Abstract
We present a method based on second linear response time-dependent density functional theory (TDDFT) to calculate permanent and transition multipoles of excited states, which are required to compute excited-state absorption/emission spectra and multiphoton optical processes, among others. In previous work, we examined computations based on second linear response theory in which linear response TDDFT was employed twice. In contrast, the present methodology requires information from only a single linear response calculation to compute the excited-state properties. These are evaluated analytically through various algebraic operations involving electron repulsion integrals and excitation vectors. The present derivation focuses on full many-body wave functions instead of single orbitals, as in our previous approach. We test the proposed method by applying it to several diatomic and triatomic molecules. This shows that the computed excited-state dipoles are consistent with respect to reference equation-of-motion coupled-cluster calculations.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 1093-1102 |
| Number of pages | 10 |
| Journal | Journal of Physical Chemistry A |
| Volume | 125 |
| Issue number | 4 |
| DOIs | |
| State | Published - Feb 4 2021 |
Funding
The authors acknowledge support from the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, through DOE grant DE-SC0004752. This research was supported in part through the computational resources and staff contributions provided for the Quest high performance computing facility at Northwestern University, which is jointly supported by the Office of the Provost, the Office for Research, and Northwestern University Information Technology. Computational efforts were also performed on the Hyalite High Performance Computing System, operated and supported by University Information Technology Research Cyberinfrastructure at Montana State University.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry