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D-backs manager Chip Hale said that Ward had been sent a contract for next season and that there were negotiations back and forth before Ward called Hale on Tuesday and told him he was going to pursue an unspecified opportunity elsewhere.
"I think it was an emotional decision for him," Hale said. "Obviously for our players it's tough at this point, but talking to each one by text or phone that I've been able to contact, I think they're excited about the idea of having somebody else to lead them in the offensive side of the game."
In-house candidates include assistant hitting coach Mark Grace, hitting coordinator Chris Cron and Triple-A Reno hitting coach Greg Gross.
One external name to keep a close eye on is Dodgers hitting coach Mark McGwire, who has a long-standing relationship with D-backs chief baseball officer Tony La Russa.
"Hey, that's a great name," Hale said when asked about McGwire. "I'm sure his name would be at the forefront of any list that we're making for hitting guy."
McGwire is not under contract for the Dodgers for next season, and with manager Don Mattingly moving on to the Marlins, McGwire was told by the organization that he is free to look for another job if he wants.
This will be Williams' second coaching stint with the D-backs. He served on their coaching staff from 2010-13 before becoming manager of the Nationals in 2014. He led the Nats to the playoffs that year, but was dismissed following last season's 83-79 finish.
When third-base coach Andy Green left the D-backs to become manager of the Padres, Williams expressed interest in rejoining the organization and Hale had already reached out to him. Williams will handle the infield positioning on defense, which Green was in charge of last year.
"I think there's a very bright future here," Williams said. "I'm really excited to be a part of it."
Hale said he talked to players, including Paul Goldschmidt, who were with the team during Williams' previous time in Arizona and got "glowing reports."
Williams said he did not consider taking a year off following his dismissal in Washington. He also declined to get into questions that dealt with his time with the Nationals, such as whether or not he feels he got a fair shake there.
"I think that's probably a discussion for another day," Williams said. "Today is about the Diamondbacks. It's about me being a part of this, and I'm extremely happy about that. That discussion, for me, no offense, I don't know if it's appropriate for right now. I just think that today is about the new guys coming on board and the direction of this organization moving forward.
"I'm in this game because I love it," Williams said. "It is my passion, to say the least. Once the opportunity arose and Chip got in touch with me, I was eager and willing to come aboard and help as much as I can."
Since retiring from playing in 2003, Alston has been with the A's organization, where he served as a Minor League coach and also as the team's rehab coordinator. Last season, he was promoted to Minor League roving pitching instructor for Oakland.
For Alston, the chance to work with the D-backs is a dream come true. He has lived in the Phoenix area for 17 years and he will now be around home more to see his daughter grow up and have the opportunity to watch his son Garvin Jr., a freshman left-hander, play for Arizona State University.
"I'm very excited to be a part of the Diamondbacks family," Alston said. "I actually didn't believe it. I was like, 'Wow, I'm a D-back.' I'd go to games whenever I had opportunities when I was here and to finally get back on the field, it's such a great feeling."
Alston developed a good relationship with Hale when the pair were with the A's organization and he interviewed for the pitching-coach job, which went to Mike Butcher, whom Alston has known since 1999.