Rai, winner of the gold medal in the same event in both the Commonwealth and Asian Games two years ago, showed rare signs of nerve going into the sixth and final series of ten shots in the qualification round and was way off the mark to end up overall 12th with a total of 554 out of 600.
The 28-year-old Nepal-born army shooter, thus, would return empty-handed from the Rio range after finishing eighth in the 10m event earlier.
However, encouraging result came from the archery range where Laishram Bambayla Devi stormed into the women's individual pre-quarter finals with successive victories over Laurence Bauldaff of Austria and Chinese Taipei's Lin Shih-Chi in the elimination phase.
She will aim to make the last eight tomorrow.
Multiple medallist at the ISSF World Cup, World Championships, Asian Games and Commonwealth Games, Jitu started the 50m pistol qualification with 91 and fired 95 in the second series.
Scores of 90 and 94 were followed by another 95, including four 10s, in the fifth series that propelled him to the fourth position at the completion of the series.
On the other hand, experienced woman archer Bombayla, hailing from Manipur, who finished 24th in the ranking round, dished out a dominating show to get the better off Lin 6-2 in the 1/16 elimination.
Earlier in the 1/32 elimination round, the 31-year-old, in her third Olympics, had rallied her way to beat Austria's Baldauff 6-2.
in the women's team event, Bombayla started with a 10 and then hit 8 and 9 to total 27 as against 24 (8, 7, 9) of her opponent.
The Indian scored 8, 9, 10 against Lin's hat-trick of 8s to clinch the second set. In the third set, the Chinese Taipei girl hit the bull's eye twice even as Bombayla came up with a 7 and 9 in the first two shots. In the final shot, the Indian hit a 10 but that was not enough to win the set.
Earlier, Bombayla showed tremendous nerves as she bounced back after losing the first set to outclass Laurence in the second, third and fourth set in the first round.
Bombayla, who was the best Indian performer in the women's team event, scored a 24-27, 28-24, 27-23, 26-24 qwin over her Austrian rival.
Another woman archer Deepika Kumari was set to make her first appearance in the individual elimination event later today.
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