By definition, a matrix $A$ is positive semidefinite if $\langle A\vec x, \vec x \rangle \ge 0 $ for all $\vec x \in V$ where $V$ is an inner-product space. Consider the matrix
$$ A=\begin{bmatrix} 1&i\newline i&1\end{bmatrix} $$
How can I determine if this matrix is positive semidefinite?
A matrix is hermitian if $A=A^{H}$ ($A$ is equal to it's conjugate transpose), which is not satisfied by your matrix.
I therefore simply assume you are given a hermitian matrix. In that case definition does make sense since $\langle Ax,x \rangle \in \mathbb{R}$ which can be proved using the fact that hermitian matrices are self-adjoint ($A=A^{H}=A^{\ast}$). Using the properties of the inner product it follows that $$\alpha := \langle Ax,x\rangle = \overline{\langle x,Ax\rangle} = \overline{\langle A^{\ast}x,\rangle} = \overline{\langle Ax,x\rangle} =\overline{\alpha} $$ and hence $\alpha=\overline{\alpha}$ which is only true for $\alpha \in \mathbb{R}$.
Assuming $\langle \cdot, \cdot \rangle $ is the canonical inner product on $\mathbb{C}^{n}$ given by $$\langle x,y \rangle := y^{H}x=\sum\limits_{i=1}^{n}x_{i}\overline{y}_{i}$$ you can can check if $A$ is positive definite (semi-definit) by calculating whether $$\langle Ax,x \rangle = \sum\limits_{i=1}^{n}\sum\limits_{j=1}^{n}a_{ij}x_{i}\overline{x_{j}} >0 (\geq 0) $$ for all $x\in \mathbb{C}^{n}$.
For example for the matrix $$ A = \left( \begin{array}{cc} 1 & i \\ -i & 1 \end{array} \right) $$ we get $$\begin{align} \langle Ax, x \rangle &= \sum\limits_{i=1}^{n}\sum\limits_{j=1}^{n}a_{ij}x_{i}\overline{x_{j}}\\ &= a_{11}x_{1}\overline{x_{1}}+a_{22}x_{2}\overline{x_{2}}+a_{12}x_{1}\overline{x_{2}}+a_{21}x_{2}\overline{x_{1}}\\ &= a_{11}|x_{1}|^{2}+a_{22}|x_{2}|^{2}+a_{12}x_{1}\overline{x_{2}}+\overline{a_{12}}x_{2}\overline{x_{1}}\\ &= a_{11}|x_{1}|^{2}+a_{22}|x_{2}|^{2}+a_{12}x_{1}\overline{x_{2}}+\overline{a_{12}x_{1}\overline{x_{2}}}\\ &= a_{11}|x_{1}|^{2}+a_{22}|x_{2}|^{2}+2Re(a_{12}x_{1}\overline{x_{2}}) \end{align} $$. Plugin in the values of $A$ this yields $\begin{align} \langle Ax, x \rangle=|x_{1}|^{2}+|x_{2}|^{2}+2Re(ix_{1}\overline{x_{2}}) \end{align} $ which can be further simplified by writing $x_{1}:=a+bi$ and x_{2}=c+di$.
Then $Re(ix_{1}x_{2})=Re(i(a+bi)(c+di)=i(ac-bd+adi+bci))=-(ad+bc)$ and $|x_{1}|^2=a^2+b^2$, $|x_{2}|^2=c^2+d^2$. Plugging in yields
$$ \begin{align} \langle Ax, x\rangle &= |x_{1}|^{2}+|x_{2}|^{2}+2Re(ix_{1}=a^2+b^2+c^2+d^2-2ad-2bc\\ &= a^{2}-2ad+c^{2}+b^{2}-2bc+d^{2}\\ &= |(a-c)+(b-c)i|^{2}\\ &= |(x_1 - x_2)|^2 \geq 0 \end{align} $$