We consider quantum tunneling in asymmetric double-well systems for which the local minima in the two wells have the same energy, but the frequencies differ slightly. In a molecular context, this situation can arise if the symmetry is broken by isotopic substitutions. We derive a generalization of instanton theory for these asymmetric systems, leading to a semiclassical expression for the tunneling matrix element and hence the energy-level splitting. We benchmark the method using a set of one- and two-dimensional models, for which the results compare favorably with numerically exact quantum calculations. Using the ring-polymer instanton approach, we apply the method to compute the level splittings in various isotopomers of malonaldehyde in full dimensionality and analyze the relative contributions from the zero-point energy difference and tunneling effects.
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