This refers to how a signal gets processed in a guitar pedal. With asymmetrical clipping, the positive and negative amplitude peaks of the waveform are not clipped evenly (symmetrically), they are clipped unevenly (asymmetrically). This can be accomplished by using an uneven number of diodes on each side (positive and negative) of the clipping circuit. Sonically, this has been said to result in more aggressive sounding clipping than symmetrical clipping. The BOSS SD-1 is a classic example of an asymmetrical clipping overdrive pedal.
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