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Matthei conceded the runoff with 70 per cent of counted votes showing that she had won only 37 per cent of the ballot against Bachelet’s 63 per cent.
In the first round on November 17, none of the nine candidates won the needed 50 percent + 1.
Bachelet – the centre-left New Majority coalition candidate – had 46 per cent while Matthei, candidate for the ruling Coalion for Change, at 25 per cent in the first round.
Voter surveys ahead of the election indicated that Matthei stood at a disadvantage because of her ties to the authoritarian Pinochet regime (which ended in 1990), and her tenure as Minister of Labor and Social Security under the widely unpopular Chilean President Sebastián Piñera.
Bachelet, who was president from 2006 to 2010, left the office with more than 80 per cent approval rating; Pinera, who stands down in March 2014, currently has 34 per cent approval rating.
While nearly 13.5 million Chileans were eligible to vote at polling stations which opened at 1100 GMT and closed 2100 GMT, only half that number voted in the first round.
The election is transformative in many ways, say observers. Not only is the runoff a contest between two former childhood friends, but it is also the first time the poll was run between two women candidates.
Bachelet, a socialist, is likely to find the media landscape much changed since she was president. The electorate have staged a number of demonstrations and protests calling for social and economic reform.
They also want the new president to implement a wealth tax to fund education and electoral law reform.
Bachelet says she now has the mandate to begin addressing poverty and inequality in Chile.