...I've heard many theories on "secondary explosve effect" or "detonation" however with exactly -ZERO- evidence to corroborate the stories over the last 50 years, I am happy to disregard them...
While I've found nothing that explains how smokeless powder detonates in a cartridge case I have found quite a bit of proof that single and double base powders CAN and in FACT do detonate and cause catastrophic damage.
I found one study entitled;
"DETONATION VELOCITIES OF SINGLE AND DOUBLE BASE PROPELLANTS"
BY Ken Okada, Tomoharu Matsumura, Yoshio Nakayama, Hisashi lguichi, Masamichi Ishiguchi, Toshihiko Uchikawa, Tetsuya Sawada, Kazushige Kato, Akihiko Yamamoto, and Masatake Yoshida
The conclusion of which was;
"...we found that smokeless powder can be detonated."
"...the DV (Detonation Velocities) of single and double base propellants...were identified as 3624 ms and 4134 ms."
Another study
"DYNAMIC COMPACTION OF POROUS BEDS"
BY H. W. SANDUSKY T. P. LIDDIARD
Another study that shows that this issue has been studied by many countries in the world is;
"Smokeless Propellants as Vehicle Borne lED Main Charges: An Initial Threat Assessment"
BY Special Agent Steven 1. Beggs Bureau of Alcohol, Tobacco, Firearms and Explosives Office of Strategic Intelligence and Information Counter Terrorism Division
All of these studies explain that all smokeless powders can be detonated with the proper initiator. They explain the process by which detonation occurs. From the research I've done it seems that smokeless powder detonation has been studied for decades with some information pointing to an awareness of this issue since at least 1944. Studies discuss the deflagration to detonation transition (DDT) process. In one report they explain that studies done with closed containers haven't been conducted to any great degree so they can't really explain how it happens in a cartridge case.
But since we do know that detonation is a fact I'd recommend being cautious when ever you deviate from the reloading manual recommendations.