Suppose $f: M \rightarrow \mathbb{R}$ is a smooth function on a manifold $M$ and $v \in T_pM$ a tangent vector at the point $p$. First let me recapitulate the definition of $df(v)$. Suppose $\gamma : (-\epsilon, \epsilon) \rightarrow M$ is a curve such that $$ \gamma(0) =p, \qquad \gamma^{\prime}(0) =v $$ then $$ df(v) := \frac{d f\circ \gamma(t)}{dt}|_{t=0} $$ where the derivative on the right hand side is the usual calculus derivative. Moreover, this is well defined (ie it doesn't depend on the curve $\gamma$ as long as its initial position and velocity are the same).
Now, given two tangent vectors $v,w \in T_pM$, I can think of two ways of defining the quantity $ d^2 f(v,w)$. My question is are these two definitions the same. Assume that $df|_p =0$, which is essential to conclude that the quantity is well defined.
Definition $1$: As before, choose a curve $\gamma : (-\epsilon, \epsilon) \rightarrow M$ passing through $p$ and haing velocity $v$ at $t=0$. Define $$ d^2 f(v,v) := \frac{d^2 f\circ \gamma(t)}{dt^2}|_{t=0} $$ And now define $d^2 f(v,w)$ as follows: $$ d^2 f(v,w) := \frac{d^2 f(v+w,v+w) - d^2 f(v,v)-d^2 f(w,w) }{2}.$$
Definition $2$: Choose a family of curves $\gamma : (-\epsilon, \epsilon) \times (-\epsilon, \epsilon) \rightarrow M$ with the following properties: $$ \gamma(0,0) =0, ~\frac{\partial \gamma(t,s)}{\partial t}|_{(0,0)} =v, ~\frac{\partial \gamma(t,s)}{\partial s}|_{(0,0)} =w.$$ Now I define $d^2 f(v,w)$ as follows: $$ d^2 f(v,w) := \frac{ \partial^2 f\circ \gamma(t,s)}{\partial t \partial s}|_{(0,0)}.$$
Is definition $1$ the same as definition $2$? And is this immediately obvious?
Assume $df_p = 0$ (that is necessary to conclude that the definitions are well defined).
How much of the properties of "second derivative" have you shown? If you have shown that for both definitions
then yes, the result is obvious.
By the polarisation identity for symmetric bilinear forms $$ f(v+w,v+w) - f(v,v) - f(w,w) = 2 f(v,w) $$
it suffices to show that the two forms agree on the diagonal $d^2 f(v,v)$. But then just choose $\gamma_2(t,s) = \gamma_1(t+s)$ where $\gamma_1$ is the $\gamma$ in definition 1 and $\gamma_2$ is the $\gamma$ in definition 2. A straightforward computation in local coordinates show that the two definitions give you the same values for this choice.