First for people that don't know undervolting is not the same thing as under/over clocking, it's 100% safe and you get 100% power for a lower voltage.
Second: the power mode you choose ofcourse improves battery life but it's more related to how much resources your machine is using at that time, For example if your playing hd movies non stop even in power saver, the battery will go down fast. But if you use only programs like Word and Onenote then you will get very close to the maximum battery(Don't forget about screen brightness).
Some programs like old versions of WinAmp have certain bugs that cause huge cpu usage that drains your battery so I recommend you always check the cpu usage. When webbrowsing, adding a addblocker(or java or something) increases the battery since you use less resources.
I also recommend installing battery bar(it callibrates itself over time) to get a much more accurate life estimate.
http://osirisdevelopment.com/BatteryBar/