A comparative study of independent particle model based approaches for thermal averages

作者：Banik Subrata^*; Roy Tapta Kanchan; Prasad M Durga

来源：Journal of Chemical Sciences, 2013, 125(5): 1267-1275.

DOI：10.1007/s12039-013-0484-9

• Self-consistent field theory
• partition function
• density matrix

A comparative study is done on thermal average calculation by using the state specific vibrational self-consistent field method (ss-VSCF), the virtual vibrational self-consistent field (v-VSCF) method and the thermal self-consistent field (t-SCF) method. The different thermodynamic properties and expectation values are calculated using these three methods and the results are compared with full configuration interaction method (FVCI). We find that among these three independent particle model based methods, the ss-VSCF method provides most accurate results in the thermal averages followed by t-SCF and the v-VSCF is the least accurate. However, the ss-VSCF is found to be computationally very expensive for the large molecules. The t-SCF gives better accuracy compared to the v-VSCF counterpart especially at higher temperatures.

• 出版日期2013-9