The issue turned out to be the Norton 360 antivirus program I am running! It seems Norton recently changed the behavior of their right-click “Disable Auto-Protect” (11/2024). In the past, when this option was selected, every function associated with Auto-Protect would be disabled, including email scanning. That’s not the case any longer. Now, when this option is selected, Auto-Protect disables protection for file scanning but not for email scanning. Disabling email scanning is found in another Norton 360 setting at Settings>Antivirus>Email Protection. The setting that causes WP Mail SMTP to fail certificate verification is the “Scan outbound mails (SMTP)”. Disabling this setting will stop the WP Mail SMTP certificate verification failure.
It would have been nice for Norton to notify its customers or provide a Help icon to let them know that the behavior of “Disable Auto-Protect” has changed, but they didn’t.