### Abstract

A new formulation is presented for the calculation of the chemical potential from molecular simulation based on a test particle removal (inverse Widom) scheme. The new formulation introduces an intermediate stage in the calculation where the test particle to be removed is substituted by a hard particle. Chemical potential calculations at high densities from NVT and NPT Monte Carlo simulations, using a fast analytical algorithm for the computation of volume accessible to the hard core particle, are presented for the pure Lennard-Jones fluid and found to be in excellent agreement with predictions from an accurate equation of state and from simulations using the test particle insertion scheme (Widom insertion scheme). Binary mixture simulations are presented also and the new scheme is applied in the Gibbs ensemble. In all cases where the system is highly dense, the new inverse Widom scheme affords a significant reduction in CPU time compared with the widely used test particle insertion method of Widom. In addition, the new scheme is compared with a recently proposed scheme based on staged insertion.

Original language | English |
---|---|

Pages (from-to) | 905-913 |

Number of pages | 9 |

Journal | Molecular Physics |

Volume | 96 |

Issue number | 6 |

Publication status | Published - 1999 |

Externally published | Yes |

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### ASJC Scopus subject areas

- Biophysics
- Molecular Biology
- Condensed Matter Physics
- Physical and Theoretical Chemistry

### Cite this

*Molecular Physics*,

*96*(6), 905-913.

**On the calculation of the chemical potential using the particle deletion scheme.** / Boulougouris, Georgios C.; Economou, Ioannis; Theodor Ou, Doros N.

Research output: Contribution to journal › Article

*Molecular Physics*, vol. 96, no. 6, pp. 905-913.

}

TY - JOUR

T1 - On the calculation of the chemical potential using the particle deletion scheme

AU - Boulougouris, Georgios C.

AU - Economou, Ioannis

AU - Theodor Ou, Doros N.

PY - 1999

Y1 - 1999

N2 - A new formulation is presented for the calculation of the chemical potential from molecular simulation based on a test particle removal (inverse Widom) scheme. The new formulation introduces an intermediate stage in the calculation where the test particle to be removed is substituted by a hard particle. Chemical potential calculations at high densities from NVT and NPT Monte Carlo simulations, using a fast analytical algorithm for the computation of volume accessible to the hard core particle, are presented for the pure Lennard-Jones fluid and found to be in excellent agreement with predictions from an accurate equation of state and from simulations using the test particle insertion scheme (Widom insertion scheme). Binary mixture simulations are presented also and the new scheme is applied in the Gibbs ensemble. In all cases where the system is highly dense, the new inverse Widom scheme affords a significant reduction in CPU time compared with the widely used test particle insertion method of Widom. In addition, the new scheme is compared with a recently proposed scheme based on staged insertion.

AB - A new formulation is presented for the calculation of the chemical potential from molecular simulation based on a test particle removal (inverse Widom) scheme. The new formulation introduces an intermediate stage in the calculation where the test particle to be removed is substituted by a hard particle. Chemical potential calculations at high densities from NVT and NPT Monte Carlo simulations, using a fast analytical algorithm for the computation of volume accessible to the hard core particle, are presented for the pure Lennard-Jones fluid and found to be in excellent agreement with predictions from an accurate equation of state and from simulations using the test particle insertion scheme (Widom insertion scheme). Binary mixture simulations are presented also and the new scheme is applied in the Gibbs ensemble. In all cases where the system is highly dense, the new inverse Widom scheme affords a significant reduction in CPU time compared with the widely used test particle insertion method of Widom. In addition, the new scheme is compared with a recently proposed scheme based on staged insertion.

UR - http://www.scopus.com/inward/record.url?scp=0000769793&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000769793&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0000769793

VL - 96

SP - 905

EP - 913

JO - Molecular Physics

JF - Molecular Physics

SN - 0026-8976

IS - 6

ER -