同位素平衡分馏的核心理论第一节.ppt

This is the expression of partition function of different molecule, the ratio of Q (involving heavy and light isotopes) includes electronic, translational, rotational, and vibrational energies. This is the expression of partition function of different molecule, the ratio of Q (involving heavy and light isotopes) includes electronic, translational, rotational, and vibrational energies. This is the expression of partition function of different molecule, the ratio of Q (involving heavy and light isotopes) includes electronic, translational, rotational, and vibrational energies. * * * It was in that trip of visiting China, Jack and I decided to work together on the stable isotope fractionation calculation using theoretical methods beyond harmonic approximation. And it resulted in this paper published on Geochimica in 2010. Here, I will introduce some results of this paper. * After that, the corrections for RPFR were addressed. Set out 5 corrections * * * * One important correction to harmonic approximation is the hindered internal rotation correction. It almost has been completely ignored by geochemists. Some such rotations are appeared on the vibrational spectra as very small wavenumber vibrations. However, such rotation need overcome the potential barriers in the molecule and they are much larger energy parts then their appearances on the vibrational spectra. Therefore, we should correct such errors. I is the moment of inertia for hindered internal rotor, W is the barrier height of the potential Considering that the expression of Pitzer-Gwinn approximation seems to be generally more accurate This and this are harmonic oscillator partition functions of the quantum mechanical and classical form * We should not ignore such large corrections when study organic molecules with hindered internal rotations. * 这一新的方法是美国加州理工大学Eiler教授研究组最近几年率先开展起来的，由于其在使用单相物质测温上的突破，Eiler教授也因此获得2009年稳定同位素地球化学Epstein奖。虽然Clumped同位素方向自2004年以来已经发表近20篇文章 * Bigeleisen-Mayer 公式 仅有一个未知数：