The Journal of Physical Chemistry A最新文献

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Reworking the Tao-Mo Exchange-Correlation Functional. III. Improved Deorbitalization Strategy and Faithful Deorbitalization. 重塑陶莫交换相关函数。III.改进脱轨策略和忠实脱轨。
IF 2.7 2区 化学
The Journal of Physical Chemistry A Pub Date : 2024-07-12 DOI: 10.1021/acs.jpca.4c02635
H Francisco, A C Cancio, S B Trickey
{"title":"Reworking the Tao-Mo Exchange-Correlation Functional. III. Improved Deorbitalization Strategy and Faithful Deorbitalization.","authors":"H Francisco, A C Cancio, S B Trickey","doi":"10.1021/acs.jpca.4c02635","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c02635","url":null,"abstract":"<p><p>We present a deorbitalization of the recent simplified, regularized Tao-Mo exchange functional ( <i>J. Chem. Phys.</i> 2023, 159, 214102) that is faithful to the parent functional. That is a major gain relative to our earlier deorbitalization which did poorly on molecular heats of formation ( <i>J. Chem. Phys.</i> 2023, 159, 214103). The improvement arises from augmentation of the Mejía-Rodríguez and Trickey deorbitalization strategy ( <i>Phys. Rev. A</i> 2017, 96, 052512) to use a smoothed replacement for the reduced density Laplacian (conventionally denoted <i>q</i>) obtained from that Laplacian itself. The augmentation also rationalizes the improvement obtained from the cutoff of <i>q</i> < 0 that was poorly understood at the time of the previous paper. The new scheme yields deorbitalized chemical region indicators that are much closer to those from the parent, orbital-dependent functional than were obtainable from the previous deorbitalization. It also replicates the good 3d elemental magnetization of the parent functional reasonably well.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141589026","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
Observation of the Infrared-Induced Structural Change in the Microscopic Hydrogen Bond Network of Phenol-Methanol Cluster Cations in a Cold-Ion Trap. 在冷离子捕集器中观察红外线诱导的苯酚-甲醇簇阳离子微观氢键网络结构变化
IF 2.7 2区 化学
The Journal of Physical Chemistry A Pub Date : 2024-07-12 DOI: 10.1021/acs.jpca.4c01998
Masayoshi Ozeki, Masataka Orito, Haruki Ishikawa
{"title":"Observation of the Infrared-Induced Structural Change in the Microscopic Hydrogen Bond Network of Phenol-Methanol Cluster Cations in a Cold-Ion Trap.","authors":"Masayoshi Ozeki, Masataka Orito, Haruki Ishikawa","doi":"10.1021/acs.jpca.4c01998","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c01998","url":null,"abstract":"<p><p>To gain insight into microscopic hydrogen bond networks, we measured ultraviolet photodissociation (UVPD) spectra of the phenol-methanol 1:3 cluster cation, [PhOH(MeOH)<sub>3</sub>]<sup>+</sup> trapped in a variable temperature ion trap. At low temperatures, an isomer with a ring-type hydrogen bond structure dominates, whereas at higher temperatures the chain-type isomers become dominant due to the flexibility of their hydrogen bond structures. We also found a clear temperature dependence of the spectral features, such as band position and width. In addition to the above measurement, we observed the infrared (IR) induced isomerization of [PhOH(MeOH)<sub>3</sub>]<sup>+</sup> to study the dynamical aspects of hydrogen bond networks. We succeeded in observing IR-induced isomerization from the ring to chain forms of [PhOH(MeOH)<sub>3</sub>]<sup>+</sup> at low temperature. The isomerization was clearly identified as a change in the UVPD spectra. The time evolution of the UVPD spectra after IR excitation indicated that the IR-induced isomerization occurs within a nanosecond. The chain-type isomers produced by the IR-induced isomerization are then converted back to the ring-type form by collisions with cold He buffer gas in the trap. This backward isomerization proceeds with a time constant of 100 μs under our experimental conditions. In this study, we evaluated the temperatures of the chain isomers during the backward isomerization on the basis of the spectral features.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141597952","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
Implementation of Nonadiabatic Molecular Dynamics for Intersystem Crossing Based on a Time-Dependent Density-Functional Tight-Binding Method. 基于依赖时间的密度函数紧密结合方法的系统间交叉非绝热分子动力学的实现。
IF 2.7 2区 化学
The Journal of Physical Chemistry A Pub Date : 2024-07-11 DOI: 10.1021/acs.jpca.4c02422
Shota Ohno, Hiroki Uratani, Hiromi Nakai
{"title":"Implementation of Nonadiabatic Molecular Dynamics for Intersystem Crossing Based on a Time-Dependent Density-Functional Tight-Binding Method.","authors":"Shota Ohno, Hiroki Uratani, Hiromi Nakai","doi":"10.1021/acs.jpca.4c02422","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c02422","url":null,"abstract":"<p><p>Intersystem crossing (ISC) and internal conversion (IC) are types of nonadiabatic transitions that play important roles in a wide range of fields, including photochemistry, photophysics, and photobiology. The nonadiabatic molecular dynamics (NA-MD) method is a powerful tool for computational simulations of dynamic phenomena involving nonadiabatic transitions. In this study, we implemented the NA-MD method, which treats ISC and IC on an equal footing, where the electronic structure is treated at the level of the time-dependent (TD) density-functional tight-binding (DFTB) method, a low-cost semiempirical analog of TD density functional theory (DFT). In particular, the spin-orbit coupling calculation algorithm was implemented in the TD-DFTB framework, and the results showed trends similar to those obtained using TD-DFT. In addition, the NA-MD method successfully reproduced ultrafast ISC of 2-nitronaphthalene.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141589024","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
Virtual Special Issue on Machine Learning in Physical Chemistry Volume 2 物理化学中的机器学习》虚拟特刊第 2 卷。
IF 2.7 2区 化学
The Journal of Physical Chemistry A Pub Date : 2024-07-11 DOI: 10.1021/acs.jpca.4c03822
Andrew L. Ferguson*,  and , Jim Pfaendtner*, 
{"title":"Virtual Special Issue on Machine Learning in Physical Chemistry Volume 2","authors":"Andrew L. Ferguson*,&nbsp; and ,&nbsp;Jim Pfaendtner*,&nbsp;","doi":"10.1021/acs.jpca.4c03822","DOIUrl":"10.1021/acs.jpca.4c03822","url":null,"abstract":"","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141578296","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
The Semiexperimental Approach at Work: Equilibrium Structure of Radical Species. 工作中的半实验方法:自由基物种的平衡结构。
IF 2.7 2区 化学
The Journal of Physical Chemistry A Pub Date : 2024-07-11 DOI: 10.1021/acs.jpca.4c01758
Silvia Alessandrini, Mattia Melosso, Luca Bizzocchi, Vincenzo Barone, Cristina Puzzarini
{"title":"The Semiexperimental Approach at Work: Equilibrium Structure of Radical Species.","authors":"Silvia Alessandrini, Mattia Melosso, Luca Bizzocchi, Vincenzo Barone, Cristina Puzzarini","doi":"10.1021/acs.jpca.4c01758","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c01758","url":null,"abstract":"<p><p>The so-called semiexperimental (SE) approach is a powerful technique for obtaining highly accurate equilibrium structures for isolated systems. This Featured Article describes its extension to open-shell species, thus providing the first systematic investigation on radical equilibrium geometries to be used for benchmarking purposes. The small yet significant database obtained demonstrates that there is no reduction in accuracy when moving from closed-shell species to radicals. We also provide an extension of the applicability of the SE approach to medium-/large-sized radicals by exploiting the so-called \"Lego-brick\" approach, which is based on the assumption that a molecular system can be seen as formed by smaller fragments for which the SE equilibrium structure is available. In this Featured Article we show that this model can be successfully applied also to open-shell species.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141589027","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
Contrast and Complexity in the Low-Temperature Kinetics of CN(v = 1) with O2 and NO: Simultaneous Kinetics and Ringdown in a Uniform Supersonic Flow. CN(v = 1) 与 O2 和 NO 的低温动力学的对比性和复杂性:均匀超音速流中的同步动力学和环流。
IF 2.7 2区 化学
The Journal of Physical Chemistry A Pub Date : 2024-07-11 DOI: 10.1021/acs.jpca.4c02737
Shameemah Thawoos, Gregory E Hall, Nicolas Suas-David, Arthur G Suits
{"title":"Contrast and Complexity in the Low-Temperature Kinetics of CN(<i>v</i> = 1) with O<sub>2</sub> and NO: Simultaneous Kinetics and Ringdown in a Uniform Supersonic Flow.","authors":"Shameemah Thawoos, Gregory E Hall, Nicolas Suas-David, Arthur G Suits","doi":"10.1021/acs.jpca.4c02737","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c02737","url":null,"abstract":"<p><p>Bimolecular rate coefficients were determined for the reaction CN(<i>v</i> = 1) + NO and O<sub>2</sub> using continuous wave cavity ringdown spectroscopy in a uniform supersonic flow (UF-CRDS). The well-matched time scales for ringdown and reaction under pseudo-first-order conditions allow for the use of the SKaR method (simultaneous kinetics and ringdown) in which the full kinetic trace is obtained on each ringdown. The reactions offer an interesting contrast in that the CN(<i>v</i> = 1) + NO system is nonreactive and proceeds by complex-mediated vibrational relaxation, while the CN(<i>v</i> = 1) + O<sub>2</sub> reaction is primarily reactive. The measured rate coefficients at 70 K are (2.49 ± 0.08) × 10<sup>-11</sup> and (10.49 ± 0.22) × 10<sup>-11</sup> cm<sup>3</sup> molecule<sup>-1</sup> s<sup>-1</sup> for the reaction with O<sub>2</sub> and NO, respectively. The rate for reaction with O<sub>2</sub> is a factor 2 lower than previously reported for <i>v</i> = 0 in the same temperature range, a surprising result, while that for NO is consistent with extrapolation of previous high-temperature measurements to 70 K. The latter is also discussed in light of theoretical calculations and measurements of the rate constants for the association reaction in the high-pressure limit. The measurements are complicated by the presence of a metastable population of high-J CN formed by photolysis of the precursor BrCN, and a kinetic model is developed to treat the competing relaxation and reaction. It is particularly problematic for reactions at low temperatures where the rotational relaxation and reaction have similar rates, precluding a reliable determination of the rate coefficients at 30 K. Also presented are important modifications to the data acquisition and control for the instrument that have yielded considerably enhanced stability and throughput.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141578290","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
Reaction Pathway Analysis of PET Deconstruction via Methanolysis and Tertiary Amine Catalysts. 通过甲醇分解和叔胺催化剂进行 PET 分解的反应途径分析。
IF 2.7 2区 化学
The Journal of Physical Chemistry A Pub Date : 2024-07-11 DOI: 10.1021/acs.jpca.4c02276
Rishabh Sanghavi, Nadia N Intan, Shaoqu Xie, Hongfei Lin, Jim Pfaendtner
{"title":"Reaction Pathway Analysis of PET Deconstruction via Methanolysis and Tertiary Amine Catalysts.","authors":"Rishabh Sanghavi, Nadia N Intan, Shaoqu Xie, Hongfei Lin, Jim Pfaendtner","doi":"10.1021/acs.jpca.4c02276","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c02276","url":null,"abstract":"<p><p>Polyethylene terephthalate (PET) is a type of polymer frequently used in plastic packaging that significantly adds the amount of plastic waste found in landfills. One of the ways to recover valuable raw materials from postconsumer plastic is by depolymerizing PET into its monomeric constituents, which are dimethyl terephthalate (DMT) and ethylene glycol. PET depolymerization is often done in methanolysis with the help of acidic or base catalysts. Tertiary amine is one of the most attractive base catalysts for PET depolymerization in methanolysis since it does not lead to the generation of potentially environmentally harmful waste, unlike metal-based catalysts. However, the mechanism by which tertiary amines catalyze PET depolymerization in methanolysis remains unexplored. Developing a detailed mechanistic understanding of this process is important for improving plastic upcycling since it opens the possibility of employing various cheaper and more environmentally friendly reaction conditions. Using density functional theory and transition state analysis, we show that in the presence of tertiary amine catalysts, methanolysis of PET consists of multiple discrete-step reactions rather than a single concerted step. Furthermore, by comparing our calculations to recent experimental results, we were able to rationalize the DMT yield from the depolymerization process by relating it to charge polarization within tertiary amine catalysts, thus opening a pathway to identify atomic descriptors for future catalyst design.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141589025","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
Femtosecond to Microsecond Observation of Photochemical Pathways in Nitroaromatic Phototriggers Using Transient Absorption Spectroscopy. 利用瞬态吸收光谱对硝基芳香族光触发器中的光化学途径进行飞秒到微秒级的观测。
IF 2.7 2区 化学
The Journal of Physical Chemistry A Pub Date : 2024-07-11 DOI: 10.1021/acs.jpca.4c02482
William Whitaker, Deborin Ghosh, Partha Malakar, Gabriel Karras, Andrew J Orr-Ewing
{"title":"Femtosecond to Microsecond Observation of Photochemical Pathways in Nitroaromatic Phototriggers Using Transient Absorption Spectroscopy.","authors":"William Whitaker, Deborin Ghosh, Partha Malakar, Gabriel Karras, Andrew J Orr-Ewing","doi":"10.1021/acs.jpca.4c02482","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c02482","url":null,"abstract":"<p><p>The synthetic accessibility and tolerance to structural modification of phototriggered compounds (PTs) based on the <i>ortho</i>- nitrobenzene (ONB) protecting group have encouraged a myriad of applications including optimization of biological activity, and supramolecular polymerization. Here, a combination of ultrafast transient absorption spectroscopy techniques is used to study the multistep photochemistry of two nitroaromatic phototriggers based on the ONB chromophore, <i>O</i>-(4,5-dimethoxy-2-nitrobenzyl)-l-serine (DMNB-Ser) and <i>O-</i>[(2-nitrophenyl)methyl]-l-tyrosine hydrochloride (NB-Tyr), in DMSO solutions on femtosecond to microsecond time scales following the absorption of UV light. From a common <i>nitro</i>-S<sub>1</sub> excited state, the PTs can either undergo excited state intramolecular hydrogen transfer (ESIHT) to an <i>aci</i>-S<sub>1</sub> isomer within the singlet state manifold, leading to direct S<sub>1</sub> → S<sub>0</sub> internal conversion through a conical intersection, or competitive intersystem crossing (ISC) to access the triplet state manifold on time scales of (1.93 ± 0.03) ps and (13.9 ± 1.2) ps for DMNB-Ser and NB-Tyr, respectively. Deprotonation of <i>aci</i>-T<sub>1</sub> species to yield triplet anions is proposed to occur in both PTs, with an illustrative time constant of (9.4 ± 0.7) ns for DMNB-Ser. More than 75% of the photoexcited molecules return to their electronic ground states within 8 μs, either by direct S<sub>1</sub> → S<sub>0</sub> relaxation or anion reprotonation. Hence, upper limits to the quantum yields of photoproduct formation are estimated to be in the range of 13-25%. Mixed DMSO/H<sub>2</sub>O solvents show the influence of the environment on the observed photochemistry, for example, revealing two <i>nitro</i>-S<sub>1</sub> lifetimes for DMNB-Ser in a 10:1 DMSO/H<sub>2</sub>O mixture of 1.95 ps and (10.1 ± 1.2) ps, which are attributed to different microsolvation environments.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141578293","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
Ligand Characterization and DNA Intercalation of Ru(II) Polypyridyl Complexes: A Local Vibrational Mode Study. Ru(II) 多吡啶络合物的配体表征和 DNA 互嵌:局部振动模式研究。
IF 2.7 2区 化学
The Journal of Physical Chemistry A Pub Date : 2024-07-11 DOI: 10.1021/acs.jpca.4c02954
Hunter La Force, Marek Freindorf, Elfi Kraka
{"title":"Ligand Characterization and DNA Intercalation of Ru(II) Polypyridyl Complexes: A Local Vibrational Mode Study.","authors":"Hunter La Force, Marek Freindorf, Elfi Kraka","doi":"10.1021/acs.jpca.4c02954","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c02954","url":null,"abstract":"<p><p>We investigated in this work ruthenium-ligand bonding across the RuN framework in 12 Ru(II) polypyridyl complexes in the gas phase and solution for both singlet and triplet states, in addition to their affinity for DNA binding through π-π stacking interactions with DNA nucleobases. As a tool to assess the intrinsic strength of the ruthenium-ligand bonds, we determined local vibrational force constants via our local vibrational mode analysis software. We introduced a novel local force constant that directly accounts for the intrinsic strength of the π-π stacking interaction between DNA and the intercalated Ru(II) complex. According to our findings, [Ru(phen)<sub>2</sub>(dppz)]<sup>2+</sup> and [Ru(phen)<sub>2</sub>(11-CN-dppz)]<sup>2+</sup> provide an intriguing trade-off between photoinduced complex excitation and the strength of the subsequent π-π stacking interaction with DNA. [Ru(phen)<sub>2</sub>(dppz)]<sup>2+</sup> displays a small singlet-triplet splitting and a strong π-π stacking interaction in its singlet state, suggesting a favorable photoexcitation but potentially weaker interaction with DNA in the excited state. Conversely, [Ru(phen)<sub>2</sub>(11-CN-dppz)]<sup>2+</sup> exhibits a larger singlet-triplet splitting and a stronger π-π stacking interaction with DNA in its triplet state, indicating a less favorable photoinduced transition but a stronger interaction with DNA postexcitation. We hope our study will inspire future experimental and computational work aimed at the design of novel Ru-polypyridyl drug candidates and that our new quantitative measure of π-π stacking interactions in DNA will find a general application in the field.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141578294","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
DOCSIC: A Mean-Field Method for Orbital-by-Orbital Self-Interaction Correction. DOCSIC:逐轨道自相互作用校正的平均场方法。
IF 2.7 2区 化学
The Journal of Physical Chemistry A Pub Date : 2024-07-10 DOI: 10.1021/acs.jpca.4c02801
Juan E Peralta, Veronica Barone, Juan I Melo, Diego R Alcoba, Gustavo E Massaccesi, Luis Lain, Alicia Torre, Ofelia B Oña
{"title":"DOCSIC: A Mean-Field Method for Orbital-by-Orbital Self-Interaction Correction.","authors":"Juan E Peralta, Veronica Barone, Juan I Melo, Diego R Alcoba, Gustavo E Massaccesi, Luis Lain, Alicia Torre, Ofelia B Oña","doi":"10.1021/acs.jpca.4c02801","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c02801","url":null,"abstract":"<p><p>We introduce a new method to remove the one-electron self-interaction error in approximate density functional calculations on an orbital-by-orbital basis, as originally proposed by Perdew and Zunger [<i>Phys. Rev. B</i> <b>1981</b>, <i>23</i>, 5048]. This method is motivated by a recent proposal by Pederson et al. [<i>J. Chem. Phys.</i> <b>2014</b>, <i>140</i>, 121103] to remove self-interaction that employs orbitals derived from the real-space density matrix, known as FLOSIC (Fermi Löwdin orbitals self-interaction correction). However, instead of Fermi Löwdin orbitals, our scheme utilizes columns of the density matrix to determine localized orbitals, like the localization procedure proposed by Fuemmeler et al. [<i>J. Chem. Theory Comput.</i> <b>2023</b>, <i>19</i>, 8572]. The new method, dubbed DOCSIC for density matrix as orbital coefficients self-interaction correction, contrasts with traditional Perdew-Zunger or FLOSIC in that it does not incorporate additional optimization parameters, and, unlike the average density self-interaction correction of Ciofini et al. [<i>Chem. Phys. Lett.</i> <b>2003</b>, <i>380</i>, 12], it makes use of localized orbitals. Another advantage of DOCSIC is that it can be implemented as a mean-field formalism. We show details of the self-consistent generalized Kohn-Sham implementation, some illustrative results, and we finally highlight its advantages and limitations.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141578292","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
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