The Journal of Physical Chemistry A最新文献_第3页

Charge Transfer with a Spin. I: A Variational Constrained-CASSCF Framework for Investigating Charge Transfer in the Presence of Spin–Orbit Coupling 带自旋的电荷转移。研究自旋-轨道耦合下电荷转移的变分约束- casscf框架

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-11-05 Epub Date: 2026-10-23 DOI: 10.1021/acs.jpca.6c05082

Alok Kumar, Zhen Tao, Joseph E. Subotnik, Tian Qiu

{"title":"Charge Transfer with a Spin. I: A Variational Constrained-CASSCF Framework for Investigating Charge Transfer in the Presence of Spin–Orbit Coupling","authors":"Alok Kumar, Zhen Tao, Joseph E. Subotnik, Tian Qiu","doi":"10.1021/acs.jpca.6c05082","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c05082","url":null,"abstract":"Charge transfer in open-shell molecular systems can involvea delicateinterplay between charge localization, orbital relaxation, and spin–orbitcoupling (SOC), particularly near ground-excited state crossings.Here, we introduce a very inexpensive variational framework for treatingthese effects in odd-electron systems by extending the electron/hole-transferDynamically weighted State-Averaged Constrained CASSCF (eDSC/hDSC)method to include SOC. Our method incorporates the SOC Hamiltoniandirectly into the variational orbital optimization through complex-valuedspinor orbitals, allowing orbital and spin degrees of freedom to relaxself-consistently while preserving the time-reversal symmetry of doubletstates. The method achieves smooth potential energy surfaces and rapidself-consistent field (SCF) convergence; moreover, from physicallysmall to artificially large SOC strengths, the calculation can beconverged to very tight thresholds across the whole potential energysurface. While the results presented here are for systems with twocharge centers, as shown in the appendix, the theory is quite generaland can be adapted to either a system of N chargecenters or a metal-molecule surface with a continuum of states, sothat charge transport (and not just charge transfer) can also be studied.The approach therefore provides a route toward ab initio studies of spin-dependent charge transfer and charge transport inmolecular systems with nontrivial spin degrees of freedom.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 44","pages":"8923–8937"},"PeriodicalIF":3.0,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149330350","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Excited-State Intramolecular Proton Transfer: A TD-DFT Study of the Delayed Fluorescence Mechanism in Triquinolonobenzene 激发态分子内质子转移：三喹啉苯延迟荧光机理的TD-DFT研究

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-11-05 Epub Date: 2026-10-27 DOI: 10.1021/acs.jpca.6c04402

Yuhui Liu, Mai-Ning Li, Si-Ying Lu, Yajing Peng, Yu Zhao, Jun Gao, Chaoyuan Zhu

{"title":"Excited-State Intramolecular Proton Transfer: A TD-DFT Study of the Delayed Fluorescence Mechanism in Triquinolonobenzene","authors":"Yuhui Liu, Mai-Ning Li, Si-Ying Lu, Yajing Peng, Yu Zhao, Jun Gao, Chaoyuan Zhu","doi":"10.1021/acs.jpca.6c04402","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c04402","url":null,"abstract":"The interplay between excited-state intramolecular protontransfer(ESIPT) and thermally activated delayed fluorescence (TADF) was investigatedin the prototypical emitter triquinolonobenzene (TQB), using angular-quinacridone(a-QD), which exhibits analogous ESIPT behavior butlacks TADF, as a reference system. Excited-state transition-stateoptimizations reveal that ESIPT is essentially barrierless in bothmolecules. Owing to the negligible spin–orbit coupling (SOC),intersystem crossing (ISC) is ineffective prior to or during the proton-transferprocess. Following ESIPT to the keto tautomer (TQB-TB), however, efficientISC channels become available, with the calculated S1 →T1 and S1 → T2 rate constantsreaching 1.10 × 108 and 1.37 × 108 s–1, respectively. More importantly, the exceptionallysmall S1–T2 energy gap (0.01 eV) enableshighly efficient reverse ISC, resulting in a T2 →S1 rate constant of 9.70 × 107 s–1, whereas the direct T1 → S1 rISC remainsvery slow (1.18 × 102 s–1) owingto the much larger S1–T1 gap. Analysisof the vibronic coupling mechanism shows that Herzberg–Tellercontributions dominate most ISC and reverse ISC processes, whereasthe Franck–Condon contribution remains indispensable for theS1 ↔ T2 channels, accounting for 41.82%(S1 → T2) and 26.10% (T2 →S1) of the corresponding rates. These results establisha comprehensive mechanistic picture in which ESIPT promotes efficientTADF by activating favorable singlet–triplet interconversionpathways in the keto tautomer, providing molecular-level insight intothe design principles of ESIPT-assisted TADF emitters.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 44","pages":"8740–8749"},"PeriodicalIF":3.0,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149330384","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Metal-Ion-Mediated Spin Coupling in Nitronyl Nitroxide Systems: From Superexchange to 4f Electron–Radical Interactions 硝基氮氧化物体系中金属-离子介导的自旋耦合：从超交换到4f电子-自由基相互作用

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-11-05 Epub Date: 2026-10-28 DOI: 10.1021/acs.jpca.6c04972

Xinyu Li, Lingli Shi, Jiarou Liu, Hui Liu, Qingchun Zhao, Yongliang Qin, Di Wang

{"title":"Metal-Ion-Mediated Spin Coupling in Nitronyl Nitroxide Systems: From Superexchange to 4f Electron–Radical Interactions","authors":"Xinyu Li, Lingli Shi, Jiarou Liu, Hui Liu, Qingchun Zhao, Yongliang Qin, Di Wang","doi":"10.1021/acs.jpca.6c04972","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c04972","url":null,"abstract":"To construct tunable spin-coupling systems and explainthe roleof metal ions in modulating radical-based exchange interactions, twophenanthroline-based nitronyl nitroxide (NN) radicals, Br–PhenPhNNand PhendiPhNN, were synthesized and then used as ligands; Cu+ and Gd3+ coordination complexes were prepared.Magnetic studies revealed distinct metal-dependent coupling mechanisms.Superconducting Quantum Interference Device (SQUID) magnetic susceptibilitymeasurements revealed antiferromagnetic interactions in the diamagneticCu+ complexes, mediated by metal-centered superexchangebetween the radical ligands, with J = −5.069cm–1 for Cu+(Br–PhenPhNN)2 and J = −1.394 cm–1 for Cu+(PhendiPhNN)2. In contrast, the paramagneticGd3+ complexes exhibit ferromagnetic 4f electron–radicalcoupling, where JGd–rad = 2.429cm–1 for Gd3+(Br–PhenPhNN)2 and 1.494 cm–1 for Gd3+(PhendiPhNN)2, accompanied by antiferromagnetic radical–radicalinteractions with Jrad–rad = −8.677and −6.694 cm–1, respectively. These resultsshow that Cu+ complexes are dominated by superexchangeinteractions, whereas Gd3+ complexes feature coexistingmultiple competing spin interactions. This distinction highlightsthe crucial role of the metal center in controlling both the typeand strength of radical spin coupling and provides guidance for therational design of molecular magnetic materials.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 44","pages":"8806–8818"},"PeriodicalIF":3.0,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149330340","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Hyperfine Coupling on Nitrogen and Phosphorus in β-Phosphorylated Nitroxide Radicals: Calculations and Models 氮磷在β-磷酸化氮氧自由基中的超精细耦合：计算和模型

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-11-05 Epub Date: 2026-10-24 DOI: 10.1021/acs.jpca.6c04856

Ana M. Toader, Cristina M. Buta, Bogdan Frecus, Gérard Audran, Jean-Patrick Joly, Gabriela Ionita, Sylvain R. A. Marque, Fanica Cimpoesu

{"title":"Hyperfine Coupling on Nitrogen and Phosphorus in β-Phosphorylated Nitroxide Radicals: Calculations and Models","authors":"Ana M. Toader, Cristina M. Buta, Bogdan Frecus, Gérard Audran, Jean-Patrick Joly, Gabriela Ionita, Sylvain R. A. Marque, Fanica Cimpoesu","doi":"10.1021/acs.jpca.6c04856","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c04856","url":null,"abstract":"This work presents computational experiments rationalizingstructure–propertycorrelations encountered in the rich experimental data on electronparamagnetic resonance (EPR) of β-phosphorylated nitroxide radicals,looking particularly at the hyperfine coupling parameters (HFC), proportionalto the spin density at N and P nuclei. The models are based on thecomplementary use of density functional theory (DFT) and valence bond(VB) calculations. Taking a sufficiently large space of resonancestructures, the VB account of HFCs becomes quantitatively comparablewith the unrestricted DFT results, in a range compatible with experiment.At nitrogen, the HFC includes spin-polarization effects and a parttuned by the s:p content of the spin carrier, determined by the localmolecular geometry embedding the NO group. The analysis performedon models of the title compounds showed that the spin density arriveson the phosphorus nucleus, in traces, by through-space distant interactionswith the nitrogen spin carrier. The geometry dependence of the HFCparameters was charted on models relevant for a large class of instrumentallycharacterized molecules.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 44","pages":"8782–8793"},"PeriodicalIF":3.0,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149330365","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Directional Roaming in Formaldehyde Revealed by Dynamics Simulations on a Machine-Learnt Potential 机器学习电位的动态模拟揭示甲醛中的定向漫游

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-11-05 Epub Date: 2026-10-24 DOI: 10.1021/acs.jpca.6c05120

Ananya Sinha, Supriyo Santra, Suman Chakrabarty, Debashree Ghosh

引用次数: 0

Shell-Nested Atomic Orbitals: Restoring the Correlation-Consistent Hierarchy inside the Molecular Virtual Space 壳层嵌套原子轨道：在分子虚拟空间内恢复相关一致的层次结构

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-11-05 Epub Date: 2026-10-20 DOI: 10.1021/acs.jpca.6c06093

Dariusz W. Szczepanik

{"title":"Shell-Nested Atomic Orbitals: Restoring the Correlation-Consistent Hierarchy inside the Molecular Virtual Space","authors":"Dariusz W. Szczepanik","doi":"10.1021/acs.jpca.6c06093","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c06093","url":null,"abstract":"Correlation-consistent basis sets enlarge the one-electronspaceatom by atom and shell by shell, but the canonical molecular virtualspace retains no comparable atom-resolved hierarchy. Extending thefrozen natural-minimal-basis (NMB) construction, we define shell-nestedatomic orbitals (SNAOs): each cycle selects the highest-occupationresidual radial function from every eligible atomic angular-momentumchannel, assembles the selected functions into a complete layer, andfreezes that layer. The levels L1 ⊂ L2 ⊂···share one parent-basisrestricted Hartree–Fock reference; only the virtual degreesof freedom available to dynamic correlation are increased. The levelindex therefore provides a common coordinate for examining radialand angular saturation. Benchmarks comprise five hydrides and Ne throughcc-pV7Z, benzene, pyrrole, and furan, and 32 closed-shell first-rowmolecules in cc-pV5Z. Rank-matched frozen natural orbitals (FNOs)recover more correlation energy at each finite dimension, as expectedfor an occupation-optimized compressor. The SNAO sequence is lesscompact but more regular: for the 32-molecule set, the three-point L2–L4 limitdiffers from the two-point cc-pV(Q,5)Z estimate by 3.2 mEh on average, compared with 13.1 mEh for FNO. SNAO thus complementsFNO by exchanging some fixed-rank recovery for a transferable, shell-resolvedsequence suited to the analysis and extrapolation of correlation freedom.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 44","pages":"9009–9019"},"PeriodicalIF":3.0,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149330249","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ensemble-Based Descriptor Analysis of Flexible Odorants: Conformational Landscapes of Geraniol, Nerol, and Linalool 基于集成的柔性气味描述符分析：香叶醇、橙花醇和芳樟醇的构象景观。

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-10-29 Epub Date: 2026-10-14 DOI: 10.1021/acs.jpca.6c04688

Beatriz Cuadrado-Benavent, Juan J. Nogueira, David Ferro-Costas

{"title":"Ensemble-Based Descriptor Analysis of Flexible Odorants: Conformational Landscapes of Geraniol, Nerol, and Linalool","authors":"Beatriz Cuadrado-Benavent, Juan J. Nogueira, David Ferro-Costas","doi":"10.1021/acs.jpca.6c04688","DOIUrl":"10.1021/acs.jpca.6c04688","url":null,"abstract":"Conformational flexibilityremains a central challenge in the molecularmodeling of odorants because thermally accessible structures may differfrom the potential-energy minima identified in conformational searches.Here, we combine automated conformational exploration, multistructuralthermodynamics, and descriptor-based statistical analysis to characterizethe conformational ensembles of three flexible acyclic terpenic alcohols:geraniol, nerol, and linalool. The conformational searches identifylarge numbers of conformers (119, 88, and 83 for geraniol, nerol,and linalool, respectively), but only a subset of these structurescontributes substantially to the finite-temperature equilibrium ensemble.Across the three systems, entropy-related contributions tend to shiftthe equilibrium toward more extended arrangements than those favoredelectronically, leading to Gibbs free-energy minima at 310 K thatcan differ from the corresponding potential-energy minima. Descriptor–energycorrelation analyses further show that, among the descriptors considered,global shape exhibits the most consistent association with thermodynamicstabilization, rather than individual local hydroxyl-mediated contacts;decomposition of the Gibbs free energies indicates that this trendis predominantly vibrational in origin. Principal component and clusteringanalyses reveal that the ensembles are better described as continuousconformational landscapes than as sharply separated structural families.These results highlight the limitations of relying only on potential-energyminima and support the use of ensemble-based, descriptor-guided molecularmodeling strategies for flexible odorants and related acyclic terpenoids.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 43","pages":"8557–8569"},"PeriodicalIF":3.0,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149293194","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Morphological Effects on the Heterogeneous Freezing of Droplets Containing Different Ice Nucleating Particles 形态对含不同冰核颗粒液滴非均质冻结的影响。

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-10-29 Epub Date: 2026-10-19 DOI: 10.1021/acs.jpca.6c04151

Rebecca A. Conner, Natalie L. Bacallao, Peyton E. Stiles, Jack H. Smith, Taylor A. Peña, Sarah D. Brooks, Ziying Lei

{"title":"Morphological Effects on the Heterogeneous Freezing of Droplets Containing Different Ice Nucleating Particles","authors":"Rebecca A. Conner, Natalie L. Bacallao, Peyton E. Stiles, Jack H. Smith, Taylor A. Peña, Sarah D. Brooks, Ziying Lei","doi":"10.1021/acs.jpca.6c04151","DOIUrl":"10.1021/acs.jpca.6c04151","url":null,"abstract":"Atmospheric aerosol particles can act as ice nucleatingparticles(INPs) and influence cloud formation, precipitation, and radiativeforcing. However, ice nucleation remains poorly understood becauseatmospheric aerosols exhibit complex chemical compositions and morphologies.In particular, how uniformly mixed and phase-separated organic particlesinfluence freezing behavior remains poorly constrained. We investigatedimmersion freezing in aqueous organic droplets with different morphologiesand containing various insoluble INPs using a custom-built coolingstage with a high-resolution camera. The chemical composition of thedifferent droplets was characterized by PTIR and Raman spectroscopy.In core-shell droplets containing diethyl sebacate (DS), the shellcrystallized at warmer temperatures of −8 to −13 °C,whereas the core froze at a much lower temperature of −21 to−25 °C. Black carbon was placed in different locationswithin the core–shell diethyl sebacate droplets, and the largestdifference between shell crystallization and core freezing temperatureswas 13 °C when black carbon was present in both regions. BothK-feldspar and silver iodide promoted warmer freezing temperaturesof the core. These results provide new insights into the role of complexorganic aerosols in mixed-phase clouds and highlight the need to incorporateparticle morphology into the parameterizations used in climate models.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 43","pages":"8668–8676"},"PeriodicalIF":3.0,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149293197","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Vibrational-Gated Intersystem Crossing in Phenolphthalein Dianion: A TDDFT Insight into the Fluorescence Quenching Mechanism 振动门控的酚酞离子体系间交叉：TDDFT对荧光猝灭机制的洞察。

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-10-29 Epub Date: 2026-10-19 DOI: 10.1021/acs.jpca.6c04683

Lu Li, Xiuming Xu, YuXin Guan, Xue Sun, FengMei Tang, Jian Luo

{"title":"Vibrational-Gated Intersystem Crossing in Phenolphthalein Dianion: A TDDFT Insight into the Fluorescence Quenching Mechanism","authors":"Lu Li, Xiuming Xu, YuXin Guan, Xue Sun, FengMei Tang, Jian Luo","doi":"10.1021/acs.jpca.6c04683","DOIUrl":"10.1021/acs.jpca.6c04683","url":null,"abstract":"The structural rigidity of molecular frameworks playsa pivotalrole in modulating intersystem crossings (ISCs). Here, we systematicallyinvestigate the distinct fluorescence behaviors of the phenolphthaleindianion (PHP2–) and the fluorescein dianion (FLU2–)─two structurally analogous xanthene derivatives.By employing time-dependent density functional theory (TDDFT), ourresults reveal that, although both dianions possess nearly degenerate 1ππ* and 3nπ* states with comparablespin–orbital couplings (∼37 cm–1)in the Franck–Condon region, the subsequent relaxation pathwaysare dictated by distinct vibrational modes. In PHP2–, the twisting of a specific phenol ring serves as the critical vibrationalgate that funnels the initially populated 1ππ*state to the 3nπ* state. This is followed by a barrierlessinternal conversion from 3nπ* to the lowest 3ππ* state, ultimately leading to complete fluorescencequenching. In stark contrast, in FLU2–, the coplanarxanthene core rigidified by an oxygen bridge effectively suppressesthis twisting motion. The available torsional modes drive the systemtoward its 1ππ* minimum, thereby precludingISC and allowing efficient radiative decay. These findings establisha clear vibrational-mode-dependent ISC mechanism, demonstrating thatmolecular rigidity does not simply alter energy gaps but rather selectivelyeliminates the specific nuclear motion required to activate ISC.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 43","pages":"8570–8575"},"PeriodicalIF":3.0,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149293299","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Sub-kJ/mol Precision at Practical Cost for Molecular Solids through Local Coupled-Cluster Approaches 通过局部耦合簇方法在实际成本下的分子固体亚kj /mol精度。

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-10-29 Epub Date: 2026-10-14 DOI: 10.1021/acs.jpca.6c05975

Khanh Ngoc Pham, Marcin Modrzejewski, Péter R. Nagy, Jiří Klimeš

{"title":"Sub-kJ/mol Precision at Practical Cost for Molecular Solids through Local Coupled-Cluster Approaches","authors":"Khanh Ngoc Pham, Marcin Modrzejewski, Péter R. Nagy, Jiří Klimeš","doi":"10.1021/acs.jpca.6c05975","DOIUrl":"10.1021/acs.jpca.6c05975","url":null,"abstract":"Generation of numerically converged coupled-cluster referenceenergiesof molecular crystals remains highly non-routine. Yet, such data pointsare critically needed as computational methodologies strive to reachcorrelated wave-function accuracy in condensed-phase systems. Localized-orbitalcoupled-cluster approaches applied within the many-body expansionpromise a scalable route to these reference results. Here, we reportsolutions to a technical challenge when using this methodology─atlong intermolecular distances, the numerical noise due to local approximationscan accumulate for some molecular crystals into a large-scale driftof the correlation energy, especially in the nonadditive three-bodycontributions. Within the local natural orbital (LNO) coupled-clustermethod, we suggest well-balanced approaches to overcome this issue.At the benchmark level, we propose more accurate LNO-CCSD(T) settingsthat remove the artifacts at long distances and attain a numericalprecision of 0.2 kJ/mol (maximum error) in the lattice energy, witha practical cost that is orders of magnitude lower than that of canonicalCCSD(T). As an even more scalable solution, we propose a multi-levelstrategy that utilizes the established routine LNO-CCSD(T) precisiontiers (Tight, vTight) but retains the numerical stability of the benchmarklevel by treating long-distance three-body systems with the random-phaseapproximation (RPA).","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 43","pages":"8707–8721"},"PeriodicalIF":3.0,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149293217","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0