The difference is that
match k with
...
when k = n -> 100
is a case that matches when some particular condition is true (k = n). The n used in the condition refers to the n that is bound as the function parameter. On the other hand
match k with
...
n -> 100
is a case that only needs to match k against a pattern variable n, which can always succeed. The n in the pattern isn't the same n as the n passed into the function.
For comparison, try the code
let rec g n k =
match k with
|_ when (k < 0) || (k > n) -> 0
| n -> n
|_ -> (g n (k+1)) + 1
and you should see that when you get to the second case, the value returned is the value of the pattern variable n, which has been bound to the value of k.
This behavior is described in the Variable Patterns section of the MSDN F# Language Reference, Pattern Matching:
Variable Patterns
The variable pattern assigns the value being matched to a variable
name, which is then available for use in the execution expression to
the right of the -> symbol. A variable pattern alone matches any
input, but variable patterns often appear within other patterns,
therefore enabling more complex structures such as tuples and arrays
to be decomposed into variables. The following example demonstrates a
variable pattern within a tuple pattern.
let function1 x =
match x with
| (var1, var2) when var1 > var2 -> printfn "%d is greater than %d" var1 var2
| (var1, var2) when var1 < var2 -> printfn "%d is less than %d" var1 var2
| (var1, var2) -> printfn "%d equals %d" var1 var2
function1 (1,2)
function1 (2, 1)
function1 (0, 0)
The use of when is described in more depth in Match Expressions.