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Goals from Cody Gakpo, Mohamed Salah, Dominik Szoboszlai, and Virgil van Dijk helped the Reds overturn a 1-0 deficit from the first leg.
Newcastle earned their Wembley ticket with an impressive 4-0 aggregate win over Arsenal, Liverpool's Premier League title rivals.
Consequently, Newcastle's Premier League match against Crystal Palace on Saturday, March 15 (10 am ET kick-off) will need to be rescheduled.
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It has already been confirmed that this rescheduled game will now take place on Wednesday, February 19 (2.30 pm kick-off).
Both clubs have this midweek slot available after progressing directly into the Champions League round of 16
Liverpool topped the new-look league phase standings, with Villa following in eighth.
The change means Liverpool will not have a midweek rest before their crucial Premier League face-off with defending champions Manchester City on Sunday, February 23 (11.30 am).
However, City have a Champions League knockout phase play-off second leg away to holders Real Madrid on the same night (February 19)
The first leg is at the Etihad on Tuesday, February 11.
Here's how Liverpool's remaining February fixtures shape up:
Sunday, February 9: Plymouth Argyle (A), FA Cup fourth round, 12 pm kick-off; Wednesday, February 12: Everton (A), Premier League, 2.30 pm kick-off; Sunday, February 16: Wolves (H), Premier League, 9 am kick-off; Wednesday, February 19: Aston Villa (A), Premier League, 2.30 pm kick-off; Sunday, February 23: Manchester City (A), Premier League, 11.30 am kick-off; Wednesday, February 26: Newcastle United (H), Premier League, 3.15 pm kick-off.
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