u can make different tones by picking ur guitar in different places (like closer or farther away from the bridge). also there's harmonics, which take a little bit of practice. but, like Re-design said, most sounds can be learned by just messin around with ur acoustic.
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Funny you should mention those two techniques in the same paragraph - they're very closely related. When you pluck an open string, the motion of the string primarily sways the whole length of the string from nut to bridge; however, there are smaller disturbances present between each primary node (namely, the nut and the bridge) and the frets where harmonics happen (which are other nodes, where the motion is at a minimum). These nodes are present at each fractional length of the whole string. When playing a harmonic, you are effectively forcing the string to move at only these specified nodes by damping all the other harmonics present in normal string motion. Conversely, when you pluck the string at a node, you remove that harmonic content (along with other constituent harmonics that share the same node) from the total vibration of the string. Try it by picking a string at the twelfth fret, then lightly touch it at the same fret to try and produce a harmonic; the string will dampen completely. Also, each harmonic naturally present in a vibrating string has some fraction of the total energy of the open string when plucked at the same intensity. Usually, this fraction is roughly the same as the fraction of string left vibrating when playing a harmonic (which is why higher harmonics are extremely difficult to play cleanly). To further turn this into an idea for the original question posed by the author, learn how to play false harmonics (this assumes you play fingerstyle, as you would need to be very dexterous to do it with a pick). Fret a note (i.e., third fret) with your left hand, then with the tip of your right index finger touch the string at a harmonic fret (i.e., fifteenth fret) and pluck it with your thumb. It's tricky at first, but once you get the hang of it you can incorporate this into your playing to bring out high melodies across chords or accentuate single notes within a chord.
There are a bajillion things you can do - it's really up to your imagination. Plus, it's up to the interpretation of what you consider a unique sound. First, start by trying alternate tunings. There are a myriad of possibilities here, and alternate tunings allow you to construct really unique chord voicings that can add a lot of musical depth to a song. One trick I use is to take a song I wrote in standard tuning and try interpreting it in an alternate tuning, approximating the chords and maybe changing the quality of each chord. Some alternate tunings may require different gauges of strings, or a combination of different strings. This brings me to the next part - the type of strings you use. Again, the sky is the limit. Try flatwounds, which have a darker sound with less sustain - they can add punch to percussively strummed songs. One of my favorite alternate tuning/stringing methods is to use the A and D gauges of strings from a separate set to replace the high B and E strings, then tune to standard tuning - it creates a very somber sound, particularly when playing barred add9 chords. Next, look for new ways of playing the instrument itself. Use an Ebow, which is a hand-held device that uses a magnetic field to "bow" the strings (it works best in the presence of a magnetic field from a pickup - without it the sound is fairly soft). Or, use an open tuning and a bow from a violin (open C works well - sounds a bit like cellos). For a more percussive sound, you could try making your own "funk fingers", which are really just short drumsticks with rubber ends for the strings that you fix to your fingers. These are just a few examples of things you can do - hopefully you can find some inspiration when you play around with it. Like I said, unique is what you make it, and if you have an open enough mind and you're willing to experiment you'll land on something unique soon enough.
Unique sounds are those that you come up with on your own. The way to find them is to play and experiment. Try playing a note or a chord in a different way. It if were easy to come up with something new then we'd all be rock stars. The most unique sound I've ever found is actually learning a song right.
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