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We present a direct observation where fragmentation of the <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msubsup><mi>CO</mi><mn>2</mn><mrow><mn>2</mn><mo>+</mo></mrow></msubsup></semantics></math></inline-formula> dication, upon highly charged ion impact, leads to the formation of molecular oxygen. We assert that molecular bending and bond stretching modes of the dication represent the underlying mechanisms driving the generation of <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msubsup><mi mathvariant="normal">O</mi><mn>2</mn><mo>+</mo></msubsup></semantics></math></inline-formula>. We conducted ab initio quantum chemistry calculations for the electronic state of the dication and found that the<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msup><mo> </mo><mn>5</mn></msup><msub><mi>A</mi><mn>1</mn></msub></mrow></semantics></math></inline-formula> state is responsible for the bond-rearrangement reaction. The branching ratios of this channel for multiple projectile beams of varying charge and velocity have been reported and are found to be independent of the projectile’s charge and velocity.