Document Type
Article
Date of Original Version
5-27-2008
Department
Chemistry
Abstract
A Monte Carlo path integral method to study the coupling between the rotation and bending degrees of freedom for water is developed. It is demonstrated that soft internal degrees of freedom that are not stretching in nature can be mapped with stereographic projection coordinates. For water, the bending coordinate is orthogonal to the stereographic projection coordinates used to map its orientation. Methods are developed to compute the classical and quantum Jacobian terms so that the proper infinitely stiff spring constant limit is recovered in the classical limit, and so that the nonconstant nature of the Riemann Cartan curvature scalar is properly accounted in the quantum simulations. The theory is used to investigate the effects of the geometric coupling between the bending and the rotating degrees of freedom for the water monomer in an external field in the 250 to 500 K range. We detect no evidence of geometric coupling between the bending degree of freedom and the orientations.
Citation/Publisher Attribution
Curotto, E., Freeman, D. L., & Doll, J. D. (2007). A Stereographic Projection Path Integral Study of the Coupling Between the Orientation and the Bending Degrees of Freedom of Water. Journal of Chemical Physics, 128(20), 204107. doi: 10.1063/1.3259047
Available at: http://dx.doi.org/10.1063/1.3259047
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All rights reserved under copyright.
Publisher Statement
© 2008 American Institute of Physics.