Search NASA⌕ Search

SEARCH · Search NASA

Results for “Polarizable continuum model”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Polarization consistent dielectric screening in polarizable continuum model calculations of solvation energies

A polarization consistent framework, where dielectric screening is affected consistently in polarizable continuum model (PCM) calculations, is employed for the study of solvation energies. The computational framework combines a screened range-separated-hybrid functional (SRSH) with PCM calculations, SRSH-PCM, where dielectric screening is imposed in both PCM self-consistent reaction field (SCRF) iterations and the electronic structure Hamiltonian. We begin by demonstrating the impact of modifying the Hamiltonian to include such dielectric screening in SCRF iterations by considering the solutions of electrostatically embedded Hartree–Fock (HF) exact exchange equations. Long-range screened HF-PCM calculations are shown to capture properly the linear dependence of gap energy of frontier orbitals on the inverse of the dielectric constant, whereas unscreened HF-PCM orbital energies are fallaciously semi-constant with respect to the dielectric constant and, therefore, inconsistent with the ionization energy gaps. Similar trends affect density functional theory (DFT) calculations that aim to achieve predictive quality. Importantly, the dielectric screened calculations are shown to significantly affect DFT- and HF PCM-based solvation energies, where screened solvation energies are smaller compared to the unscreened values. Importantly, SRSH-PCM, therefore, appears to reduce the tendency of DFT-PCM to overestimate solvation energies, where we find the effect to increase with the dielectric constant and the polarity of the molecular solute, trends that enhance the quality of DFT-PCM calculations of solvation energy. Understanding the relationship of dielectric screening in the Hamiltonian and DFT-PCM calculations can ultimately benefit on-going efforts for the design of predictive and parameter free descriptions of solvation energies.

Chemistry↗
DOE OSTI2020

Screened Range-Separated Hybrid Functional with Polarizable Continuum Model Overcomes Challenges in Describing Triplet Excitations in the Condensed Phase Using TDDFT

Long range-corrected (LRC) or range-separated hybrid (RSH) functionals where the long-range (LR) limit of electronic interactions is set to the exact exchange have been shown to correct the tendency of traditional density functional theory (DFT) to underestimate the frontier orbital gap. Consequently, the use of such functionals in calculating electronic excited states using linear response based time-dependent DFT (TDDFT) has been successful in correcting the tendency for underestimating the energies of charge transfer states by DFT-based calculations. More recently formulations of functionals that attenuate the LR limit to address condensed-phase effects to polarize the electronic density have been reported. In particular screened RSH (SRSH) combined with polarizable continuum model (PCM) was benchmarked successfully in reproducing the fundamental gap and charge transfer state energies of molecular systems in the condensed phase. Here we use SRSH-PCM to address triplet excited states, and show its success in obtaining correspondence of the low-lying triplet states to the singlet–triplet gap in a similar way that the fundamental orbital gap corresponds to electron removal and addition energies. Importantly, the accuracy of the SRSH-PCM in calculating triplet excitations stands on the polarization consistent framework in addressing the scalar dielectric constant and without affecting the optimal tuning by triplet energies. Finally, the prospect of even further improving the SRSH-PCM accuracy in calculating triplet states can be achieved by optimal tuning on the basis of the spin multiplicity gap.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

How Aqueous Solvation Impacts the Frequencies and Intensities of Infrared Absorption Bands in Flavin: The Quest for a Suitable Solvent Model

FTIR spectroscopy accompanied by quantum chemical simulations can reveal important information about molecular structure and intermolecular interactions in the condensed phase. Simulations typically account for the solvent either through cluster quantum mechanical (QM) models, polarizable continuum models (PCM), or hybrid quantum mechanical/molecular mechanical (QM/MM) models. Recently, we studied the effect of aqueous solvent interactions on the vibrational frequencies of lumiflavin, a minimal flavin model, using cluster QM and PCM models. Those models successfully reproduced the relative frequencies of four prominent stretching modes of flavin’s isoalloxazine ring in the diagnostic 1450–1750 cm−1 range but poorly reproduced the relative band intensities. Here, we extend our studies on this system and account for solvation through a series of increasingly sophisticated models. Only by combining elements of QM clusters, QM/MM, and PCM approaches do we obtain an improved agreement with the experiment. The study sheds light more generally on factors that can impact the computed frequencies and intensities of IR bands in solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Data-Driven Recommendation of Optimal Tuning Scheme for Range-Separated Hybrid Functionals in Solution-Phase UV/Vis Absorption Energy Prediction

Time-dependent density functional theory (TDDFT) combined with range-separated hybrid (RSH) functionals and a tuned range-separation parameter γ offers a computationally economical approach for high-throughput excited- state property predictions. The γ-tuning procedure in the gas phase is well established. However, no agreement on the best γ- tuning procedure has been made when considering the solvent effect with implicit solvent models like the polarizable continuum model (PCM). To answer that question, this study created a diverse dataset with 937 molecules with experimental solutionphase UV/vis absorption spectra. Three γ-tuning methods, the gasphase γ-tuning (GPγT), the partial vertical γ-tuning (PVγT), and the strict vertical γ-tuning (SVγT), were evaluated for the ωPBEh functional over the entire dataset. Additional benchmarks are done for the optimally tuned screened range-separated hybrid combined with the PCM approach (SRSH-PCM) and the solvation-mediated tuning procedure (sol-med-OT). Our findings revealed that the optimal γ-values obtained by the PVγT and the SVγT are significantly smaller than the GPγT. This trend holds consistently across all molecules in our dataset, and we explained the origin of this phenomenon. TDDFT calculations with PVγTand SVγT-tuned γ-values and default global Fock exchange fraction achieve superior performance compared to those using GPγTtuned or default γ and slightly outperform SRSH-PCM and sol-med-OT with similar or lesser computational cost. Furthermore, we found that the smaller γ-values from SVγT captured the expected 1/(εR) asymptotic behavior in the solution phase, resulting in accurate prediction of solution-phase CT excitations, consistent with the screened asymptote behavior encoded in SRSH-PCM. These results show that SVγT is the best scheme for high-throughput UV/vis absorption spectrum calculations using the ωPBEh functional from a data-driven perspective.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

A comprehensive study on three typical photoacid generators using photoelectron spectroscopy and ab initio calculations

Conducting a comprehensive molecular-level evaluation of a photoacid generator (PAG) and its subsequent impact on lithography performance can facilitate the rational design of a promising 193 nm photoresist tailored to specific requirements. In this study, we integrated spectroscopy and computational techniques to meticulously investigate the pivotal factors of three prototypical PAG anions, p-toluenesulfonate (pTS - ), 2-(trifluoromethyl)benzene-1-sulfonate (TFMBS - ), and triflate (TF - ), in the lithography process. Our findings reveal a significant redshift in the absorption spectra caused by specific PAG anions, attributed to their involvement in electronic transition processes, thereby enhancing the transparency of the standard PAG cation, triphenylsulfonium (TPS + ), particularly at ~193 nm. Furthermore, the electronic stability of PAG anions can be enhanced by solvent effects with varying degrees of strength. Here we observed the lowest vertical detachment energy of 6.6 eV of pTS - in PGMEA solution based on the polarizable continuum model, which prevents anion loss at 193 nm lithography. In addition, our findings indicate gas-phase proton affinity values of 316.4 kcal/mol for pTS - , 308.1 kcal/mol for TFMBS - , and 303.2 kcal/mol for TF - , which suggest the increasing acidity strength, yet even the weakest acid pTS - is still stronger than strong acid HBr. The photolysis of TPS + -based PAG, TPS + ·pTS - , generated an excited state leading to homolysis bond cleavage with the lowest reaction energy of 83 kcal/mol. Overall, the PAG anion pTS - displayed moderate acidity, possessed the lowest photolysis reaction energy, and demonstrated an appropriate redshift. These properties collectively render it a promising candidate for an effective acid producer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Assessing Implicit and Explicit Polarizable Solvation Models for Nuclear–Electronic Orbital Systems: Quantum Proton Polarization and Solvation Energetics

Accurate simulations of many chemical processes require the inclusion of both nuclear quantum effects and a solvent environment. The nuclear–electronic orbital (NEO) approach, which treats electrons and select nuclei quantum mechanically on the same level, combined with a polarizable continuum model (PCM) for the solvent environment, addresses this challenge in a computationally practical manner. In this work, the NEO-PCM approach is extended beyond the IEF-PCM (integral equation formalism PCM) and C-PCM (conductor PCM) approaches to the SS(V)PE (surface and simulation of volume polarization for electrostatics) and ddCOSMO (domain decomposed conductor-like screening model) approaches. IEF-PCM, SS(V)PE, C-PCM, and ddCOSMO all exhibit similar solvation energies as well as comparable nuclear polarization within the NEO framework. The calculations show that the nuclear density does not leak out of the molecular cavity because it is much more localized than the electronic density. Finally, the polarization of quantized protons is analyzed in both continuum solvent and explicit solvent environments described by the polarizable MB-pol model, illustrating the impact of specific hydrogen-bonding interactions captured only by explicit solvation. Furthermore, these calculations highlight the relationship among solvation formalism, nuclear polarization, and energetics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

First Principles Simulations of Electrified Interfaces in Electrochemistry

This chapter discusses some of the recent advances made in the first principles modeling of electrochemical catalysts. It also discusses the key development, namely the ability to explicitly treat the effects of surface electrification due to electrochemical processes and applied voltages in a computationally efficient manner. The chapter introduces the thermodynamics and statistical mechanics of electrified metal-solution interfaces. It then discusses the structure of the electrode-electrolyte interface and the effects of applied voltages, followed by an overview of the first-principles model and a motivating example. The chapter also provides a brief summary of classical thermodynamics and describes the basics of thermodynamic detour. It considers the thermodynamics of macroscopic systems and introduces several useful fundamental relations. Here, the chapter also considers a system to exist in a certain macrostate, which is a particular thermodynamic state specified by a set of fixed properties such as constant particle number, constant volume, and constant temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Hydrated Anions: From Clusters to Bulk Solution with Quasi-Chemical Theory

The interactions of hydrated ions with molecular and macromolecular solution and interface partners are strong on a chemical energy scale. Here we recount the foremost ab initio theory for the evaluation of the hydration free energies of ions, namely, quasi-chemical theory (QCT). We focus on anions, particularly halides but also the hydroxide anion, because they have been outstanding challenges for all theories. For example, this work supports understanding the high selectivity for F – over Cl – in fluoride-selective ion channels despite the identical charge and the size similarity of these ions. QCT is built by the identification of inner-shell clusters, separate treatment of those clusters, and then the integration of those results into the broader-scale solution environment. Recent work has focused on a close comparison with mass-spectrometric measurements of ion-hydration equilibria. We delineate how ab initio molecular dynamics (AIMD) calculations on ion-hydration clusters, elementary statistical thermodynamics, and electronic structure calculations on cluster structures sampled from the AIMD calculations obtain just the free energies extracted from the cluster experiments. That theory–experiment comparison has not been attempted before the work discussed here, but the agreement is excellent with moderate computational effort. This agreement reinforces both theory and experiment and provides a numerically accurate inner-shell contribution to QCT. The inner-shell complexes involving heavier halides display strikingly asymmetric hydration clusters. Asymmetric hydration structures can be problematic for the evaluation of the QCT outer-shell contribution with the polarizable continuum model (PCM). Nevertheless, QCT provides a favorable setting for the exploitation of PCM when the inner-shell material shields the ion from the outer solution environment. For the more asymmetrically hydrated, and thus less effectively shielded, heavier halide ions clustered with waters, the PCM is less satisfactory. We therefore investigate an inverse procedure in which the inner-shell structures are sampled from readily available AIMD calculations on the bulk solutions. This inverse procedure is a remarkable improvement; our final results are in close agreement with a standard tabulation of hydration free energies, and the final composite results are independent of the coordination number on the chemical energy scale of relevance, as they should be. Finally, a comparison of anion hydration structure in clusters and bulk solutions from AIMD simulations emphasize some differences: the asymmetries of bulk solution inner-shell structures are moderated compared with clusters but are still present, and inner hydration shells fill to slightly higher average coordination numbers in bulk solution than in clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Solvated Nuclear–Electronic Orbital Structure and Dynamics

Nonadiabatic dynamical processes such as proton-coupled electron transfer and excited state intramolecular proton transfer have been the subject of much research. One of the promising theoretical methods to describe these processes is the nuclear–electronic orbital (NEO) approach. This approach inherently accounts for nuclear quantum effects within quantum chemistry calculations, and it has recently been extended to directly simulate nonadiabatic processes with the development of real-time NEO methods. These processes can also be significantly dependent on the surrounding chemical environment, however, and capturing the effects of the environment is often necessary for analyzing experimentally relevant systems. This work couples the NEO density functional theory and real-time time-dependent density functional theory approaches with solvation through the polarizable continuum model. Here, the effects of this coupling are investigated for ground state properties, solvent-dependent vibrational frequencies, and direct excited state intramolecular proton transfer dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Nuclear–Electronic Orbital QM/MM Approach: Geometry Optimizations and Molecular Dynamics

Hybrid quantum mechanical/molecular mechanical (QM/MM) methods allow simulations of chemical reactions in atomistic solvent and heterogeneous environments such as proteins. Herein, the nuclear–electronic orbital (NEO) QM/MM approach is introduced to enable the quantization of specified nuclei, typically protons, in the QM region using a method such as NEO-density functional theory (NEO-DFT). This approach includes proton delocalization, polarization, anharmonicity, and zero-point energy in geometry optimizations and dynamics. Expressions for the energies and analytical gradients associated with the NEO-QM/MM method, as well as the previously developed polarizable continuum model (NEO-PCM), are provided. Geometry optimizations of small organic molecules hydrogen bonded to water in either dielectric continuum solvent or explicit atomistic solvent illustrate that aqueous solvation can strengthen hydrogen-bonding interactions for the systems studied, as indicated by shorter intermolecular distances at the hydrogen-bond interface. We then performed a real-time direct dynamics simulation of a phenol molecule in explicit water using the NEO-QM/MM method. Furthermore, these developments and initial examples provide the foundation for future studies of nuclear–electronic quantum dynamics in complex chemical and biological environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Anion–Cation–Anion Ion Triplet Characterization by Computation and Photoelectron Spectroscopy

Ion triplets of the chloride salts of two commonly used weakly coordinating cations are reported (i.e., Cl – ·NMe 4 + Cl – (1 – ) and Cl – ·PPh 4 + Cl – (2 – )). Negative ion photoelectron spectra at 20 K afford vertical and adiabatic detachment energies of 5.18 and 5.00 eV (1 – ) and 5.03 and 4.70 eV (2 – ), respectively. These results are well reproduced by coupled cluster calculations with single, double, and perturbative triple excitations (CCSD(T)) whereas M06-2X is systematically too small by ~0.3 eV (i.e., 7 kcal mol –1 ). The structures of both 1 – and 2 – have five or six C–H···Cl – interactions that stabilize these cluster anions by 32 (1 – ) and 27 (2 – ) kcal mol –1 as given by their chloride dissociation enthalpies. In conclusion, these values drop to 7.4 and 3.8 kcal mol –1 in dichloromethane based up conductor-like polarizable continuum model calculations and suggest that X – ·M + X – ion triplets with a weakly coordinating cation maybe the reactive form of salts under some conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Solvent Induced Proton Polarization within the Nuclear–Electronic Orbital Framework

To explicitly account for nuclear quantum effects and solvent environments in simulations of chemical processes, the nuclear-electronic orbital approach is coupled with a polarizable continuum model (PCM). This NEO–PCM approach is used to explore the influence of solvation on nuclear polarization through applications to a water dimer and a set of protonated water tetramers. Nuclear polarization in these species is analyzed in terms of changes in proton density and oxygen–hydrogen bond length. Solvation is shown to enhance nuclear polarization with increasing dielectric constant. For the water dimer, the internal, hydrogen-bonded proton is shown to polarize more than the external, free proton. Moreover, proton quantization leads to greater solvent polarization through their mutual polarization. Furthermore, these calculations highlight the complex interplay among electronic, nuclear, and solvent polarization in chemical systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Modification at the C2'-O-Position with 2-Methylbenzothiophene Induces Unique Structural Changes and Thermal Transitions on Duplexes of RNA and DNA

Oligonucleotides can be chemically modified for a variety of applications that include their use as biomaterials, in therapeutics, or as tools to understand biochemical processes, among others. This work focuses on the functionalization of oligonucleotides of RNA and DNA (12- or 14-nucleotides long) with methylbenzothiophene (BT), at the C2'-O-position, which led to unique structural features. Circular dichroism (CD) analyses showed that positioning the BT units on one strand led to significant thermal destabilization, while duplexes where each strand contained 4-BT rings formed a distinct arrangement with cooperativity/interactions among the modifications (evidenced from the appearance of a band with positive ellipticity at 235 nm). Interestingly, the structural arrays displayed increased duplex stabilization (>10 °C higher than the canonical analogue) as a function of [Na + ] with an unexpected structural rearrangement at temperatures above 50 °C. Density functional theory–polarizable continuum model (DFT-PCM) calculations were carried out, and the analyses were in agreement with induced structural changes as a function of salt content. A model was proposed where the hydrophobic surface allows for an internal nucleobase rearrangement into a more thermodynamically stable structure, before undergoing full denaturation, with increased heat. While this behavior is not common, B- to Z-form duplex transitions can occur and are dependent on parameters that were probed in this work, i.e., temperature, nature of modification, or ionic content. To take advantage of this phenomenon, we probed the ability of the modified duplexes to be recognized by Zα (an RNA binding protein that targets Z-form RNA) via electrophoretic analysis and CD. Interestingly, the protein did not bind to canonical duplexes of DNA or RNA; however, it recognized the modified duplexes, in a [monovalent/divalent salt] dependent manner. Overall, the findings describe methodology to attain unique structural motifs of modified duplexes of DNA or RNA, and control their behavior as a function of salt concentration. While their affinity to RNA binding proteins, and the corresponding mechanism of action, requires further exploration, the tunable properties can be of potential use to study this, and other, types of modifications. The novel arrays that formed, under the conditions described herein, provide a useful way to explore the structure and behavior of modified oligonucleotides, in general.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Improving scalability of electronic structure code for molecular simulations in the presence of environment

A scalable density functional electronic code with Gaussian basis set, called UTEP-NRLMOL, is developed to perform simulations of molecular systems in the presence of the environment with particular attention to the memory requirements. In the electronic structure calculations, the memory and computation time are proportional to the number of atoms. Memory requirements for density functional calculations scale as N*N, where N is the number of atoms. While the recent advances in HPC offer platforms with large numbers of cores, the limited amount of memory available on a given node and poor scalability of the electronic structure codes hinder their efficient usage of these platforms. We have introduced new scaling and parallelization paradigms using MPI-3 shared-memory functionality combined with usage of sparse algebra and storage of matrices in sparse format. This extends the range of applicability of the UTEP-NRLMOL code to large systems over 10,000 atoms, or using up to 67,000 basis functions, and making use of HPC architectures using over 6,000 processors utilizing all available cores. We have also interfaced code with effective fragment potential and polarizable continuum model libraries. The code was used in simulations of several applications which are published in reputed scientific journals.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Solvent Dynamics Are Critical to Understanding Carbon Dioxide Dissolution and Hydration in Water

Simulations of carbon dioxide (CO 2 ) in water may aid in understanding the impact of its accumulation in aquatic environments and help advance technologies for carbon capture and utilization (via, e.g., mineralization). Quantum mechanical (QM) simulations based on static molecular models with polarizable continuum solvation poorly reproduce the energetics of CO 2 hydration to form carbonic acid in water, independent of the level of QM theory employed. Only with density-functional-theory-based molecular dynamics and rare-event sampling, followed by energy corrections based on embedded correlated wavefunction theory (in conjunction with density functional embedding theory), can a close agreement between theory and experiment be achieved. Such multilevel simulations can serve as benchmarks for simpler, less costly models, giving insight into potential errors of the latter. The strong influence of sampling/averaging over dynamical solvent configurations on the energetics stems from the difference in polarity of both the transition state and product (both polar) versus the reactant (nonpolar). When a solute undergoes a change in polarity during reaction, affecting its interaction with the solvent, careful assessment of the energetic contribution of the solvent response to this change is critical. Here, we show that static models (without structural sampling) that incorporate three explicit water molecules can yield far superior results than models with more explicit water molecules because fewer water molecules yield less configurational artifacts. Static models intelligently incorporating both explicit (molecules directly participating in the reaction) and implicit solvation, along with a proper QM theory, e.g., CCSD(T) for closed-shell systems, can close the accuracy gap between static and dynamic models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Predicting Excitation Energies of Twisted Intramolecular Charge-Transfer States with the Time-Dependent Density Functional Theory: Comparison with Experimental Measurements in the Gas Phase and Solvents Ranging from Hexanes to Acetonitrile

Electronically excited states characterized by intramolecular charge transfer play an essential role in many biological processes and optical devices. The ability to make quantitative ab initio predictions of the relative energetics involved is a challenging yet desirable goal, especially for large molecules in solution. In this work, we present a data set of 61 experimental measurements of absorption and emission processes, both in the gas phase and in solvents representing a broad range of polarities, which involve intramolecular charge transfer mediated by a nonzero, "twisted" dihedral angle between one or more donor and acceptor subunits. Among a variety of density functionals investigated within the framework of linear-response theory, the "optimally tuned" LRC-ωPBE functional, which utilizes a system-specific yet nonempirical procedure to specify the range-separation parameter, emerges as the preferred choice. For the entire set of excitation energies, involving changes in dipole moment ranging from 4 to >20 Debye, the mean signed and absolute errors are 0.02 and 0.18 eV, respectively (compared, e.g., to -0.30 and 0.30 for PBE0, 0.44 and 0.47 for LRC-ωPBEh, 0.83 and 0.83 for ωB97X-V). We analyze the performance of polarizable continuum solvation models available in Q-Chem that partition the solvent response into fast and slow time scales, and clear trends emerge when measurements corresponding to the four small 4-(dimethylamino)benzonitrile (DMABN)-like molecules and a charged species are excluded. We make the case that the large errors found only for small molecules in the gas phase and weak solvents cannot be expected to improve via the optimal tuning procedure, which enforces a condition that is exact only in the well-separated donor-acceptor limit, and present empirical evidence implicating the outsized importance for small donor-acceptor systems of relaxation effects that cannot be accounted for by the linear-response time-dependent density functional theory within the adiabatic approximation. Finally, we demonstrate the utility of the optimally tuned density functional approach by targeting the charge-transfer states of a large biomimetic model system for light-harvesting structures in Photosystem II.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Impact of solvation on the GW quasiparticle spectra of molecules

First-principles calculations for electrochemistry require accurate treatment of both electronic structure and solvation. The perturbative GW approximation starting from density functional theory (DFT) calculations accurately models materials systems with varying dimensionality. Continuum solvation models enable efficient treatment of solvation effects in DFT calculations, but their applications with beyond-DFT electronic structure methods such as GW have been limited. Here, we introduce the frequency-dependent liquid polarizability from a nonlocal continuum solvation model in the screened Coulomb interaction of full-frequency GW calculations with a solvated DFT starting point. In this study, we show that the liquid screening contributions substantially reduce the HOMO–LUMO gap of molecules by 3–5 eV, while solvent effects on the DFT starting point negligibly impact the GW gap. The resulting framework facilitates the simultaneous electronic and solvation accuracy needed for first-principles electrochemistry.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗