diff --git a/QMC.org b/QMC.org index f53235e..40d0c44 100644 --- a/QMC.org +++ b/QMC.org @@ -33,7 +33,7 @@ * Introduction - This web site contains the QMC tutorial of the 2021 LTTC winter school + This website contains the QMC tutorial of the 2021 LTTC winter school [[https://www.irsamc.ups-tlse.fr/lttc/Luchon][Tutorials in Theoretical Chemistry]]. We propose different exercises to understand quantum Monte Carlo (QMC) @@ -45,7 +45,8 @@ associated with a given wave function, and apply this approach to the hydrogen atom. Finally, we present the diffusion Monte Carlo (DMC) method which - we use here to estimate the exact energy of the hydrogen atom and of the H_2 molecule. + we use here to estimate the exact energy of the hydrogen atom and of the H_2 molecule, + starting from an approximate wave function. Code examples will be given in Python and Fortran. You can use whatever language you prefer to write the program. @@ -61,41 +62,29 @@ * Numerical evaluation of the energy - In this section we consider the Hydrogen atom with the following + In this section, we consider the hydrogen atom with the following wave function: $$ \Psi(\mathbf{r}) = \exp(-a |\mathbf{r}|) $$ - We will first verify that, for a given value of $a$, $\Psi$ is an + We will first verify that, for a particular value of $a$, $\Psi$ is an eigenfunction of the Hamiltonian $$ \hat{H} = \hat{T} + \hat{V} = - \frac{1}{2} \Delta - \frac{1}{|\mathbf{r}|} $$ - To do that, we will check if the local energy, defined as + To do that, we will compute the local energy, defined as $$ E_L(\mathbf{r}) = \frac{\hat{H} \Psi(\mathbf{r})}{\Psi(\mathbf{r})}, $$ - is constant. + and check whether it is constant. - - The probabilistic /expected value/ of an arbitrary function $f(x)$ - with respect to a probability density function $p(x)$ is given by - - $$ \langle f \rangle_p = \int_{-\infty}^\infty p(x)\, f(x)\,dx. $$ - - Recall that a probability density function $p(x)$ is non-negative - and integrates to one: - - $$ \int_{-\infty}^\infty p(x)\,dx = 1. $$ - - - The electronic energy of a system is the expectation value of the + In general, the electronic energy of a system, $E$, can be rewritten as the expectation value of the local energy $E(\mathbf{r})$ with respect to the 3N-dimensional electron density given by the square of the wave function: @@ -104,8 +93,24 @@ = \frac{\int \Psi(\mathbf{r})\, \hat{H} \Psi(\mathbf{r})\, d\mathbf{r}}{\int \left[\Psi(\mathbf{r}) \right]^2 d\mathbf{r}} \\ & = & \frac{\int \left[\Psi(\mathbf{r})\right]^2\, \frac{\hat{H} \Psi(\mathbf{r})}{\Psi(\mathbf{r})}\,d\mathbf{r}}{\int \left[\Psi(\mathbf{r}) \right]^2 d\mathbf{r}} = \frac{\int \left[\Psi(\mathbf{r})\right]^2\, E_L(\mathbf{r})\,d\mathbf{r}}{\int \left[\Psi(\mathbf{r}) \right]^2 d\mathbf{r}} - = \langle E_L \rangle_{\Psi^2} + = \langle E_L \rangle_{\Psi^2}\,, \end{eqnarray*} + where $\mathbf{r}$ is the vector of the 3N-dimensional electronic coordinates ($N=1$ for the hydrogen atom). + + For a small number of dimensions, one can compute $E$ by evaluating the integrals on a grid. However, + + The probabilistic /expected value/ of an arbitrary function $f(x)$ + with respect to a probability density function $p(x)$ is given by + + $$ \langle f \rangle_p = \int_{-\infty}^\infty p(x)\, f(x)\,dx, $$ + + where probability density function $p(x)$ is non-negative + and integrates to one: + + $$ \int_{-\infty}^\infty p(x)\,dx = 1. $$ + + + ** Local energy :PROPERTIES: