Document Type

Article

Publication Date

7-14-2014

Abstract

Working within the Tamm-Dancoff approximation, we calculate the derivative couplings between time-dependent density-functional theory excited states by assuming that the Kohn-Sham superposition of singly excited determinants represents a true electronic wavefunction. All Pulay terms are included in our derivative coupling expression. The reasonability of our approach can be established by noting that, for closely separated electronic states in the infinite basis limit, our final expres- sion agrees exactly with the Chernyak-Mukamel expression (with transition densities from response theory). Finally, we also validate our approach empirically by analyzing the behavior of the derivative couplings around the T1/T2 conical intersection of benzaldehyde.

Comments

This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Q. Ou et al., J. Chem. Phys. 141, 024114 (2014) and may be found at http://dx.doi.org/10.1063/1.4887256.

DOI

10.1063/1.4887256

Included in

Chemistry Commons

Share

COinS
 
 

To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.