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The Accurate Evaluation of an Equilibrium Isotope Effect involving Diatomic Molecules

 

作者: C.-L. Chen,   M. Wolfsberg,  

 

期刊: Isotopenpraxis Isotopes in Environmental and Health Studies  (Taylor Available online 1987)
卷期: Volume 23, issue 6  

页码: 205-209

 

ISSN:0021-1915

 

年代: 1987

 

DOI:10.1080/10256018708623792

 

出版商: Taylor & Francis Group

 

关键词: deuterium;isotope effects;partition functions;statistical mechanics;thermodynamics

 

数据来源: Taylor

 

摘要:

The equilibrium constant for the gas phase isotopic exchange reaction D2+ 2 HCl ⇋ H2+ 2 DCl is evaluated by means of isotopic partition function ratios. A number of methods of calculation are explored. The preferred method here is the variational calculation of rotational-vibrational energy levels corresponding to appropriate potential curves, followed by the calculation of the partition functions by direct summation. In order to obtain agreement with experiment, it is necessary to introduce corrections to the Born-Oppenheimer approximation.

 

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