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.

One-particle transition density matrices and natural transition orbitals enable quantitative description of electronic transitions and interstate properties involving correlated many-body wave functions within the molecular orbital framework. Here we extend the formalism to the analysis of tensor properties, such as spin–orbit couplings (SOCs), which involve states of different spin projection. By using spinless density matrices and Wigner–Eckart’s theorem, the approach allows one to treat the transitions between states with arbitrary spin projections in a uniform way. In addition to a pictorial representation of the transition, the analysis also yields quantitative contributions of hole–particle pairs into the overall many-body matrix elements. In particular, it helps to rationalize the magnitude of computed SOCs in terms of El-Sayed’s rules. The capabilities of the new tool are illustrated by the analysis of the equation-of-motion coupled-cluster calculations of two transition metal complexes.

Standard implementations of nonrelativistic excited-state calculations compute only one component of spin multiplets (i.e., Ms = 0 triplets); however, matrix elements for all components are necessary for deriving spin-dependent experimental observables. Wigner-Eckart's theorem allows one to circumvent explicit calculations of all multiplet components. We generate all other spin-orbit matrix elements by applying Wigner-Eckart's theorem to a reduced one-particle transition density matrix computed for a single multiplet component. In addition to computational efficiency, this approach also resolves the phase issue arising within Born-Oppenheimer's separation of nuclear and electronic degrees of freedom. A general formalism and its application to the calculation of spin-orbit couplings using equation-of-motion coupledcluster wave functions are presented. The two-electron contributions are included via the mean-field spin-orbit treatment. Intrinsic issues of constructing spin-orbit mean-field operators for open-shell references are discussed, and a resolution is proposed. The method is benchmarked by using several radicals and diradicals. The merits of the approach are illustrated by a calculation of the barrier for spin inversion in a high-spin tris(pyrrolylmethyl)amine Fe(II) complex.

We present an extension of the equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) theory for computing x-ray Ledge spectra, both in the absorption (XAS) and photoelectron (XPS) regimes. The approach is based on the perturbative evaluation of spin-orbit couplings using the Breit-Pauli Hamiltonian and nonrelativistic wave-functions described by the fc-CVS-EOM-CCSD ansatz (EOM-CCSD within the frozen-core core-valence separated (fc-CVS) scheme). The formalism is based on spinless one-particle density matrices. The approach is illustrated by modeling XAS and XPS of several model systems ranging from argon atoms to small molecules containing sulfur and silicon. File list (2) download file view on ChemRxiv Ledges .pdf (1.93 MiB) download file view on ChemRxiv L-edges_SI.pdf (259.57 KiB)

This work reveals via a combined experimental, computational, and astrochemical modeling study that racemic propylene oxide (c-C3H6O)—the first chiral molecule detected outside Earth toward the high-mass star-forming region Sagittarius B2(N)—can be synthesized by non-equilibrium reactions initiated by the effects of secondary electrons generated in the track of cosmic rays interacting with ice-coated interstellar grains through excited-state and spin-forbidden reaction pathways operating within low-temperature interstellar ices at 10 K. Our findings confront traditional hypotheses that thermal chemistries followed by processing of interstellar grains dictate the formation of complex organic molecules (COMs) in molecular clouds. Instead, we reveal a hitherto poorly quantified reaction class involving excited-state and spin-forbidden chemistry leading to racemic mixtures of COMs inside interstellar ices prior to their sublimation in star-forming regions. This fundamental production mechanism is of essential consequence in aiding our understanding of the origin and evolution of chiral molecules in the universe.