Numerical solving of the vibrational time-independent Schrödinger equation in one and two dimensions using the variational method Original Research Article

A program package for variational solving of the time-independent Schrödinger equation (SE) in one and two dimensions is described. The first part of the the program package includes the fitting program (FIT) with which the ab initio or DFT calculated points are fitted to a computationally inexpensive functional form. Proper fitting of the potential energy surface is crucial for the quality of the results. The second part of the package consists of a program for variational solving of the SE (2DSCHRODINGER) using either a shifted Gaussian basis set or the rectangular basis set proposed by Balint-Kurti and coworkers [J. Chem. Phys. 91 (1989) 3571]. The third part of the program package consists of the calculation of the expectation values, IR and Raman spectra XPECT), and the visualization of results (PLOT). The program package is applied to study a quantum harmonic oscillator and an intramolecular, strong hydrogen bond in picolinic acid N-oxide. For the former system analytical solutions exist, while for the latter system a comparison with the experimental data is made. The advantages and disadvantages of the applied methods are discussed.