The Journal of Chemical Physics · 2015 · 28 citations · 59 references
Natural SciencesPhysicsComputational PhysicsMolecular PhysicsSpectroscopyAb Initio MethodsApproximation MethodsEigenvalue ProblemsMatrix ComputationVibrational StructureComputational Vibrational SpectroscopyDiscrete Energy LevelsEigenvalue AlgorithmsEigenvalue ComputationGaussian Basis FunctionsGaussian Basis SetsVibrational Energy LevelsVibrational Hamiltonians
Although phase-space localized Gaussians are themselves poor basis functions, they can be used to effectively contract a discrete variable representation basis [A. Shimshovitz and D. J. Tannor, Phys. Rev. Lett. 109, 070402 (2012)]. This works despite the fact that elements of the Hamiltonian and overlap matrices labelled by discarded Gaussians are not small. By formulating the matrix problem as a regular (i.e., not a generalized) matrix eigenvalue problem, we show that it is possible to use an iterative eigensolver to compute vibrational energy levels in the Gaussian basis.
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