# Justification for using valence bond theory and molecular orbital theory together?

Elementary gen chem books will make the careful distinction between the two theories and then proceed to claim that chemists can use both to complement each other to explain the behavior of certain electrons. The classic example is Benzene, held together by a $$\sigma$$ bond framework with delocalized $$\pi$$ orbitals. In general, resonance uses MOs and VBT describes the framework to hold the molecule together.

What is the justification for utilizing both theories at once? The construction of the wavefunctions are dramatically different. My only guess is that you need the concept of hybridization from VBT and afterwards, you are constructing molecular orbitals that are superpositions of various hybridized orbitals and other atomic orbitals, is this the right idea?

• This is quite the can of worms you're opening. At the level of your textbook, the justification is pretty much just following the time-proven tradition in chemistry of "I don't care if it's wrong as long as it looks simple." The "orbitals" you see in your textbook are so far away from the actual maths and physics behind them that it's hard to bridge that gap without going way beyond the elementary level. For an actual discussion of how this mixing of wavefunction approaches is or isn't wrong, you'll need to go a lot deeper into a discussion that is still ongoing in theoretical chemistry. Nov 17 '21 at 19:49
• This might be beyond the scope of an elementary general chemistry textbook, but it is far away from a can of worms. It is quite simple actually. The two theories are essentially equivalent and once you take them to their respective mathematical limit within the same framework of approximations they produce the same wave function. They simply approach the problem from different perspectives. However, the way these theories are used and abused by some textbooks is a different story. Suffice to say, neither theory can be a justification of the other, but neither can one refute the other. Nov 18 '21 at 0:51
• pubs.acs.org/doi/pdf/10.1021/acs.jchemed.1c00919 might be of interest Nov 19 '21 at 17:18
• @Martin-マーチン The overall wavefunction stays the same, but only for MO are the constituent orbitals actually static and have energies. In VB, you can't just pick one orbital and investigate its shape and energy, because the former isn't fixed in time and the latter doesn't exist. Thus, displaying a bonding electron pair using a localized orbital is extremely misleading. But then you have to put the caveat that this discussion is confined to a one-electron picture anyway. And then you have to discuss whether static one-electron orbitals are actually a useful physical thing or not. Can of worms. Nov 19 '21 at 18:09