Brame, 44, was pronounced dead at 5:52 p.m. at St. Joseph Medical Center in Tacoma, Pierce County Sheriff's Detective Ed Troyer said.
His 35-year-old wife, Crystal Brame, was flown to Harborview Medical Center in Seattle in critical condition with a gunshot wound to the head.
The two had been going through a divorce.
The shootings happened around 3:10 p.m. in the parking lot of a shopping center in this town northwest of Tacoma. The chief and his wife arrived in the parking lot in separate cars in what appeared to be a pre-arranged meeting, Troyer said.
The couple's two children were in Crystal Brame's vehicle. At one point, the chief put the children in his car, then went back to his wife's car and got inside. A heated conversation ensued, with the chief in the driver's seat of the car and his wife standing outside the car on the driver's side.
Witnesses reported hearing two quick shots, Troyer said.
Medics found Crystal Brame lying on the pavement beside her car with the driver's door ajar. The chief was found slumped over inside the car with a gunshot wound to the head, Troyer said.
A witness reported seeing people in the parking lot running around and screaming after the shootings.
"They had no idea. They were just running for safety," said Kirsten Oakland, 36, a hair stylist at Harbor Cutter, a shop that looks out onto the parking lot.
Dana Mossman, 43, said she was standing in front of a Starbucks shop when she heard a "pop, pop" sound, went to the scene of the shooting and saw a woman lying in a pool of blood.
The Brames' children ran toward their mother's car after hearing the shots, Troyer said.
"I heard one of the children say, 'Daddy shot Mommy,' words to that effect," Mossman said.
Another woman in the parking lot scooped up the kids - an 8-year-old girl and 5-year-old boy - and took them into a video store in the strip mall.
The children were placed in the care of their mother's parents, Troyer said.
Officers recovered a Glock .45-caliber semi-automatic handgun from the crime scene. Troyer would not say whether it was the chief's service weapon or precisely where the gun was found.
"It's a bad day for law enforcement," Troyer said. "This is somebody everybody knew and respected."
Catherine Woodard, assistant chief for criminal investigations, was named acting chief, the first woman to head the police force in the city of 194,000.
Brame started working for the Tacoma Police Department in 1981 and became police chief in January 2002.
"He was exactly what you want," Troyer added, "rose up through the ranks, worked very hard and made chief."
On Friday, the Seattle Post-Intelligencer reported that documents in the couple's divorce case recounted a stormy, sometimes violent relationship.
Crystal Brame accused her husband of pointing his gun at her, trying to choke her in November and saying he "could snap my neck if he wanted to."
It was the fourth time in 2002 that he had tried to choke her, she said. After each time he sent flowers to apologize, she added.
Brame claimed he had been victimized in the relationship. He accused his wife of having a "ferocious temper" and being emotionally unstable.
In court papers, Brame said his wife scratched, bruised and pushed him during two fights in September 1996. Brame was 6-foot-1 and 175 pounds; Crystal Brame is 5 feet tall and weighs about 105 pounds.
Brame said he reported the fights to his boss at the time, interim Chief Ken Monner; to another Tacoma officer who photographed his bruises, and to police in Gig Harbor, where he was living at the time.
But Gig Harbor Police Chief Mitchell Barker said that when Brame reported marital problems, he was "vague" and did not mention any physical assault.
Crystal Brame, in her court filings, said David Brame refused to let her use their credit card without permission, checked her car's odometer to monitor trips to the grocery store and left his loaded service revolver on a bedroom shelf within reach of their two children.
Shortly before they separated in February, Brame pointed his service revolver at her, "telling me, 'Accidents happen,"' according to the court filings.
Neither incident was reported to police, and Brame denied choking or pointing his gun at her.
Crystal Brame filed a sworn statement on March 26, stating that Brame threatened her again, court papers said. She indicated she might ask for a restraining order, but the court file does not reflect that she actually did so.
It was David Brame's second marriage. His first ended in divorce in 1987 after he and his former wife agreed the marriage was "irretrievably broken."
For More Information On Domestic Violence Programs:
Eastside Domestic Violence -- >www.edvp.org. They also have a 24-Hour Crisis Line at (425) 746-1940 or 1-800-562-6025(V/TTY available 8am-6pm)