### Abstract

We evaluate the accuracy of density functional theory quantum calculations of biomolecular subsystems using a simple electrostatic embedding scheme. Our scheme is based on dividing the system of interest into a primary and secondary subsystem. A finite difference discretization of the Kohn-Sham equations is used for the primary subsystem, while its electrostatic environment is modeled with a simple one-electron potential. Force-field atomic partial charges are used to generate smeared Gaussian charge densities and to model the secondary subsystem. We illustrate the utility of this approach with calculations of truncated dipeptide chains. We analyze quantitatively the accuracy of this approach by calculating atomic forces and comparing results with full QM calculations. The impact of the choice made in terminating dangling bonds at the frontier of the QM region is also investigated.

Original language | English (US) |
---|---|

Pages (from-to) | 2257-2264 |

Number of pages | 8 |

Journal | Journal of Chemical Theory and Computation |

Volume | 5 |

Issue number | 9 |

DOIs | |

State | Published - Sep 2009 |

Externally published | Yes |

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### ASJC Scopus subject areas

- Physical and Theoretical Chemistry
- Computer Science Applications

### Cite this

*Journal of Chemical Theory and Computation*,

*5*(9), 2257-2264. https://doi.org/10.1021/ct900209y

**Quantitative assessment of electrostatic embedding in density functional theory calculations of biomolecular systems.** / Fattebert, J. L.; Law, R. J.; Bennion, B.; Lau, Edmond Y; Schwegler, E.; Lightstone, Felice C.

Research output: Contribution to journal › Article

*Journal of Chemical Theory and Computation*, vol. 5, no. 9, pp. 2257-2264. https://doi.org/10.1021/ct900209y

}

TY - JOUR

T1 - Quantitative assessment of electrostatic embedding in density functional theory calculations of biomolecular systems

AU - Fattebert, J. L.

AU - Law, R. J.

AU - Bennion, B.

AU - Lau, Edmond Y

AU - Schwegler, E.

AU - Lightstone, Felice C

PY - 2009/9

Y1 - 2009/9

N2 - We evaluate the accuracy of density functional theory quantum calculations of biomolecular subsystems using a simple electrostatic embedding scheme. Our scheme is based on dividing the system of interest into a primary and secondary subsystem. A finite difference discretization of the Kohn-Sham equations is used for the primary subsystem, while its electrostatic environment is modeled with a simple one-electron potential. Force-field atomic partial charges are used to generate smeared Gaussian charge densities and to model the secondary subsystem. We illustrate the utility of this approach with calculations of truncated dipeptide chains. We analyze quantitatively the accuracy of this approach by calculating atomic forces and comparing results with full QM calculations. The impact of the choice made in terminating dangling bonds at the frontier of the QM region is also investigated.

AB - We evaluate the accuracy of density functional theory quantum calculations of biomolecular subsystems using a simple electrostatic embedding scheme. Our scheme is based on dividing the system of interest into a primary and secondary subsystem. A finite difference discretization of the Kohn-Sham equations is used for the primary subsystem, while its electrostatic environment is modeled with a simple one-electron potential. Force-field atomic partial charges are used to generate smeared Gaussian charge densities and to model the secondary subsystem. We illustrate the utility of this approach with calculations of truncated dipeptide chains. We analyze quantitatively the accuracy of this approach by calculating atomic forces and comparing results with full QM calculations. The impact of the choice made in terminating dangling bonds at the frontier of the QM region is also investigated.

UR - http://www.scopus.com/inward/record.url?scp=73349091858&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=73349091858&partnerID=8YFLogxK

U2 - 10.1021/ct900209y

DO - 10.1021/ct900209y

M3 - Article

AN - SCOPUS:73349091858

VL - 5

SP - 2257

EP - 2264

JO - Journal of Chemical Theory and Computation

JF - Journal of Chemical Theory and Computation

SN - 1549-9618

IS - 9

ER -