Two- and one-photon absorption spectra of aqueous thiocyanate anion highlight the role of symmetry in the condensed phase.

We present the two-photon absorption (2PA) spectrum of aqueous thiocyanate calculated using high-level quantum-chemistry methods. The 2PA spectrum is compared to the one-photon absorption (1PA) spectrum computed using the same computational protocol. Although the two spectra probe the same set of electronic states, the intensity patterns are different, leading to an apparent red-shift of the 2PA spectrum relative to the 1PA spectrum.

Theory, implementation, and disappointing results for two-photon absorption cross sections within the doubly electron-attached equation-of-motion coupled-cluster framework.

The equation-of-motion coupled-cluster singles and doubles method with double electron attachment (EOM-DEA-CCSD) is capable of computing reliable energies, wave functions, and first-order properties of excited states in diradicals and polyenes that have a significant doubly excited character with respect to the ground state, without the need for including the computationally expensive triple excitations. Here, we extend the capabilities of the EOM-DEA-CCSD method to the calculations of a multiphoton property, two-photon absorption (2PA) cross sections. Closed-form expressions for the 2PA cross sections are derived within the expectation-value approach using response wave functions.

Cherry-Picking Resolvents: Recovering the Valence Contribution in X-ray Two-Photon Absorption within the Core-Valence-Separated Equation-of-Motion Coupled-Cluster Response Theory.

Calculations of first-order response wave functions in the X-ray regime often diverge within correlated frameworks such as equation-of-motion coupled-cluster singles and doubles (EOM-CCSD), a consequence of the coupling with the valence ionization continuum. Here, we extend our strategy of introducing a hierarchy of approximations to the EOM-EE-CCSD resolvent (or, inversely, the model Hamiltonian) involved in the response equations for the calculation of X-ray two-photon absorption (X2PA) cross sections. We exploit the frozen-core core-valence separation (fc-CVS) scheme to first decouple the core and valence Fock spaces, followed by a separate approximate treatment of the valence resolvent.

Probing Molecular Chirality of Ground and Electronically Excited States in the UV-vis and X-ray Regimes: An EOM-CCSD Study.

We present several strategies for computing electronic circular dichroism (CD) spectra across different frequency ranges at the equation-of-motion coupled-cluster singles and doubles level of theory. CD spectra of both ground and electronically excited states are discussed. For selected cases, the approach is compared with coupled-cluster linear response results as well as time-dependent density functional theory.

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.

The orbital picture of the first dipole hyperpolarizability from many-body response theory.

We present an approach for obtaining a molecular orbital picture of the first dipole hyperpolarizability (β) from correlated many-body electronic structure methods. Ab initio calculations of β rely on quadratic response theory, which recasts the sum-over-all-states expression of β into a closed-form expression by calculating a handful of first- and second-order response states; for resonantly enhanced β, damped response theory is used. These response states are then used to construct second-order response reduced one-particle density matrices (1PDMs), which, upon visualization in terms of natural orbitals (NOs), facilitate a rigorous and black-box mapping of the underlying electronic structure with β.

Cherry-picking resolvents: A general strategy for convergent coupled-cluster damped response calculations of core-level spectra.

Damped linear response calculations within the equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) framework usually diverge in the x-ray regime. This divergent behavior stems from the valence ionization continuum in which the x-ray response states are embedded. Here, we introduce a general strategy for removing the continuum from the response manifold while preserving important spectral properties of the model Hamiltonian.

Correction: How to stay out of trouble in RIXS calculations within equation-of-motion coupled-cluster damped response theory? Safe hitchhiking in the excitation manifold by means of core-valence separation.

Correction for 'How to stay out of trouble in RIXS calculations within equation-of-motion coupled-cluster damped response theory? Safe hitchhiking in the excitation manifold by means of core-valence separation' by Kaushik D. Nanda et al., Phys.

A simple molecular orbital picture of RIXS distilled from many-body damped response theory.

Ab initio calculations of resonant inelastic x-ray scattering (RIXS) often rely on damped response theory, which prevents the divergence of response solutions in the resonant regime. Within the damped response theory formalism, RIXS moments are expressed as the sum over all electronic states of the system [sum-over-states (SOS) expressions]. By invoking resonance arguments, this expression can be reduced to a few terms, an approximation commonly exploited for the interpretation of computed cross sections.

How to stay out of trouble in RIXS calculations within equation-of-motion coupled-cluster damped response theory? Safe hitchhiking in the excitation manifold by means of core-valence separation.

We present a novel approach for computing resonant inelastic X-ray scattering (RIXS) cross sections within the equation-of-motion coupled-cluster (EOM-CC) framework. The approach is based on recasting the sum-over-states expressions for RIXS moments into closed-form expressions by using damped response theory. Damped response formalism allows one to circumvent problems of divergent behavior of response equations in the resonant regime.

The effect of polarizable environment on two-photon absorption cross sections characterized by the equation-of-motion coupled-cluster singles and doubles method combined with the effective fragment potential approach.

We report an extension of a hybrid polarizable embedding method incorporating solvent effects in the calculations of two-photon absorption (2PA) cross sections. We employ the equation-of-motion coupled-cluster singles and doubles method for excitation energies (EOM-EE-CCSD) for the quantum region and the effective fragment potential (EFP) method for the classical region. We also introduce a rigorous metric based on 2PA transition densities for assessing the domain of applicability of QM/MM (quantum mechanics/molecular mechanics) schemes for calculating 2PA cross sections.

Communication: The pole structure of the dynamical polarizability tensor in equation-of-motion coupled-cluster theory.

In this letter, we investigate the pole structure of dynamical polarizabilities computed within the equation-of-motion coupled-cluster (EOM-CC) theory. We show, both theoretically and numerically, that approximate EOM-CC schemes such as, for example, the EOM-CC singles and doubles model exhibit an incorrect pole structure in which the poles that reflect the excitations from the target state (i.e.

Effect of the diradical character on static polarizabilities and two-photon absorption cross sections: A closer look with spin-flip equation-of-motion coupled-cluster singles and doubles method.

We present static polarizabilities and two-photon absorption (2PA) cross sections for the low-lying electronic states of prototypical diradicals such as benzynes and analogues of m-xylylene and p-quinodimethane computed with the spin-flip equation-of-motion coupled-cluster singles and doubles (EOM-SF-CCSD) method. The static polarizabilities were calculated as analytic second derivatives of the EOM energies, and the 2PA cross sections were calculated using the expectation-value approach. We explain the trends in the nonlinear responses of the SF target states by constructing few-states models based on truncated sum-over-states expressions for these nonlinear properties.

Visualizing the Contributions of Virtual States to Two-Photon Absorption Cross Sections by Natural Transition Orbitals of Response Transition Density Matrices.

Observables such as two-photon absorption cross sections cannot be computed from the wave functions of initial and final states alone because of their nonlinear nature. Rather, they depend on the entire manifold of the excited states, which follows from the familiar sum-over-states expressions of second- and higher-order properties. Consequently, the interpretation of the computed nonlinear optical properties in terms of molecular orbitals is not straightforward and usually relies on approximate few-states models.

Static polarizabilities for excited states within the spin-conserving and spin-flipping equation-of-motion coupled-cluster singles and doubles formalism: Theory, implementation, and benchmarks.

We present the theory and implementation for calculating static polarizabilities within the equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) framework for electronically excited states and its spin-flip variant. We evaluate the second derivatives of the EOM-CCSD Lagrangian with respect to electric-field perturbations. The relaxation of reference molecular orbitals is not included.

Predicting finite-temperature properties of crystalline carbon dioxide from first principles with quantitative accuracy.

Molecular crystal structures, thermodynamics, and mechanical properties can vary substantially with temperature, and predicting these temperature-dependencies correctly is important for many practical applications in the pharmaceutical industry and other fields. However, most electronic structure predictions of molecular crystal properties neglect temperature and/or thermal expansion, leading to potentially erroneous results. Here, we demonstrate that by combining large basis set second-order Møller-Plesset (MP2) or even coupled cluster singles, doubles, and perturbative triples (CCSD(T)) electronic structure calculations with a quasiharmonic treatment of thermal expansion, experimentally observable properties such as the unit cell volume, heat capacity, enthalpy, entropy, sublimation point and bulk modulus of phase I crystalline carbon dioxide can be predicted in excellent agreement with experiment over a broad range of temperatures.

Two-photon absorption cross sections within equation-of-motion coupled-cluster formalism using resolution-of-the-identity and Cholesky decomposition representations: Theory, implementation, and benchmarks.

The equation-of-motion coupled-cluster (EOM-CC) methods provide a robust description of electronically excited states and their properties. Here, we present a formalism for two-photon absorption (2PA) cross sections for the equation-of-motion for excitation energies CC with single and double substitutions (EOM-CC for electronically excited states with single and double substitutions) wave functions. Rather than the response theory formulation, we employ the expectation-value approach which is commonly used within EOM-CC, configuration interaction, and algebraic diagrammatic construction frameworks.

Prediction of organic molecular crystal geometries from MP2-level fragment quantum mechanical/molecular mechanical calculations.

The fragment-based hybrid many-body interaction (HMBI) model provides a computationally affordable means of applying electronic structure wavefunction methods to molecular crystals. It combines a quantum mechanical treatment of individual molecules in the unit cell and their short-range pairwise interactions with a polarizable molecular mechanics force-field treatment of long-range and many-body interactions. Here, we report the implementation of analytic nuclear gradients for the periodic model to enable full relaxation of both the atomic positions and crystal lattice parameters.