Abstract
The structural correlation and the geometric isotope effects in hydrogen-bond crystals are studied by the semiquantal time-dependent Hartree (SQTDH) approach recently developed [K. Ando, J. Chem. Phys. 121, 7136 (2004)]. The theory is demonstrated to provide accurate ground state wave functions for both weak and strong hydrogen bonds via a simple potential minimization procedure in an extended phase space of the variational parameters. It is shown that the asymmetry of the potential energy surface plays a significant role in affecting the correlation between A-H and A\ensuremath{\cdots}B distances in A-H\ensuremath{\cdots}B hydrogen bonds in such a way as to explain the observed variation of experimental data from a variety of compounds. The calculated geometric isotope effect on the A\ensuremath{\cdots}B distance induced by deuteration is $0.02\phantom{\rule{0.3em}{0ex}}\mathrm{\AA{}}$ or less, in agreement with experiments on normal compounds. The origin of the exceptionally large geometric isotope effects observed in some crystals having zero dimensional hydrogen-bond network is discussed on the basis of the present results.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
