"Nashville" stars Clare Bowen and Sam Palladio heat up the TV screen week after week as songwriting and singing partners, Scarlett O'Connor and Gunnar Scott, who have undeniable chemistry. But while their voices may sound like they were born to sing together, the actors reveal they never actually performed with one another until they started filming the hit TV show.

"We'd just met that morning for the first time," Sam recalls to CMT of their initial encounter. "Buddy Miller turned up; he's obviously an incredible singer and producer. He took us up to one of the hotel rooms while sort of gritting his teeth. And we were doing the same, because the audition process hadn't involved singing together. They'd just thrown us in the deep end. Buddy started playing the riff of 'If I Didn't Know Better,' and Clare started singing and sounded incredible. I thought, 'Oh, my God, I've got to up my game because she sounds great!'"

"But then he started singing, and it sounded beautiful," Clare chimes in.

With Sam based in London and Clare originally from Australia, the city of Nashville seemed, rightfully so, worlds away. Still, both stars have quickly found they feel just at home in Music City as they did in their own hometowns.

"I didn't have a preconception of the place," Clare maintains. "I knew that it was an amazing music town and I knew that this was where a lot of American music started, but I could have never prepared myself for what we've been given and what we've been welcomed into."

"For me, it had a kind of bluegrass image that I was aware of, but coming here, you find such a cosmopolitan city and a melting pot of so many different styles of music," adds Sam. "I sort of associated it with very traditional country and bluegrass. I thought I knew what I was going to get when I thought of Nashville because it was probably going to be like that. But it's so far removed from that in terms of the scope of talent and the music that's happening here. My eyes were opened."

The twosome can already cross one major event off their bucket list -- performing on the Grand Ole Opry, which they did in November at the Ryman Auditorium. Now, they can cross another milestone off, since they are featured on the TV show's new soundtrack, with their duet, "If I Didn't Know Better."

"The power of the music hadn't really crossed my mind until the airing of the pilot episode,'" Sam concedes. "Then 12 hours later, Clare and I were on the iTunes country charts with 'If I Didn't Know Better,' which suddenly rocketed up to the Top 10, then the Top 5. And that was the first indication that, wow, this is going to be a crazy ride."

The "Nashville" soundtrack also features songs by the show's two main characters, played by Connie Britton and Hayden Panettiere. The musical drama airs on Wednesday nights at 10:00 PM ET on ABC. Purchase the soundtrack here.

Watch an Interview With Clare & Sam