Error analysis of molecular dynamics and fractal time approximants from a combinatorial perspective.

Trotter's theorem forms the theoretical basis of most modern molecular dynamics. In essence this theorem states that a time displacement operator (a Lie operator) constructed by exponentiating a sum of noncommuting operators can be approximated by a product of single operators provided the time interval is 'very small.' In theory 'very small' implies infinitesimally small (at which point the approximate product becomes exact), while in practical analysis a finite time interval is divided into several small subintervals or steps. It follows, therefore, that the larger the number of steps the better the approximation to the exact time displacement operator. The question therefore arises: How many steps are sufficient? For bounded operators, standard theorems are available to provide the answer. In this paper we show that a very simple combinatorial formula can be derived which allows the computation of the global differences (as a function of the number of steps) between the Taylor coefficients of the exact time displacement operator and an approximate one constructed by using a finite number of steps. The formula holds for both bounded and nonbounded operators and shows, quantitatively, what is qualitatively expected-that the error decreases with increasing number of steps. Furthermore, the formula applies irrespective of the complexity of the system, boundary conditions, or the thermodynamic ensemble employed for averaging the initial conditions. The analysis yields explicit expressions for the Taylor coefficients which are then used to compute the errors. In the case of the algorithmically based practical numerical simulations in which fixed, albeit small, steps are repeatedly applied, the rise in the number of steps does not reduce the size of the steps but increases the total time of interest. The combinatorial formula shows that, here, the errors diverge. Furthermore, this work can be used to supplement other efforts such as the use of shadow Hamiltonians where the truncation of the series expansion of the latter will produce errors in the higher order propagator moments. [ABSTRACT FROM AUTHOR]