The ads focus on this stark but little known fact: Roughly 40 percent of cigarettes sold in the U.S. are smoked by people with mental health issues, including depression, anxiety or substance-abuse problems.
The ads also note that 38 percent of military smokers start after enlisting.
Robin Koval, chief executive of Truth Initiative, accused tobacco companies of exploiting the mentally ill and military for profit.
"As the number of smokers drops, the industry is finding it harder and harder to find those replacement smokers," Koval said in an interview. "So the industry is targeting people based on their challenges in life, on who they are. It's shocking and appalling."
But many groups have been left behind by those gains — not just the mentally ill and military but rural smokers and others who are low-income, including Native Americans and minorities.
Among the mental ill, smoking remains high at 33 percent. Among people with a high school equivalency diploma, the smoking rate stands at more than 40 percent, according to the Centers for Disease Control and Prevention.
Tobacco companies for the most part have not responded to the growing accusations that they are targeting vulnerable populations. In response to a recent Washington Post article on the socioeconomic divide in smokers, the country's largest tobacco company, Altria, said it uses the same marketing approach across the country. And the company pointed to more than $112 billion that tobacco companies have handed over to help smokers and encourage smoking prevention as part of the 1998 Tobacco Master Settlement Agreement.
The latest ads from Truth cite internal tobacco industry documents that discuss ways to make inroads into the mentally ill population. They note that tobacco companies even distributed free cigarettes to psychiatric facilities at one point, and tried to sell the idea that they would help steady patients' nerves.
For years, experts say, psychiatrists and therapists often resisted counseling their patients to quit smoking. Their reasoning was that patients would be overburdened by trying to quit smoking, said Cliff Douglas, director of American Cancer Society's Tobacco Control Center.
"The real truth is quitting actually helps their mental condition," said Koval. "Those who are addicted and quit smoking when in recovery are less likely to relapse. Depression, anxiety, all those issues are helped when people try to quit."
The change in approach has begun to spark new partnerships and joint programs between tobacco-control groups and groups like the National Alliance for Mental Illness and American Psychiatric Association.
At the same time, concern has also increased about smoking among military service members, because of the particularly young and vulnerable age when most enlist.
According to a 2012 Surgeon General's Report, 99 percent of smokers start before the age of 26.
A 2011 Defense Department survey found that almost half of all military service members had used a nicotine product in the past 12 months, and 24 percent on active duty smoked regularly. The U.S. Marine Corps had the highest rate at 31 percent, followed by the Army at 27 percent and the Air Force was lowest with 17 percent.
"I find it deeply disturbing that somehow we think that asking our brave young men and women to put lives on the line for our country, makes it okay for them to be targets for Big Tobacco's bottom line," Koval said. The ads that will air Sunday call the tobacco company's marketing efforts "un-American."
Defense Department officials have expressed concern that the smoking problem is impacting the U.S. military's readiness for battle, and the tobacco-related cost from health problems and lost days at work among soldiers and veterans has been estimated to be in the billions.