Carlos Mesa had distanced himself from the president in recent weeks
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Bolivia's new president has called for national unity, hours after his predecessor was forced out by weeks of violent anti-government protests.
The new leader, Carlos Mesa - the former vice president - quickly offered to hold early elections and promised to do more for the indigenous Indian population.
In a special session, the Bolivian Congress accepted the dramatic resignation of Gonzalo Sanchez de Lozada - just 14 months into his term.
He was brought down after more than a month of protests over plans to export natural gas which have left scores of people dead.
Mr Sanchez de Lozada's resignation - conveyed in a letter he
wrote before leaving the presidential palace for the airport at Santa Cruz - was accepted 84-26 in an emergency session of congress.
The former president, who has flown to Miami with his family and political associates, said he hoped his resignation would help to solve Bolivia's problems.
'Transitional government'
The US State Department has praised the former president and expressed regret for the circumstances that led to him stepping down.
The US military is sending a small team of security specialists to the American embassy in the administrative capital La Paz to assess the situation.
A respected journalist and political independent, Mr Mesa immediately pledged to hold "a binding referendum" on the plan to export gas to the US and Mexico.
He said he would not complete Mr Sanchez de Lozada's term, which ends in 2007 - describing himself as heading a "transitional government".
The new president promised to address the grievances of Bolivia's indigenous Indian majority, who had complained bitterly about Mr Sanchez de Lozada's free-market policies.
"Bolivia is still not a country of equals. We must understand our peoples, our (indigenous) Quechuas and Aymaras," he told congress.
Massive protests
Mr Sanchez de Lozada quit after he lost the support of a key coalition partner on Friday.
As vice president, Mr Mesa had already withdrawn his support for the president's policies and Minister of Economic Development Jorge Torres Oblea had already resigned.
The Bolivian president had already been forced to postpone the controversial gas export scheme until 31 December.
In his resignation letter, Mr Sanchez de Lozada said his departure was "an unfortunate precedent for democracy in Bolivia and the continent".
As the letter was read out, some lawmakers shouted "murderer!"
A demonstration in La Paz on Friday was one of the biggest protests since the crisis over the gas exports began more than a month ago, with about 50,000 people taking part.
Estimates of the number of people killed when demonstrations turned violent in recent weeks range from 60 to more than 80.
Mr Sanchez de Lozada, a US-educated millionaire mining magnate, was seen as
out of touch with the poverty-stricken Indian population.
He took office in August 2002 after a bitter contest against his top rival, leftist Evo Morales, who led the protests against him.
Mr Morales welcomed the new president's decision to hold a referendum and said the opposition would give Mr Mesa time to settle into the job.
The opposition had rejected Mr Sanchez de Lozada's offer of a referendum on the gas exports, saying it would accept nothing less than his resignation.