Analysis of Localized Diabatic States beyond the Condon Approximation for Excitation Energy Transfer Processes

In a previous paper [Fatehi, S.; et al. J. Chem. Phys. 2013, 139, 124112], we demonstrated a practical method by which analytic derivative couplings of Boys-localized CIS states can be obtained. In this paper, we now apply that same method to the analysis of triplet–triplet energy transfer systems studied by Closs and collaborators [Closs, G. L.; et al. J. Am. Chem. Soc.1988, 110, 2652]. For the systems examined, we are able to conclude that (i) the derivative coupling in the BoysOV basis is negligible, and (ii) the diabatic coupling will likely change little over the configuration space explored at room temperature. Furthermore, we propose and evaluate an approximation that allows for the inexpensive calculation of accurate diabatic energy gradients, called the “strictly diabatic” approximation. This work highlights the effectiveness of diabatic state analytic gradient theory in realistic systems and demonstrates that localized diabatic states can serve as an acceptable approximation to strictly diabatic states

TD-DFT spin-adiabats with analytic nonadiabatic derivative couplings

Wepresent an algorithm for efficient calculation of analytic nonadiabatic derivative couplings between spin-adiabatic, time-dependent density functional theory states within the Tamm-Dancoff approximation. Our derivation is based on the direct differentiation of the Kohn-Sham pseudowavefunction using the framework of Ou et al. Our implementation is limited to the case of a system with an even number of electrons in a closed shell ground state, and we validate our algorithm against finite difference at an S1/T2 crossing of benzaldehyde. Through the introduction of a magnetic field spin-coupling operator, we break time-reversal symmetry to generate complex valued nonadiabatic derivative couplings. Although the nonadiabatic derivative couplings are complex valued, we find that a phase rotation can generate an almost entirely real-valued derivative coupling vector for the case of benzaldehyde

TD-DFT spin-adiabats with analytic nonadiabatic derivative couplings

Wepresent an algorithm for efficient calculation of analytic nonadiabatic derivative couplings between spin-adiabatic, time-dependent density functional theory states within the Tamm-Dancoff approximation. Our derivation is based on the direct differentiation of the Kohn-Sham pseudowavefunction using the framework of Ou et al. Our implementation is limited to the case of a system with an even number of electrons in a closed shell ground state, and we validate our algorithm against finite difference at an S1/T2 crossing of benzaldehyde. Through the introduction of a magnetic field spin-coupling operator, we break time-reversal symmetry to generate complex valued nonadiabatic derivative couplings. Although the nonadiabatic derivative couplings are complex valued, we find that a phase rotation can generate an almost entirely real-valued derivative coupling vector for the case of benzaldehyde

The Requisite Electronic Structure Theory To Describe Photoexcited Nonadiabatic Dynamics: Nonadiabatic Derivative Couplings and Diabatic Electronic Couplings

Conspectus Electronically photoexcited dynamics are complicated because there are so many different relaxation pathways: fluorescence, phosphorescence, radiationless decay, electon transfer, etc. In practice, to model photoexcited systems is a very difficult enterprise, requiring accurate and very efficient tools in both electronic structure theory and nonadiabatic chemical dynamics. Moreover, these theoretical tools are not traditional tools. On the one hand, the electronic structure tools involve couplings between electonic states (rather than typical single state energies and gradients). On the other hand, the dynamics tools involve propagating nuclei on multiple potential energy surfaces (rather than the usual ground state dynamics). In this Account, we review recent developments in electronic structure theory as directly applicable for modeling photoexcited systems. In particular, we focus on how one may evaluate the couplings between two different electronic states. These couplings come in two flavors. If we order states energetically, the resulting adiabatic states are coupled via derivative couplings. Derivative couplings capture how electronic wave functions change as a function of nuclear geometry and can usually be calculated with straightforward tools from analytic gradient theory. One nuance arises, however, in the context of time-dependent density functional theory (TD-DFT): how do we evaluate derivative couplings between TD-DFT excited states (which are tricky, because no wave function is available)? This conundrum was recently solved, and we review the solution below. We also discuss the solution to a second, pesky problem of origin dependence, whereby the derivative couplings do not (strictly) satisfy translation variance, which can lead to a lack of momentum conservation. Apart from adiabatic states, if we order states according to their electronic character, the resulting diabatic states are coupled via electronic or diabatic couplings. The couplings between diabatic states |ΞA⟩ and |ΞB⟩ are just the simple matrix elements, ⟨ΞA|H|ΞB⟩. A difficulty arises, however, because constructing exactly diabatic states is formally impossible and constructing quasi-diabatic states is not unique. To that end, we review recent advances in localized diabatization, which is one approach for generating adiabatic-to-diabatic (ATD) transformations. We also highlight outstanding questions in the arena of diabatization, especially how to generate multiple globally stable diabatic surfaces

State of the Art of Technology for Rural Water System Development

The objective of this study was to review the current state of the art in rural water system technology. This was to be accomplished by a literature review of the Water Resources Scientific Information Center (WRSIC), National Technical Information Service (NTIS), and Smithsonian Science Information Exchange (SSIE). This literature search was to be augmented by interviews with consulting engineers, operating system managers and industrial literature. Both groundwater and surface water technology was to be reviewed. The technology was then to be grouped into four classes: (1) current technology, (2) technology which has been developed, but not currently being used, (3) technology under development which looks promising, and (4) research needed. After the searches were conducted, it became feasible to combine group (2) and (3) into one group entitled technology under development but not fully utilized

Real-time observation of multiexcitonic states in ultrafast singlet fission using coherent 2D electronic spectroscopy.

Singlet fission is the spin-allowed conversion of a spin-singlet exciton into a pair of spin-triplet excitons residing on neighbouring molecules. To rationalize this phenomenon, a multiexcitonic spin-zero triplet-pair state has been hypothesized as an intermediate in singlet fission. However, the nature of the intermediate states and the underlying mechanism of ultrafast fission have not been elucidated experimentally. Here, we study a series of pentacene derivatives using ultrafast two-dimensional electronic spectroscopy and unravel the origin of the states involved in fission. Our data reveal the crucial role of vibrational degrees of freedom coupled to electronic excitations that facilitate the mixing of multiexcitonic states with singlet excitons. The resulting manifold of vibronic states drives sub-100 fs fission with unity efficiency. Our results provide a framework for understanding singlet fission and show how the formation of vibronic manifolds with a high density of states facilitates fast and efficient electronic processes in molecular systems.This is the author accepted manuscript. The final version is available from NPG via http://dx.doi.org/10.1038/nchem.237

Software for the frontiers of quantum chemistry:An overview of developments in the Q-Chem 5 package

This article summarizes technical advances contained in the fifth major release of the Q-Chem quantum chemistry program package, covering developments since 2015. A comprehensive library of exchange–correlation functionals, along with a suite of correlated many-body methods, continues to be a hallmark of the Q-Chem software. The many-body methods include novel variants of both coupled-cluster and configuration-interaction approaches along with methods based on the algebraic diagrammatic construction and variational reduced density-matrix methods. Methods highlighted in Q-Chem 5 include a suite of tools for modeling core-level spectroscopy, methods for describing metastable resonances, methods for computing vibronic spectra, the nuclear–electronic orbital method, and several different energy decomposition analysis techniques. High-performance capabilities including multithreaded parallelism and support for calculations on graphics processing units are described. Q-Chem boasts a community of well over 100 active academic developers, and the continuing evolution of the software is supported by an “open teamware” model and an increasingly modular design