apply Greater Psionic Shot after the first round, since she can't regain psionic focus, re-electrify and fire all in one turn, so there's a bit of a drop in damage after the first shot, but still -- sustained railgun fire!
For targets that don't warrant pulling out the signature attack, the Railgun can also fall back on (electrified) unarmed strikes, electricity lash (which, with two-handed Power Attack as a ranged touch, puts out some pretty decent damage), and bolts of electricity.
I must admit, I shamelessly based this build on a character from an anime. Namely, this one:

So...anyone care to guess how much punch we can pack into as few shuriken as possible with the restriction of using an electricity-focused psionic build? The answer may surprise you!
No, it's not exactly up to par with your typical high-optimization damage-dealing builds, but it's certainly enough to obliterate most level-appropriate enemies, or at least take out a very significant chunk of their health.
Let's build us a Railgun.
Assembling a Railgun
First and foremost, what ability scores does the Railgun need?
Dex is by far the most important stat for the Railgun, providing accuracy and (at short range) power for the railgun attack itself as well as helping her other electricity-based attacks hit. And the extra AC and initiative certainly don't hurt either!
Wis is good to have as much as you can, as it benefits the Railgun's AC, power points, and Will save (her weakest save). It's a distant second in priority to Dex, though.
Con is always good to have as high as you can get for any character, and since all of the Railgun's classes have d8 HD, a high score is definitely helpful. It's probably not quite as high-priority as Dex or Wis, though, since hp is about all it's really needed for.
Str needs to be at least 13 by level 18, but doesn't really need to be any higher than that.
Int is good to keep at least out of the negatives to maintain a decent amount of skill points, but otherwise is unnecessary.
Cha is entirely dispensable for the Railgun. And really, even from a flavor perspective of trying to emulate the anime character as closely as possible, it wouldn't be all that inappropriate to have this a bit below average (a certain teleporter's opinion notwithstanding).
Using a 32-point buy, I'd personally build the Railgun as a human with starting stats of 12 Str, 16 Dex, 14 Con, 10 Int, 16 Wis, and 8 Cha. Stat increases will go to Dex at every level except 16, where it will go to Str instead. Unless the DM rules that item-based ability score increases count for meeting feat prereqs, in which case it all goes to Dex and you just pick up a +2 Str item at some point before level 18. (While this is the ruling favored by the FAQ, the FAQ is not strictly RAW and I know many groups disagree with this point.)
You could also go strongheart halfling, for the Dex bonus and size bonuses to hit and AC, though the Str hit would make getting that 13 Str a little trickier (particularly if the DM doesn't allow items to count). Personally, I prefer the human skill point bonus regardless.
Any other race wouldn't really work unless flaws are allowed, as you really need that extra feat at level 1. Unless you can talk your DM into houseruling Point Blank Shot to be a default part of the ranged weapon rules rather than a feat, and thereby strike it from all places where it appears as a prerequisite -- which, frankly, is probably easier to do than getting permission to take flaws.
Now that we have our base attributes, let's look at the Railgun's build.
[TABLE="width: 90%, align: center"] [TR] [TD="align: center"]Level[/TD] [TD="align: center"]BAB[/TD] [TD="align: center"]Saves (F/R/W)[/TD] [TD="align: center"]Feats[/TD] [TD="align: center"]Special[/TD] [/TR] [TR] [TD]1-Monk1[/TD] [TD="align: center"]+0[/TD] [TD="align: center"]2/2/2[/TD] [TD]Point Blank Shot, Precise Shot, Power Attack[/TD] [TD]AC bonus, Decisive strike (-2), Unarmed strike 1d6[/TD] [/TR] [TR] [TD]2-Monk2[/TD] [TD="align: center"]+1[/TD] [TD="align: center"]3/3/3[/TD] [TD]Monastic Training (Electromaster)[/TD] [TD]Evasion[/TD] [/TR] [TR] [TD]3-Monk3[/TD] [TD="align: center"]+2[/TD] [TD="align: center"]3/3/3[/TD] [TD]Weapon Focus (Shuriken)[/TD] [TD]Fast movement +10 ft, Still mind[/TD] [/TR] [TR] [TD]4-Psychic Warrior 1[/TD] [TD="align: center"]+2[/TD] [TD="align: center"]5/3/3[/TD] [TD]Dead Eye[/TD] [TD]
[/TD] [/TR] [TR] [TD]5-Psychic Warrior 2[/TD] [TD="align: center"]+3[/TD] [TD="align: center"]6/3/3[/TD] [TD]Psionic Shot[/TD] [TD]
[/TD] [/TR] [TR] [TD]6-Electromaster 1[/TD] [TD="align: center"]+3[/TD] [TD="align: center"]8/5/3[/TD] [TD]Tashalatora[/TD] [TD]Electricity lash, Unarmed strike 1d8[/TD] [/TR] [TR] [TD]7-Electromaster 2[/TD] [TD="align: center"]+4[/TD] [TD="align: center"]9/6/3[/TD] [TD]
[/TD] [TD]AC +1, Decisive strike (-1), Electricity adaptation, Hand electrified[/TD] [/TR] [TR] [TD]8-Electromaster 3[/TD] [TD="align: center"]+5[/TD] [TD="align: center"]9/6/4[/TD] [TD]
[/TD] [TD]Bolt of electricity[/TD] [/TR] [TR] [TD]9-Electromaster 4[/TD] [TD="align: center"]+6[/TD] [TD="align: center"]10/7/4[/TD] [TD]Greater Psionic Shot[/TD] [TD]Weapon electrified[/TD] [/TR] [TR] [TD]10-Master Thrower 1[/TD] [TD="align: center"]+7[/TD] [TD="align: center"]10/9/4[/TD] [TD]Quick Draw[/TD] [TD]Palm Throw[/TD] [/TR] [TR] [TD]11-Electromaster 5[/TD] [TD="align: center"]+7[/TD] [TD="align: center"]10/9/4[/TD] [TD]
[/TD] [TD]Nimbus, Unarmed strike 1d10[/TD] [/TR] [TR] [TD]12-Electromaster 6[/TD] [TD="align: center"]+8[/TD] [TD="align: center"]11/10/5[/TD] [TD]Psionic Meditation[/TD] [TD]Decisive strike (+0), Lightning walk[/TD] [/TR] [TR] [TD]13-Electromaster 7[/TD] [TD="align: center"]+9[/TD] [TD="align: center"]11/10/5[/TD] [TD]
[/TD] [TD]AC +2, Fear no lightning[/TD] [/TR] [TR] [TD]14-Electromaster 8[/TD] [TD="align: center"]+10[/TD] [TD="align: center"]12/11/5[/TD] [TD]
[/TD] [TD]Decisive strike (2 attacks), Greater weapon electrified[/TD] [/TR] [TR] [TD]15-Master Thrower 2[/TD] [TD="align: center"]+11[/TD] [TD="align: center"]12/12/5[/TD] [TD]Brutal Throw[/TD] [TD]Improved evasion[/TD] [/TR] [TR] [TD]16-Master Thrower 3[/TD] [TD="align: center"]+12[/TD] [TD="align: center"]13/12/6[/TD] [TD]
[/TD] [TD]Defensive throw[/TD] [/TR] [TR] [TD]17-Master Thrower 4[/TD] [TD="align: center"]+13[/TD] [TD="align: center"]13/13/6[/TD] [TD]Snatch Arrows[/TD] [TD]
[/TD] [/TR] [TR] [TD]18-Master Thrower 5[/TD] [TD="align: center"]+14[/TD] [TD="align: center"]13/13/6[/TD] [TD]Power Throw[/TD] [TD]Weak spot[/TD] [/TR] [TR] [TD]19-Swordsage1[/TD] [TD="align: center"]+14[/TD] [TD="align: center"]13/15/8[/TD] [TD]
[/TD] [TD]Discipline focus (Weapon Focus), Quick to act +1[/TD] [/TR] [TR] [TD]20-Swordsage2[/TD] [TD="align: center"]+15[/TD] [TD="align: center"]13/16/9[/TD] [TD]
[/TD] [TD]AC bonus[/TD] [/TR] [/TABLE]
Powers known: Offensive Prescience, one other of your choice
Maneuvers known: Moment of Perfect Mind, Counter Charge, five others of your choice
Stances known: Giant Killing Style, one other of your choice
Notable gear (at level 20):
Maneuvers known: Moment of Perfect Mind, Counter Charge, five others of your choice
Stances known: Giant Killing Style, one other of your choice
Notable gear (at level 20):
[*=1]Gloves of Dexterity +6 [36k gp]
[*=1]Manual of Quickness of Action +4 (assuming points from levels must be spent to increase Str to qualify for Power Throw) or +5 (if a Str-boosting item can be used to qualify for Power Throw) [110k or 137.5k gp]
[*=1]Goggles of the Ebon Hunter (MIC) [18k gp]
[*=1]+5 Collision Returning Distance adamantine shuriken; eleven sets of four with Bane keyed to types expected to be needed against, and six with Magebane [103k gp]
[*=1]Dorje of Hustle [4500 gp]
How the Railgun Works
Essentially, the Railgun tries to stack loads of static damage bonuses onto shuriken attacks to be doubled with Decisive Strike, along with a little extra from Greater Psionic Shot and Weapon Electrified (for flavor as much as anything). With the Tashalatora feat, her electromaster levels advance her decisive strike all the way to the point of making two attacks at no penalty to hit (at least assuming the DM is reasonable enough to allow the feat to apply to decisive strike rather than flurry of blows, which DS replaces). The Railgun takes advantage of the fact that shuriken, being considered ammunition, are dirt cheap to get in small quantities even with very extensive enchantment. Granted, shuriken are technically destroyed when used, but most DMs would presumably not apply this rule for adamantine shuriken, given that the whole point of adamantine is that it's nigh-indestructible. Thus, you simply carry around a handful of +N Collision Returning adamantine shuriken. At higher levels, when you have more gold to throw around, you can have a sizable collection of shuriken consisting of a number of different Bane varieties keyed to different enemy types. If you were to invest as much in your shuriken collection as you would in a primary weapon, you could easily have enough different types to have a set of +N Collision Returning XBane shuriken on hand for most any X you come across that you'd really want to pull the railgun on. Maybe throw Distance on them too, because shuriken have piddly range normally.
A large chunk of the Railgun's damage comes from the Dead Eye feat (from Dragon Compendium), allowing her to add her Dex bonus to damage against crit-susceptible targets within 30 ft. While this does mean the Railgun suffers from many of the same restrictions as sneak-attack-based damage dealers for peak effectiveness, the amount of other, unconditional bonuses that can be accrued make the attack retain a reasonable degree of effectiveness even against targets immune to or too far away to be affected by Dead Eye's bonus. The targetteer variant fighter from Dragon Magazine #310 could allow Dex to damage without range restrictions, but since this feature replaces your Str bonus to damage it would not be applicable in conjunction with the tricks from Master Thrower (which do not allow you to apply your Str bonus to damage). Dead Eye, rather than replacing your Str bonus, adds Dex as an extra bonus, and thus should be valid with the Master Thrower's tricks.
Those tricks, by the way, are what really bump the Railgun up from "passable" to "shockingly potent" (pun 100% effective). Palm Throw doubles the damage of each attack in your decisive strike (and this is a real-math doubling, not a D&D-math stacking multiplier, as it actually has you resolve damage twice for each attack), while Weak Spot lets you dump all of your BAB into Power Throw while making ranged touch attacks. Technically. A lot of DMs might take issue with using Power Throw on an attack that doesn't allow Str to damage, in which case you'll probably want to cut Master Thrower off at a one-level dip for Palm Throw and instead take four levels of fighter to get Weapon Specialization and Ranged Weapon Mastery by level 18. It's not as good as ranged-touch Power Throws, but it's still not too shabby.
Finishing off the build with two levels of swordsage loses you a point of BAB, but shore up the Railgun's weak Will save, provides a variety of useful maneuvers, and most importantly, gives access to Giant Killing Style. This stance is one of the few Tome of Battle tricks that can apply to ranged attacks, and while it only applies to enemies that are bigger than you, most things that have huge pools of hp you'd want to railgun through are bigger. And for those that aren't, the Railgun's psychic warrior levels allow her to use a dorje of Compression to make sure the bonus applies.
And speaking of dorjes, with a dorje of Hustle the Railgun can significantly improve the efficacy of her signature attack. At higher levels, she can make two attacks in a round with decisive strike, using Hustle to regain psionic focus as a swift action between attacks thanks to Psionic Meditation and thus apply Greater Psionic Shot to both shots rather than just one. If sustained fire is needed, the Railgun can Hustle to re-electrify the shuriken at the start of each turn after the first. She won't be able to apply Greater Psionic Shot after the first round, since she can't regain psionic focus, re-electrify and fire all in one turn, so there's a bit of a drop in damage after the first shot, but still -- sustained railgun fire!
For targets that don't warrant pulling out the signature attack, the Railgun can also fall back on (electrified) unarmed strikes, electricity lash (which, with two-handed Power Attack as a ranged touch, puts out some pretty decent damage), and bolts of electricity.
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