The shooting happened yesterday afternoon inside a home on Lawson's Bottom Road, near Burkesville, Kentucky.
The State Medical Examiner's Office in Louisville is expected to perform an autopsy on the two-year-old girl. Police say the toddler was shot by her five-year old brother, local WKYT TV reported.
Cumberland County Coroner Gary White said that he was called to the hospital by emergency room doctors. White said the doctors worked on Caroline Starks for an hour to revive her, but were unsuccessful.
White said that the children's mother was home at the time of the accident.
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"She was actually cleaning her house, and she had went out on the porch. She said no more than three minutes had went by and she actually heard the rifle go off. She ran back in and found the little girl," White said.
The coroner said that the boy is used to shooting the gun, and that the boy often goes shooting with his father on their property.