Proof assistants such as Isabelle/HOL work on a syntactical level on a logical calculus. Imagine you have the modus ponens rule (MP)
$\qquad \displaystyle P\to Q, P\ \Longrightarrow\ Q$
and the proof goal
$\qquad \displaystyle (a \lor b) \to (c \land d), a \lor b \ \overset{!}{\Longrightarrow} c\land d$
We humans see immediately that this follows with modus ponens, but the machine has to match goal to rule syntactically (wether you do apply rule mp
or apply simp
), and this is what unification does. The algorithm finds $\varphi$ with $\varphi(P) = a\lor b$ and $\varphi(Q) = c \land d$, instantiates the rule and applies it.
The good thing about assistants' methods like simp
now is that if your goal is
$\qquad \displaystyle (a \lor b) \to (c \land d), a \ \overset{!}{\Longrightarrow} d$
that they will find a suitable sequence of applications of rules MP, $P \land Q \Longrightarrow P$ and $P \Longrightarrow P \lor Q$ with compatible unifications for the respective steps and solve the goal.
Notation: With $\Gamma = \{\varphi_1, \dots, \varphi_n\}$ a set of logical formulae, the notation
$\qquad \Gamma \Longrightarrow \psi$
means the following:
If I have derived/proven all formulae in $\Gamma$ (i.e. they are valid) then this rule asserts that $\psi$ is also valid.
In a sense, the rule $\Gamma \Longrightarrow \psi$ is the last step in a (long) proof for $\psi$. Proofs are nothing but chains of such rule applications.
Note that rules usually contain schematic variables ($P$ and $Q$ in the above) that can be replaced by arbitrary formulae as long as the same variable is replaced with the same formula in all instances; the result of that format is the concrete rule instance (or intuitively, a proof step). This replacement is above denoted by $\varphi$ which was found by unification.
Often people use $\models$ instead of $\Longrightarrow$.