We propose a new algorithm for calculation of vibrational spectra of molecules using tensor train decomposition. Under the assumption that eigenfunctions lie on a low-parametric manifold of low-rank tensors we suggest using well-known iterative methods that utilize matrix inversion (locally optimal block preconditioned conjugate gradient method, inverse iteration) and solve corresponding linear systems inexactly along this manifold. As an application, we accurately compute vibrational spectra (84 states) of acetonitrile molecule CH3CN on a laptop in one hour using only 100 MB of memory to represent all computed eigenfunctions.
@cite_14: There has been continued interest in seeking a theorem describing optimal low-rank approximations to tensors of order 3 or higher that parallels the Eckart-Young theorem for matrices. In this paper, we argue that the naive approach to this problem is doomed to failure because, unlike matrices, tensors of order 3 or higher can fail to have best rank- @math approximations. The phenomenon is much more widespread than one might suspect: examples of this failure can be constructed over a wide range of dimensions, orders, and ranks, regardless of the choice of norm (or even Bregman divergence). Moreover, we show that in many instances these counterexamples have positive volume: they cannot be regarded as isolated phenomena. In one extreme case, we exhibit a tensor space in which no rank-3 tensor has an optimal rank-2 approximation. The notable exceptions to this misbehavior are rank-1 tensors and order-2 tensors (i.e., matrices). In a more positive spirit, we propose a natural way of overcoming the ill-posedness of the low-rank approximation problem, by using weak solutions when true solutions do not exist. For this to work, it is necessary to characterize the set of weak solutions, and we do this in the case of rank 2, order 3 (in arbitrary dimensions). In our work we emphasize the importance of closely studying concrete low-dimensional examples as a first step toward more general results. To this end, we present a detailed analysis of equivalence classes of @math tensors, and we develop methods for extending results upward to higher orders and dimensions. Finally, we link our work to existing studies of tensors from an algebraic geometric point of view. The rank of a tensor can in theory be given a semialgebraic description; in other words, it can be determined by a system of polynomial inequalities. We study some of these polynomials in cases of interest to us; in particular, we make extensive use of the hyperdeterminant @math on @math .
@cite_23: We propose an iterative method for computing vibrational spectra that significantly reduces the memory cost of calculations. It uses a direct product primitive basis, but does not require storing vectors with as many components as there are product basis functions. Wavefunctions are represented in a basis each of whose functions is a sum of products (SOP) and the factorizable structure of the Hamiltonian is exploited. If the factors of the SOP basis functions are properly chosen, wavefunctions are linear combinations of a small number of SOP basis functions. The SOP basis functions are generated using a shifted block power method. The factors are refined with a rank reduction algorithm to cap the number of terms in a SOP basis function. The ideas are tested on a 20-D model Hamiltonian and a realistic CH3CN (12 dimensional) potential. For the 20-D problem, to use a standard direct product iterative approach one would need to store vectors with about 1020 components and would hence require about 8 × 1011 GB...
Canonical tensor decomposition (also called CP decomposition or CANDECOMP PARAFAC model) of the eigenvectors of vibrational problems was considered in work by Leclerc and Carrington @cite_23 . The authors used rank-reduced block power method (RRBPM). Each iteration of this method involves matrix-by-vector product, which can be efficiently implemented in tensor formats. The problem is that this method has poor convergence. Moreover, canonical decomposition is known to have stability issues @cite_14 .