New Scaled Atoms-in-Molecules Theory for Predicting Diatomic Potential-Energy Curves III. Refined Applications to the X 1Σg+ and E 1Σg+ States of H2
- 1 May 1969
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 50 (9), 3942-3946
- https://doi.org/10.1063/1.1671652
Abstract
Scaled atoms‐in‐molecules theory is applied to the ground and first excited states of H2. Five basis functions are included, corresponding to , , , , and . Variational scaling parameters are introduced into the A‐ and B‐atom eigenfunctions comprising each basis function; the ground and first excited state energy roots of the secular determinant are independently minimized with respect to these scaling parameters. For computing interatomic contributions to the energy and overlap matrix elements, three different approximations to the 1S H− ground‐state eigenfunction are used. Scaled atoms‐in‐molecules theory in this approximation yields an H2 ground‐state energy which is 6.5 kcal/mole above the exact result. An excited‐state curve is obtained with the proper double minimum; the predicted energy at the outer minimum is almost exact, and at the inner minimum it is about 7.5 kcal/mole too high.
Keywords
This publication has 16 references indexed in Scilit:
- First excited state of the hydrogen molecule and its isotopesJournal of Molecular Spectroscopy, 1968
- Correlation of Electrons Within the Hydride IonThe Journal of Chemical Physics, 1968
- New Scaled Atoms-in-Molecules Theory for Predicting Diatomic Potential-Energy Curves. II. Studies of the Calibration Technique and Applications to HeH+, HeH, He2+, H2−, and He2The Journal of Chemical Physics, 1968
- New Scaled Atoms-in-Molecules Theory for Predicting Diatomic Potential-Energy Curves. I. General Theory and Application to H2 and He2+ +The Journal of Chemical Physics, 1967
- The Rydberg States of Molecules. VI. Potential Curves and Dissociation Behavior of (Rydberg and Other) Diatomic States1Journal of the American Chemical Society, 1966
- Accurate Electronic Wave Functions for theMoleculeReviews of Modern Physics, 1960
- Variation Theorem for Excited StatesPhysical Review B, 1958
- The Theory and Calculation of Screening ConstantsPhysical Review B, 1930
- Neue Berechnung der Energie des Heliums im Grundzustande, sowie des tiefsten Terms von Ortho-HeliumThe European Physical Journal A, 1929
- The Problem of the Normal Hydrogen Molecule in the New Quantum MechanicsPhysical Review B, 1928