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WIREs Comput Mol Sci
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Coupled cluster theory in the condensed phase within the singles‐T density scheme for the environment response

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Abstract Reliable simulations of molecules in condensed phase require the combination of an accurate quantum mechanical method for the core region, and a realistic model to describe the interaction with the environment. Additionally, this combination should not significantly increase the computational cost of the calculation compared to the corresponding in vacuo case. In this review, we describe the combination of methods based on coupled cluster (CC) theory with polarizable classical models for the environment. We use the polarizable continuum model (PCM) of solvation to discuss the equations, but we also show how the same theoretical framework can be extended to polarizable force fields. The theory is developed within the perturbation theory energy and singles‐T density (PTES) scheme, where the environmental response is computed with the CC single excitation amplitudes as an approximation for the full one‐particle reduced density. The CC‐PTES combination provides the best compromise between accuracy and computational effort for CC calculations in condensed phase, because it includes the response of the environment to the correlation density at the same computational cost of in vacuo CC. We discuss a number of numerical applications for ground and excited state properties, based on the implementation of CC‐PTES with single and double excitations (CCSD‐PTES), which show the reliability and computational efficiency of the method in reproducing experimental or full‐CC data. This article is characterized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Electronic Structure Theory > Combined QM/MM Methods Software > Quantum Chemistry
Convergence of the CCSD‐PTED‐PCM equations for the calculation of the solvation free energy (kcal/mol) of pyridine in water. Reproduced with permission from Reference . Copyright 2010 American Chemical Society
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Panel a: solvatochromic shifts in the excitation energies of acrolein with two to six water molecules (N) computed at EOM‐CCSD/aug‐cc‐pVDZ level. Panel b: corresponding relative errors for the four EOM‐CCSD/MMPol1 schemes. For the gas phase solute ω = 6.8 eV and f = 0.29. Reproduced with permission from Reference . Copyright 2019 American Chemical Society
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Relative energy (eV) of the GS, LE, and CT electronic states of DMABN at the various optimized geometries in acetonitrile solution. The reference energy is the minimum GS energy in the gas phase. The x axis reports the electronic state for which the geometry was optimized. The labels Eq and Neq refer to the equilibrium and nonequilibrium solvation regime, respectively. All calculations are performed with the LR formalism except those with the SS label, where ES stands for excited state. Reproduced with permission from Reference . Copyright 2019 Wiley‐VCH Verlag GmbH & Co. KGaA
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Relative energy (eV) of the GS, LE, and CT electronic states of DMABN at the various optimized geometries in cyclohexane solution. The reference energy is the minimum GS energy in the gas phase. The x axis reports the electronic state for which the geometry was optimized. The labels Eq and Neq refer to the equilibrium and nonequilibrium solvation regimes, respectively. All calculations are performed with the LR formalism except those with the SS label, where ES stands for excited state. Reproduced with permission from Reference . Copyright 2019 Wiley‐VCH Verlag GmbH & Co. KGaA
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Relative energy (eV) of the GS, LE, and CT electronic states of DMABN at the various optimized geometries in the gas phase. The reference energy is the minimum GS energy. The x axis reports the electronic state for which the geometry was optimized. Reproduced with permission from Reference . Copyright 2019 Wiley‐VCH Verlag GmbH & Co. KGaA
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Optimized geometry of DMABN in the ground state (a), the LE state (b), and the CT state (c) in the gas phase. The optimized structures in solution are similar. Reproduced with permission from Reference . Copyright 2019 Wiley‐VCH Verlag GmbH & Co. KGaA
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Solvation free energy (kcal/mol) for the H2[FeH(PP)2] + complex in THF at various H–H bond distances. R is a scaling factor from the equilibrium bond distance. Reproduced with permission from Reference . Copyright 2011 AIP Publishing
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Cumulative, signed relative error (%) of PTES‐LR compared to PTED‐LR for the excitation energy (E[ω]), the oscillator strength with the nonsize intensive (E[f‐nsi]) and with the size intensive approaches (E[f‐si]) for the 16 molecules of Reference ; the label x‐y indicates state y of molecule x (as in Reference ). Reproduced with permission from Reference . Copyright 2018 AIP Publishing
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Test set used for the benchmarking of LR‐CCSD‐PCM against experiment. This includes 16 molecules divided in four groups: Nitroso, NQ, AB, and U, and the solvents in which measurements were performed. Reproduced with permission from Reference . Copyright 2017 American Chemical Society
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Software > Quantum Chemistry
Electronic Structure Theory > Combined QM/MM Methods
Electronic Structure Theory > Ab Initio Electronic Structure Methods

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