Path integral formulation

The Path integral formulation is an elegant method by which quantum mechanical contributions can be incorporated within a classical simulation using Feynman path integrals (Refs. 1-7). Such simulations are particularly applicable to light atoms and molecules such as hydrogen, helium, neon and argon, as well as quantum rotators such as methane and water.

Principles

In the path integral formulation the canonical partition function (in one dimension) is written as (Ref. 4 Eq. 1)

Q(\beta ,V)=\int {\mathrm {d} }x_{1}\int _{x_{1}}^{x_{1}}Dx(\tau )e^{-S[x(\tau )]}

where $S[x(\tau )]$ is the Euclidian action, given by (Ref. 4 Eq. 2)

S[x(\tau )]=\int _{0}^{\beta \hbar }H(x(\tau ))

where $x(\tau )$ is the path in time $\tau$ and $H$ is the Hamiltonian. This leads to (Ref. 4 Eq. 3)

Q_{P}=\left({\frac {mP}{2\pi \beta \hbar ^{2}}}\right)^{P/2}\int ...\int {\mathrm {d} }x_{1}...{\mathrm {d} }x_{P}e^{-\beta \Phi _{P}(x_{1}...x_{P};\beta )}

where the Euclidean time is discretised in units of

\varepsilon ={\frac {\beta \hbar }{P}},P\in {\mathbb {Z} }

x_{t}=x(t\beta \hbar /P)

x_{P+1}=x_{1}

and (Ref. 4 Eq. 4)

\Phi _{P}(x_{1}...x_{P};\beta )={\frac {mP}{2\beta ^{2}\hbar ^{2}}}\sum _{t=1}^{P}(x_{t}-x_{t+1})^{2}+{\frac {1}{P}}\sum _{t=1}^{P}V(x_{t})

.

where $P$ is the Trotter number. In the Trotter limit, where $P\rightarrow \infty$ these equations become exact. In the case where $P=1$ these equations revert to a classical simulation. It has long been recognised that there is an isomorphism between this discretised quantum mechanical description, and the classical statistical mechanics of polyatomic fluids, in particular flexible ring molecules (Ref. 3), due to the periodic boundary conditions in imaginary time. It can be seen from the first term of the above equation that each particle $x_{t}$ interacts with is neighbours $x_{t-1}$ and $x_{t+1}$ via a harmonic spring. The second term provides the internal potential energy. Thus in three dimensions one has the density operator

{\hat {\rho }}(\beta )=\exp \left[-\beta {\hat {H}}\right]

which thanks to the Trotter formula we can tease out $\exp \left[-\beta (U_{\mathrm {spring} }+U_{\mathrm {internal} })\right]$ , where

U_{\mathrm {spring} }={\frac {mP}{2\beta ^{2}\hbar ^{2}}}\sum _{t=1}^{P}|\mathbf {r} _{t}-\mathbf {r} _{t+1}|^{2}

and

U_{\mathrm {internal} }={\frac {1}{P}}\sum _{t=1}^{P}V(\mathbf {r} _{t})

The internal energy is given by

\langle U\rangle ={\frac {3NP}{2\beta }}-\langle U_{\mathrm {spring} }\rangle +\langle U_{\mathrm {internal} }\rangle

The average kinetic energy is known as the primitive estimator, i.e.

\langle K_{P}\rangle ={\frac {3NP}{2\beta }}-\langle U_{\mathrm {spring} }\rangle

Harmonic oscillator

The density matrix for a harmonic oscillator is given by (Ref. 1 Eq. 10-44)

\rho (x',x)={\sqrt {\frac {m\omega }{2\pi \hbar \sinh \omega \beta \hbar }}}\exp \left(-{\frac {m\omega }{2\hbar (\sinh \omega \beta \hbar )^{2}}}\left((x^{2}+x'^{2})\cosh \omega \beta \hbar -2xx'\right)\right)

Related reading

Rotational degrees of freedom

In the case of systems having ( $d$ ) rotational degrees of freedom the Hamiltonian can be written in the form (Ref. 8 Eq. 2.1):

{\hat {H}}={\hat {T}}^{\mathrm {translational} }+{\hat {T}}^{\mathrm {rotational} }+{\hat {V}}

where the rotational part of the kinetic energy operator is given by (Ref. 8 Eq. 2.2)

T^{\mathrm {rotational} }=\sum _{i=1}^{d^{\mathrm {rotational} }}{\frac {{\hat {L}}_{i}^{2}}{2\Theta _{ii}}}

where ${\hat {L}}_{i}$ are the components of the angular momentum operator, and $\Theta _{ii}$ are the moments of inertia. For a rigid three dimensional asymmetric top the kernel is given by (Ref. 9 Eq. 5):