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Publication# Instanton theory of ground-state tunneling splittings with general paths

Abstract

We derive a multidimensional instanton theory for calculating ground-state tunneling splittings in Cartesian coordinates for general paths. It is an extension of the method by Mil'nikov and Nakamura [J. Chem. Phys. 115, 6881 (2001)] to include asymmetric paths that are necessary for calculating tunneling splitting patterns in multi-well systems, such as water clusters. The approach avoids multiple expensive matrix diagonalizations to converge the fluctuation prefactor in the ring-polymer instanton (RPI) method, and instead replaces them by an integration of a Riccati differential equation. When combined with the string method for locating instantons, we avoid the need to converge the calculation with respect to the imaginary time period of the semiclassical orbit, thereby reducing the number of convergence parameters of the optimized object to just one: the number of equally spaced system replicas used to represent the instanton path. The entirety of the numerical effort is thus concentrated in optimizing the shape of the path and evaluating hessians along the path, which is a dramatic improvement over RPI. In addition to the standard instanton approximations, we neglect the coupling of vibrational modes to external rotations. The method is tested on the model potential of malonaldehyde and on the water dimer and trimer, giving close agreement with RPI at a much-reduced cost. Published under license by AIP Publishing.

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Related concepts (34)

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Instanton

An instanton (or pseudoparticle) is a notion appearing in theoretical and mathematical physics. An instanton is a classical solution to equations of motion with a finite, non-zero action, either in quantum mechanics or in quantum field theory. More precisely, it is a solution to the equations of motion of the classical field theory on a Euclidean spacetime. In such quantum theories, solutions to the equations of motion may be thought of as critical points of the action.

Rotation

Rotation or rotational motion is the circular movement of an object around a central line, known as axis of rotation. A plane figure can rotate in either a clockwise or counterclockwise sense around a perpendicular axis intersecting anywhere inside or outside the figure at a center of rotation. A solid figure has an infinite number of possible axes and angles of rotation, including chaotic rotation (between arbitrary orientations), in contrast to rotation around a axis.

Rotation formalisms in three dimensions

In geometry, various formalisms exist to express a rotation in three dimensions as a mathematical transformation. In physics, this concept is applied to classical mechanics where rotational (or angular) kinematics is the science of quantitative description of a purely rotational motion. The orientation of an object at a given instant is described with the same tools, as it is defined as an imaginary rotation from a reference placement in space, rather than an actually observed rotation from a previous placement in space.

Ontological neighbourhood

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