Mrs Merkel has been hoping to bring an end to political uncertainty in her country, after she was unable to secure a majority in September’s general election.
And her close ally Annegret Kramp-Karrenbauer was involved in a collision with a truck just outside Berlin this morning.
Mrs Kramp-Karrenbauer – who hopes to leave hospital tomorrow – has been tipped as a possible future leader of Mrs Merkel’s Christian Democratic Unionist Party.
The German leader is seeking to form a coalition with the CDU’s sister party the Christian Social Union (CSU) and the Social Democrats (SPD).
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She entered talks in apparently high spirits despite the crash, and told reporters outside the SPD’s headquarters: “I’m going into this day with great energy.
“The people expect us to find solutions.”
The German leader added: “There are still big hurdles in the way that need to be cleared.
“So it will be a hard day.”
The three parties have clashed over immigration, Europe and finance.
Martin Schulz, leader of the SPD, has called for a United States of Europe by 2025.
Mrs Merkel’s CDU are wary of the affect such ambitious reform could have on taxpayer’s cash.
If the German leader, who is under pressure to end political uncertainty, fails to reach an agreement by Thursday night the talks could be extended or another election could be called.
Should an agreement be reached, formal coalition talks will begin followed by a vote by SPD members in Bonn on January 21.
Merkel’s party polled first in Germany’s election last year but failed to secure a majority.
The Free Democratic Party and the Greens were seen as the only plausible coalition partners.
When talks between the parties collapsed in November last year, Mrs Merkel hinted that another election would be preferable to trying to run a minority government.
The Alternative for Deutschland (AfD) managed to secure 94 out of 709 seats in the German parliament.
It marked the first time far-right MPs had made into the Bundestag in more than half a century.