The General Atomic and Molecular Electronic Structure System (GAMESS): Novel Methods on Novel Architectures.

The primary focus of GAMESS over the last 5 years has been the development of new high-performance codes that are able to take effective and efficient advantage of the most advanced computer architectures, both CPU and accelerators. These efforts include employing density fitting and fragmentation methods to reduce the high scaling of well-correlated (e.g., coupled-cluster) methods as well as developing novel codes that can take optimal advantage of graphical processing units and other modern accelerators. Because accurate wave functions can be very complex, an important new functionality in GAMESS is the quasi-atomic orbital analysis, an unbiased approach to the understanding of covalent bonds embedded in the wave function. Best practices for the maintenance and distribution of GAMESS are also discussed.

Converging high-level coupled-cluster energetics via adaptive selection of excitation manifolds driven by moment expansions.

A novel approach to rapidly converging high-level coupled-cluster (CC) energetics in an automated fashion is proposed. The key idea is an adaptive selection of excitation manifolds defining higher--than--two-body components of the cluster operator inspired by CC(P;Q) moment expansions. The usefulness of the resulting methodology is illustrated by molecular examples where the goal is to recover the electronic energies obtained using the CC method with a full treatment of singly, doubly, and triply excited clusters (CCSDT) when the noniterative triples corrections to CCSD fail.

High-level coupled-cluster energetics by merging moment expansions with selected configuration interaction.

Inspired by our earlier semi-stochastic work aimed at converging high-level coupled-cluster (CC) energetics [J. E. Deustua, J. Shen, and P. Piecuch, Phys. Rev. Lett. 119, 223003 (2017) and J. E. Deustua, J. Shen, and P. Piecuch, J. Chem. Phys. 154, 124103 (2021)], we propose a novel form of the CC(P; Q) theory in which the stochastic Quantum Monte Carlo propagations, used to identify dominant higher-than-doubly excited determinants, are replaced by the selected configuration interaction (CI) approach using the perturbative selection made iteratively (CIPSI) algorithm. The advantages of the resulting CIPSI-driven CC(P; Q) methodology are illustrated by a few molecular examples, including the dissociation of F2 and the automerization of cyclobutadiene, where we recover the electronic energies corresponding to the CC calculations with a full treatment of singles, doubles, and triples based on the information extracted from compact CI wave functions originating from relatively inexpensive Hamiltonian diagonalizations.

Is Externally Corrected Coupled Cluster Always Better Than the Underlying Truncated Configuration Interaction?

The short answer to the question in the title is "no". We identify classes of truncated configuration interaction (CI) wave functions for which the externally corrected coupled-cluster (ec-CC) approach using the three-body (T3) and four-body (T4) components of the cluster operator extracted from CI does not improve the results of the underlying CI calculations. Implications of our analysis, illustrated by numerical examples, for the ec-CC computations using truncated and selected CI methods are discussed. We also introduce a novel ec-CC approach using the T3 and T4 amplitudes obtained with the selected CI scheme abbreviated as CIPSI, correcting the resulting energies for the missing T3 correlations not captured by CIPSI with the help of moment expansions similar to those employed in the completely renormalized CC methods.

Non-Uniform Excited State Electronic-Vibrational Coupling of Pigment-Protein Complexes.

Photosynthetic organisms exploit interacting quantum degrees of freedom, namely intrapigment electron-vibrational (vibronic) and interpigment dipolar couplings (J-coupling), to rapidly and efficiently convert light into chemical energy. These interactions result in wave function configurations that delocalize excitation between pigments and pigment vibrations. Our study uses multidimensional spectroscopy to compare two model photosynthetic proteins, the Fenna-Matthews Olson (FMO) complex and light harvesting 2 (LH2), and confirm that long-lived excited state coherences originate from the vibrational modes of the pigment. Within this framework, the J-coupling of vibronic pigments should have a cascading effect in modifying the structured spectral density of excitonic states. We show that FMO effectively couples all of its excitations to a uniform set of vibrations while in LH2, its two chromophore rings each couple to a unique vibrational environment. We simulate energy transfer in a simple model system with non-uniform vibrational coupling to demonstrate how modification of the vibronic coupling strength can modulate energy transfer. Because increasing vibronic coupling increases internal relaxation, strongly coupled vibronic states can act as an energy funnel, which can potentially benefit energy transport.

Coherent and dissipative quantum process tensor reconstructions in two-dimensional electronic spectroscopy.

A major goal of time-resolved spectroscopy is to resolve the dynamical processes that follow photoexcitation. This amounts to identifying all the quantum states involved and the rates of population transfer between them. Unfortunately, such quantum state and kinetic reconstructions are ambiguous using one-dimensional methods such as transient absorption even when all the states of the system are fully resolved. Higher-dimensionality methods like two-dimensional spectroscopy lift some of the ambiguity, but unless the spectral features are well-separated, current inversion methods generally fail. Here, we show that, using both coherence and population signals of the nonlinear response, it is indeed possible to accurately extract both static and dynamic information from the 2D spectrum even when features are highly congested. Coherences report on the positions of the vibronic states of the system, providing a useful constraint for extracting the full kinetic scheme. We model time-resolved 2D photon echo spectra using a sum-over-states approach and show in which regimes the Hamiltonian and kinetic schemes may be recovered. Furthermore, we discuss how such algorithms may be applied to experimental data and where some of the underlying assumptions may fail. The ability to systematically extract the maximal information content of multidimensional spectroscopic data is an important step toward utilizing the full power of these techniques and elucidating the structure and dynamics of increasingly complex molecular systems.

Electronic coherence lifetimes of the Fenna-Matthews-Olson complex and light harvesting complex II.

The study of coherence between excitonic states in naturally occurring photosynthetic systems offers tantalizing prospects of uncovering mechanisms of efficient energy transport. However, experimental evidence of functionally relevant coherences in wild-type proteins has been tentative, leading to uncertainty in their importance at physiological conditions. Here, we extract the electronic coherence lifetime and frequency using a signal subtraction procedure in two model pigment-protein-complexes (PPCs), light harvesting complex II (LH2) and the Fenna-Matthews-Olson complex (FMO), and find that the coherence lifetimes occur at the same timescale (<100 fs) as energy transport between states at the energy level difference equal to the coherence energy. The pigment monomer bacteriochlorophyll a (BChla) shows no electronic coherences, supporting our methodology of removing long-lived vibrational coherences that have obfuscated previous assignments. This correlation of timescales and energy between coherences and energy transport reestablishes the time and energy scales that quantum processes may play a role in energy transport.