# Extending molecular simulation time scales: Parallel in time integrations for high-level quantum chemistry and complex force representations

## Abstract

Parallel in time simulation algorithms are presented and applied to conventional molecular dynamics (MD) and ab initio molecular dynamics (AIMD) models of realistic complexity. Assuming that a forward time integrator, f , (e.g. Verlet algorithm) is available to propagate the system from time ti (trajectory positions and velocities xi = (ri; vi)) to time ti+1 (xi+1) by xi+1 = fi(xi), the dynamics problem spanning an interval from t0 : : : tM can be transformed into a root finding problem, F(X) = [xi - f (x(i-1)]i=1;M = 0, for the trajectory variables. The root finding problem is solved using a variety of optimization techniques, including quasi-Newton and preconditioned quasi-Newton optimization schemes that are all unconditionally convergent. The algorithms are parallelized by assigning a processor to each time-step entry in the columns of F(X). The relation of this approach to other recently proposed parallel in time methods is discussed and the effectiveness of various approaches to solving the root finding problem are tested. We demonstrate that more efficient dynamical models based on simplified interactions or coarsening time-steps provide preconditioners for the root finding problem. However, for MD and AIMD simulations such preconditioners are not required to obtain reasonable convergence and theirmore »

- Authors:

- Publication Date:

- Research Org.:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)

- Sponsoring Org.:
- USDOE

- OSTI Identifier:
- 1091975

- Report Number(s):
- PNNL-SA-97206

39395; KJ0402000

- DOE Contract Number:
- AC05-76RL01830

- Resource Type:
- Journal Article

- Journal Name:
- Journal of Chemical Physics, 139(7):Article No. 074114

- Additional Journal Information:
- Journal Name: Journal of Chemical Physics, 139(7):Article No. 074114

- Country of Publication:
- United States

- Language:
- English

- Subject:
- Parallel; quantum chemistry; molecular dynamics; NWChem; ab initio molecular dynamics; Environmental Molecular Sciences Laboratory

### Citation Formats

```
Bylaska, Eric J., Weare, Jonathan Q., and Weare, John H.
```*Extending molecular simulation time scales: Parallel in time integrations for high-level quantum chemistry and complex force representations*. United States: N. p., 2013.
Web. doi:10.1063/1.4818328.

```
Bylaska, Eric J., Weare, Jonathan Q., & Weare, John H.
```*Extending molecular simulation time scales: Parallel in time integrations for high-level quantum chemistry and complex force representations*. United States. doi:10.1063/1.4818328.

```
Bylaska, Eric J., Weare, Jonathan Q., and Weare, John H. Wed .
"Extending molecular simulation time scales: Parallel in time integrations for high-level quantum chemistry and complex force representations". United States. doi:10.1063/1.4818328.
```

```
@article{osti_1091975,
```

title = {Extending molecular simulation time scales: Parallel in time integrations for high-level quantum chemistry and complex force representations},

author = {Bylaska, Eric J. and Weare, Jonathan Q. and Weare, John H.},

abstractNote = {Parallel in time simulation algorithms are presented and applied to conventional molecular dynamics (MD) and ab initio molecular dynamics (AIMD) models of realistic complexity. Assuming that a forward time integrator, f , (e.g. Verlet algorithm) is available to propagate the system from time ti (trajectory positions and velocities xi = (ri; vi)) to time ti+1 (xi+1) by xi+1 = fi(xi), the dynamics problem spanning an interval from t0 : : : tM can be transformed into a root finding problem, F(X) = [xi - f (x(i-1)]i=1;M = 0, for the trajectory variables. The root finding problem is solved using a variety of optimization techniques, including quasi-Newton and preconditioned quasi-Newton optimization schemes that are all unconditionally convergent. The algorithms are parallelized by assigning a processor to each time-step entry in the columns of F(X). The relation of this approach to other recently proposed parallel in time methods is discussed and the effectiveness of various approaches to solving the root finding problem are tested. We demonstrate that more efficient dynamical models based on simplified interactions or coarsening time-steps provide preconditioners for the root finding problem. However, for MD and AIMD simulations such preconditioners are not required to obtain reasonable convergence and their cost must be considered in the performance of the algorithm. The parallel in time algorithms developed are tested by applying them to MD and AIMD simulations of size and complexity similar to those encountered in present day applications. These include a 1000 Si atom MD simulation using Stillinger-Weber potentials, and a HCl+4H2O AIMD simulation at the MP2 level. The maximum speedup obtained by parallelizing the Stillinger-Weber MD simulation was nearly 3.0. For the AIMD MP2 simulations the algorithms achieved speedups of up to 14.3. The parallel in time algorithms can be implemented in a distributed computing environment using very slow TCP/IP networks. Scripts written in Python that make calls to a precompiled quantum chemistry package (NWChem) are demonstrated to provide an actual speedup of 8.2 for a 2.5 ps AIMD simulation of HCl+4H2O at the MP2/6-31G* level. Implemented in this way these algorithms can be used for long time high-level AIMD simulations at a modest cost using machines connected by very slow networks such as WiFi, or in different time zones connected by the Internet. The algorithms can also be used with programs that are already parallel. By using these algorithms we are able to reduce the cost of a MP2/6-311++G(2d,2p) simulation that had reached its maximum possible speedup in the parallelization of the electronic structure calculation from 32 seconds per time step to 6.9 seconds per time step.},

doi = {10.1063/1.4818328},

journal = {Journal of Chemical Physics, 139(7):Article No. 074114},

number = ,

volume = ,

place = {United States},

year = {2013},

month = {8}

}