Nonstationarity and related measures for time-dependent hartree–fock and multiconfigurational models
Article first published online: 9 JUN 2013
Copyright © 2013 Wiley Periodicals, Inc.
International Journal of Quantum Chemistry
Volume 113, Issue 23, pages 2489–2505, 5 December 2013
How to Cite
How to cite this article: Int. J. Quantum Chem. 2013, 113, 2489–2505. DOI: 10.1002/qua.24487.
- Issue published online: 22 OCT 2013
- Article first published online: 9 JUN 2013
- Manuscript Accepted: 15 MAY 2013
- Manuscript Revised: 14 MAY 2013
- Manuscript Received: 11 JAN 2013
- real time time-dependent models;
- nonstationarity degree;
- energy and dipole fluctuations;
- laser fields;
- electron correlation;
- number of effectively unpaired electrons
Based on an earlier article (Eberly and Singh, Phys. Rev. D 1973, 7, 359) and related works on short-time evolution, this article proposes a many-electron formulation for the nonstationarity degree which can be assigned to quantum system at each time point. The key measure introduced, , is a nonstationarity index that can be thought of as an inverse nominal lifetime at each instance of time. The index is directly computed from the time derivative of one-electron density matrix and is a size-consistent quantity. In this article, the approach is developed for the time-dependent Hartree–Fock (TDHF), single-excitation (TDCIS), and time-dependent full configuration interaction (TDFCI) models. As a rule, nonstationarity effects are more pronounced in correlated electron systems, and a joint analysis of and the multiconfigurational character of wave functions apparently provide a deeper insight into dynamical molecular processes. The performed calculations on small molecules in laser fields show a preference for the TDCIS model when comparing TDCIS and TDHF with the “exact” TDFCI model. © 2013 Wiley Periodicals, Inc.