Hole-Hole Tamm-Dancoff-Approximated Density Functional Theory: A Highly Efficient Electronic Structure Method Incorporating Dynamic and Static Correlation

12 February 2020, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

The study of photochemical reaction dynamics requires accurate as well as computationally efficient electronic structure methods for the ground and excited states. While time-dependent density functional theory (TDDFT) is not able to capture static correlation, complete active space self-consistent field (CASSCF) methods are deficient in their ability to describe dynamic correlation. Hence, inexpensive methods that encompass both static and dynamic electron correlation effects are of high interest. Here, we describe the hole-hole Tamm- Dancoff approximated (hh-TDA) density functional theory method, which is closely related to the previously established particle-particle random phase approximation (pp-RPA) and its TDA variant (pp-TDA). In hh-TDA, the N-electron electronic states are obtained through double annihilations starting from a doubly anionic (N+2 electron) reference state. In this way, hh-TDA treats ground and excited states on equal footing, thus allowing for conical intersections to be correctly described. The treatment of dynamic correlation is introduced through the use of commonly-employed density functional approximations to the exchange-correlation potential. hh-TDA appears to be a promising candidate to efficiently treat the photochemistry of organic and biochemical systems that involve several low-lying excited states – particularly those with both low-lying pipi* and npi* states where inclusion of dynamic correlation is essential to describe the relative energetics. In contrast to the existing literature on pp-TDA, we employ a functional- dependent choice for the response kernel in pp- and hh-TDA, which closely resembles the response kernels occurring in linear response and collinear spin-flip TDDFT.

Keywords

Static Correlation
Excited State Electronic Structures
Method Development
density functional theory

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.