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Charley Hull and Nelly Korda will face each other in Friday's opening match of this year's Solheim Cup in Virginia.
Play gets under way at 07:05 (12:05 BST) on Friday with four foursomes (alternate shot) matches.
Experienced English player Hull is partnered with German rookie Esther Henseleit, while world number one Korda is once again paired with Allisen Corpuz after the Americans won both their foursomes matches in last year's contest.
"It's nice to get Charley going, she doesn't like to sit around and wait," said Europe captain Suzann Pettersen.
Her US counterpart Stacy Lewis said the thinking behind putting Korda out first was simple.
"I wanted to send experience out first and there is no better than the world number one and a pairing that was very successful," she added.
The United States swept the opening session 4-0 at Finca Cortesin last year, but Europe fought back to earn a 14-14 draw.
As holders, Europe need 14 points to retain the trophy for a record fourth time, while the US need 14½ to regain the title they last won in 2017.
Europe's other debutant Albane Valenzuela is out in the second match, alongside France's Celine Boutier, who is the team's highest-ranked player at 10 in the world.
"Let's send them out and experience it," said Pettersen of her decision to blood both her new players in the opening session.
"There's no point for them to sit around and wonder what it's going to be like."
Lewis said it was "a bonus to get them both out there", having also selected her two rookies in the opening matches.
Lauren Coughlin, who won last month's Women's Scottish Open, is making her debut at the age of 31 alongside former world number one amateur Rose Zhang, 21, against Valenzuela and Boutier.
Sarah Schmelzel, who is the lowest ranked US player at 58, will partner world number two Lilia Vu in the bottom match against Sweden's Linn Grant and Spain's Carlota Ciganda, who secured the point to ensure Europe retained the trophy last year in her homeland.
The other match features Sweden's Maja Stark and Denmark's Emily Pedersen against Ally Ewing and Jennifer Kupcho.
Among the players sitting out are Ireland's Leona Maguire, who is missing a session for the first time after playing five matches in both her previous appearances.
"To sit Leona in a foursome is a tough call," conceded Pettersen. "But you go a little bit with the gut. She has a great record and is a feisty Solheim player and you'll see her."
Lewis also defended her decision not to use Lexi Thompson and Megan Khang, who won both their foursomes matches last year. "I don't think you're going to see that pairing," she added.
"We have a lot of good pairings and not everybody is going to play this session," she added. "I don't think I'll have anybody play all five."
The 19th edition of the Solheim Cup is being held at the 6,741-yard Robert Trent Jones Golf Club, on the shores of Lake Manassas, about an hour west of Washington DC.
It opened for play in 1991 and, given its proximity to the American capital, has played host to many US presidents, with Barack Obama still a member of the club.
Europe and the United States will play a mix of foursome, fourball and singles matches over three days in Virginia, with 28 points up for grabs.
The pairings for Friday's fourballs, where players play their own ball with the best score counting, will be announced towards the end of the foursomes session.
Saturday will feature four more foursomes matches, followed by four fourballs, with all 24 players contesting 12 singles matches on Sunday.
The US lead the series 10-7 with one tied match. Europe have only won twice on US soil, but those have come in the past three contests, in 2013 and 2021.