Constant pressure ensembles in statistical mechanics
作者:
W.Byers Brown,
期刊:
Molecular Physics
(Taylor Available online 1958)
卷期:
Volume 1,
issue 1
页码: 68-82
ISSN:0026-8976
年代: 1958
DOI:10.1080/00268975800100091
出版商: Taylor & Francis Group
数据来源: Taylor
摘要:
A new statistical procedure is described for obtaining the thermodynamic properties of a molecular system directly as functions of the pressure. This procedure differs in principle from that suggested by Guggenheim [3] in that the members of the representative ensemble are envisaged as being in constant mechanical equilibrium with the exterior. The quantal and classical theories of petit micro-canonical and canonical ensembles of systems at constant pressure are presented, and shown to lead to the established results for perfect and imperfect gases, and for a hypothetical one-dimensional system. The conclusion that the statistical compressibility of a molecular system is essentially positive follows directly from the theory. An alternative procedure which leads to a more satisfactory form of Guggenheim's equation is also described, and its relation to the new approach is shown.
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