Columbo's deductive flourishes — as revealed to his target at the end — sometimes approach this. As do the occasional brief scenes in which he drops the fawning and tells the perp exactly what he thinks of him.
One of the rare times Columbo is seen upset is in "A Stitch In Crime," when he's facing Leonard Nimoy's character of Dr. Mayfield. Dr. Mayfield is an open heart surgeon who's working on a crucial research project with a senior partner, Dr. Hiderman. Mayfield also has to operate on his partner, by repairing his heart valves with permanent sutures. He instead uses dissolving sutures, which when dissolved will cause his partner's heart to rupture, killing him in a few weeks, leaving Mayfield to hog all the credit for the project. Sharon Martin, a nurse, discovers this and Mayfield kills her (which is how Columbo first gets on the case). In a genuinely chilling moment, Columbo abruptly drops all pretense and actually slams a coffee cup onto a table! He angrily informs Mayfield that if his partner dies anytime soon, Columbo will have a full autopsy performed to see if the real cause of death was that the surtures that were so supposed to keep his heart valves in place were no longer there. This forces Mayfield to re-operate on his partner, forcing him to save the life of the man he was initially plotting to murder.
In "An Exercise in Fatality," Columbo gets so fed up with Milo Janus that he tells him "she thinks you killed him, and you know what? So do I."
This followed by him laying out that he knows Milo's alibi for the time of the murder is hogwash and that he fully intends to nail the guy. Oh, and does all this in front of half-a-dozen startled hospital guests.
Pretty much every episode of Columbo ends with a CMoA when the villain realises how Columbo has pwned him.
In "Negative Reaction", Paul Galesko is convinced that Columbo is both an incompetent cop and an incompetent photographer to boot. When Columbo produces a photograph of the crime scene that seems to blow Galesko's alibi, he says that Columbo has managed to flip the image of a clock and picks up a camera in the police laboratory to get the negative. Columbo then asks how Galesko knew which camera to pick up. The look on his face when he realises that not only has he given himself away but that Columbo managed to get him to give himself away is one to treasure.
In "A Friend in Deed", Columbo has to bust his own superior, the police commissioner, who has attempted to make a Detective Patsy out of him. The commissioner's (and the audience's) realization that Columbo has so ingeniously outwitted him—"He doesn't live here. I live here."—is a series highlight.
At the beginning of "Death Lends A Hand," Columbo says he believes in astrology and palm reading, then to prove a point, he reads the palms of the murderer and the husband of the victim. It's easy to throw that just as another of his Obfuscating Stupidity quirks... until the end of the episode, where it's revealed Columbo carefully inspected the ring the murderer was wearing and was able to match it to the cut on the victim's cheek, which then led to him focusing his efforts on the murderer. The murderer's face upon hearing that is priceless. Then, seconds later, it turns out the way the murderer was caught was a particularly clever plan by Columbo.
In "The Bye-Bye Sky High IQ Murder Case," an Insufferable Genius who had murdered a fellow member of a Mensa-like organization asked Columbo if he had ever been tested himself. After Columbo said no, the killer pulled down a book with an example test in it and asked him a random question, which Columbo answered correctly after only a moment's thought. The killer was almost relieved to have been caught by what he now considered a Worthy Opponent.
Any of the four episodes with Patrick McGoohan as the guest villain. Pure classics, and McGoohan won two Emmys for his guest roles. (He also directed five episodes and wrote the scripts for two).
In "Any Old Port in a Storm", Adrian Carsini had killed his half-brother by locking him in a wine cellar with the ventilation system shut off, sealing the room. Columbo nicked a bottle of wine from the cellar and set up an opportunity for Carsini to sample it at a restaurant, claiming it was his own. Carsini notices that the wine was heat damaged, and though he did not realize it was from his own collection, this caused him to realize the contents of the wine cellar were damaged as well. His subsequent action of destroying his own damaged collection confirmed for Columbo where the murder actually took place.
Every episode when he says "Just one more thing..." — that is, until the later seasons where most bad guys are wise to his act.
While it's a case of Characterization Marches On, it's pretty awesome in Prescription: Murder when Columbo shows he's not bumbling, confronts the murderer's accomplice and even screams at her for her crime.
In "Ransom For A Dead Man," the second pilot movie, Columbo explains to Leslie Williams what her mistake was: "Mrs. Williams, you have no conscience and that's your weakness. Did it ever occur to you that there are very few people who would take money to forget about a murder? It didn't, did it? I knew it wouldn't."
In "Undercover," Columbo, undercover as Artie Stokes, is walking to the apartment of Mo Weinberg, one of the criminals to meet him for an arranged deal. He looks through the key hole and sees the guy with a gun. Columbo takes out his notepad, writes "you're a horse's ass" on a piece of paper and slips it through the crack in the door. As the criminal takes the paper, Columbo kicks the door in and points his own gun at the guy! It was quite a moment of Took a Level in Badass for Columbo.