Second-order correction to the Bigeleisen-Mayer equation due to the nuclear field shift

被引:33
作者
Bigeleisen, J [1 ]
机构
[1] SUNY Stony Brook, Dept Chem, Stony Brook, NY 11794 USA
关键词
reduced partition-function ratios; Born-Oppenheimer approximation;
D O I
10.1073/pnas.95.9.4808
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
The nuclear field shift affects the electronic, rotational, and vibrational energies of polyatomic molecules. The theory of the shifts in molecular spectra has been studied by Schlembach and Tiemann [Schlembach, J. & Tiemann, E. (1982) Chem. Phys, 68, 21]; measurements of the electronic and rotational shifts of the diatomic halides of Pb and Tl have been made by Tiemann et nl, [Tiemann, E., Knockel, H. & Schlembach, J, (1982) Ber. Bunsenges. Phys. Chem. 86, 821], These authors have estimated the relative shifts in the harmonic frequencies of these compounds due to the nuclear field shift to be of the order of 10(-6). I have used this estimate of the relative shift in vibrational frequency to calculate the correction to the harmonic oscillator approximation to the isotopic reduced partition-function ratio (PbS)-Pb-208-S-32/(PbS)-Pb-207-S-32. The correction is 0.3% of the harmonic oscillator value at 300 K. In the absence of compelling evidence to the contrary, it suffices to calculate the nuclear field effect on the total isotopic partition-function ratio from its shift of the electronic zero point energy and the unperturbed molecular vibration.
引用
收藏
页码:4808 / 4809
页数:2
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