Roy, Tapta Kanchan ; Durga Prasad, M.
(2009)
*A thermal self-consistent field theory for the calculation of molecular vibrational partition functions*
Journal of Chemical Physics, 131
(11).
114102_1-114102_7.
ISSN 0021-9606

Full text not available from this repository.

Official URL: http://jcp.aip.org/resource/1/jcpsa6/v131/i11/p114...

Related URL: http://dx.doi.org/10.1063/1.3213568

## Abstract

A new approach for the calculation of anharmonic molecular vibrational partition functions is developed based on a separable ansatz to the thermal density matrix. The parameters appearing in the effective single particle Hamiltonians that generate the thermal density matrices are determined variationally. The resulting equations are the thermal analogs of the vibrational self-consistent field approximation. The method has the formal property that the free energy calculated by this approach is an upper bound to the exact free energy. Thermodynamic quantities calculated by this approach are generally in good agreement with the results of numerically converged calculations. This approach is more efficient than the standard sum over state approaches in that the computational resources scale with N where N is the number of vibrational degrees of freedom. Thus it can be applied to fairly large systems.

Item Type: | Article |
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Source: | Copyright of this article belongs to American Institute of Physics. |

Keywords: | Free Energy; SCF Calculations; Vibrational States |

ID Code: | 79359 |

Deposited On: | 25 Jan 2012 13:14 |

Last Modified: | 25 Jan 2012 13:14 |

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