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Italy had seemed on course for back-to-back Six Nations victories for only the second time in their history having led 8-6 at halftime thanks to full-back Andrea Masi's score.
But Scotland scored 15 unanswered points after the break with full-back Chris Paterson contributing 11 points with the boot.
While Italy headed into the match riding the crest of the wave from their first ever Six Nations defeat of France, Scotland were still licking their wounds from a bruising 22-16 loss to England.
But it was Scotland who came flying out of the blocks and won an early penalty after Sean Lamont led them into the Italian 22 which was converted by Paterson.
Mirco Bergamasco, who was in such fine form with the boot in the Azzurri's second-half comeback against France, reverted to his erratic self by missing the chance to level the scores on seven minutes.
But Italy's other hero against Les Bleus, tryscorer Masi, repeated his trick in the 11th minute when he sliced through a gaping hole in the defensive line between Joe Ansbro and Walker to run in from the 22.
Bergamasco failed to add the extras from a difficult angle when his conversion hit the post.
Italy though were undoing much of their good work at the lineout and after their own throw was pinched by Scotland for the fourth straight time, Ansbro surged downfield.
Walker was just centimetres short of the line but despite battering away Scotland could not find the breakthrough and had to settle for a second Paterson penalty which put them 6-5.
However Ansbro was injured in the build up and had to be replaced by de Luca while Luke McLean came on for Masi after Bergamasco had put Italy ahead with a penalty in front of the posts.
On the stroke of halftime, it seemed as if Scotland would go into the break ahead when they scrum-half Rory Lawson won a penalty 40m out on the right.
But Paterson's 100per cent kicking record in the 2011 Championship came to an ugly end when he shanked his penalty wide.
Despite Italy starting the half on the front foot going through the phases deep inside the Scottish half, it was the hosts who regained the lead.
A loose pass in the Italian midfield was seized upon by Lamont but despite kicking ahead he could not outpace Italy hooker Leonardo Ghiraldini to the loose ball.
Nevertheless Scotland were awarded a 5m scrum and when they moved the ball left, replacement de Luca darted past Kris Burton to touch down his first international try. Paterson's conversion from a difficult angle drifted just wide to keep the score at 11-8.
But moments later Murrayfield was celebrating a second try when Paterson's inside ball fed the rampaging Walker who brushed through McLean's weak tackle to bag his sixth international try. Paterson's conversion gave Scotland some breathing space.
Italy mustered a stirring comeback from 12 points down to France the previous week but despite enjoying plenty of phases of possession they could not make any inroads against a determined Scottish defence.
A third Paterson penalty on 67 minutes took Scotland 13 points ahead but the full-back's work was not done there for the afternoon.
Just as he did against England, Scotland's record points scorer produced a fabulous try-saving tackle on McLean just as he seemed poised to sneak in the corner as Italy had to settle for their fourth consecutive Wooden Spoon.
|Scotland Score Card|
|Nick De Luca||1||5|
|Italy Score Card|