Electronic Structure最新文献_第9页

Theoretical and experimental insight into nano-optoelectronics 纳米光电子学的理论和实验见解

IF 2.6

Electronic Structure Pub Date : 2022-12-01 DOI: 10.1088/2516-1075/aca944

DattatrayJ. Late, S. Duhm

引用次数: 0

Computational investigations of the excited state dynamics and quenching mechanisms of polycyclic aromatic hydrocarbon DNA adducts in solution 溶液中多环芳烃DNA加合物激发态动力学和猝灭机制的计算研究

IF 2.6

Electronic Structure Pub Date : 2022-11-22 DOI: 10.1088/2516-1075/aca4ff

Solomon Yamoah Effah, W. Kaushalya, M. Hix, Alice R. Walker

{"title":"Computational investigations of the excited state dynamics and quenching mechanisms of polycyclic aromatic hydrocarbon DNA adducts in solution","authors":"Solomon Yamoah Effah, W. Kaushalya, M. Hix, Alice R. Walker","doi":"10.1088/2516-1075/aca4ff","DOIUrl":"https://doi.org/10.1088/2516-1075/aca4ff","url":null,"abstract":"Synthetically modified fluorescent nucleotides (SFNs) are highly popular in a variety of experiments to explore biochemistry in molecular imaging, but the connection between their photodynamics and quenching mechanisms to their molecular structure remain relatively unstudied computationally. We combine various levels of theory, including classical force field dynamics and excited state quantum mechanic/molecular mechanic Born–Oppenheimer dynamics to characterize a set of polycyclic aromatic hydrocarbon based substituents bound to cytidine (dC) and guanine (dG) nucleobases. We specifically focus on perylene (P) bound to C5 and C6 of dC, and the naturally occurring benzo[a]pyrene diol epoxide (B[a]PDE) on dG. We find that specific angles of the connection points between them modulate mechanisms of intramolecular charge transfer, where an electron moves from P to dC and dG to B[a]PDE once an optimal angle is reached. Functionalization location and flexibility of the substituent affect access to these angles and, therefore, the amount of rapid charge transfer quenching of the fluorescence that we observe. This work demonstrates that the choice of functionalization location for SFNs changes the accessibility of charge transfer mechanisms via steric hindrance, and suggest that this feature can be applied for future tuning of fluorescence properties.","PeriodicalId":42419,"journal":{"name":"Electronic Structure","volume":" ","pages":""},"PeriodicalIF":2.6,"publicationDate":"2022-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49285513","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 1

Reparameterized semi-empirical methods for computing anharmonic vibrational frequencies of multiply-bonded hydrocarbons 计算多键碳氢化合物非谐波振动频率的重参数化半经验方法

IF 2.6

Electronic Structure Pub Date : 2022-11-18 DOI: 10.1088/2516-1075/aca458

B. R. Westbrook, Joshua P Layfield, Timothy J. Lee, R. Fortenberry

{"title":"Reparameterized semi-empirical methods for computing anharmonic vibrational frequencies of multiply-bonded hydrocarbons","authors":"B. R. Westbrook, Joshua P Layfield, Timothy J. Lee, R. Fortenberry","doi":"10.1088/2516-1075/aca458","DOIUrl":"https://doi.org/10.1088/2516-1075/aca458","url":null,"abstract":"Reparameterized semi-empirical methods can reproduce gas-phase experimental vibrational frequencies to within 24 cm−1 or better for a 100-fold decrease in computational cost in the anharmonic fundamental vibrational frequencies. To achieve such accuracy and efficiency, the default parameters in the PM6 semi-empirical model are herein optimized to reproduce the experimental and high-level theoretical vibrational spectra of three small hydrocarbon molecules, C2H2, c-C3H2, and C2H4, with the hope that these same parameters will be applicable to large polycyclic aromatic hydrocarbons (PAHs). This massive cost reduction allows for the computation of explicit anharmonic frequencies and the inclusion of resonance corrections that have been shown to be essential for accurate predictions of anharmonic frequencies. Such accurate predictions are necessary to help to disentangle the heretofore unidentified infrared spectral features observed around diverse astronomical bodies and hypothesized to be caused by PAHs, especially with the upcoming influx of observational data from the James Webb Space Telescope. The optimized PM6 parameters presented herein represent a substantial step in this direction with those obtained for ethylene (C2H4) yielding a 37% reduction in the mean absolute error of the fundamental frequencies compared to the default PM6 parameters.","PeriodicalId":42419,"journal":{"name":"Electronic Structure","volume":" ","pages":""},"PeriodicalIF":2.6,"publicationDate":"2022-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46802091","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 3

High-level quantum chemistry exploration of reduction by group-13 hydrides: insights into the rational design of bio-mimic CO2 reduction 13族氢化物还原的高级量子化学探索:对生物模拟CO2还原的合理设计的见解

IF 2.6

Electronic Structure Pub Date : 2022-11-07 DOI: 10.1088/2516-1075/ac9bb3

B. Chan, Masanari Kimura

{"title":"High-level quantum chemistry exploration of reduction by group-13 hydrides: insights into the rational design of bio-mimic CO2 reduction","authors":"B. Chan, Masanari Kimura","doi":"10.1088/2516-1075/ac9bb3","DOIUrl":"https://doi.org/10.1088/2516-1075/ac9bb3","url":null,"abstract":"In the present study, we have used computational quantum chemistry to explore the reduction of various types of substrates by group-13 hydrides. We use the high-level L-W1X method to obtain the energies for the constituent association and hydride transfer reactions. We find that the hydride transfer reactions are highly exothermic, while the preceding association reactions are less so. Thus, improving the thermodynamics of substrate association may improve the overall process. Among the various substrates, amine and imine show the strongest binding, while CO2 shows the weakest. Between the group-13 hydrides, alanes bind most strongly with the substrates, and they also have the most exothermic hydride transfer reactions. To facilitate CO2 binding, we have examined alanes with electron-withdrawing groups, and we indeed find CF3 groups to be effective. Drawing inspiration from the RuBisCO enzyme for CO2 fixation, we have further examined the activation of CO2 with two independent AlH(CF3)2 molecules, with the results showing an even more exothermic association. This observation may form the basis for designing an effective dialane reagent for CO2 reduction. We have also assessed a range of lower-cost computational methods for the calculation of systems in the present study. We find the DSD-PBEP86 double-hybrid DFT method to be the most suitable for the study of related medium-sized systems.","PeriodicalId":42419,"journal":{"name":"Electronic Structure","volume":" ","pages":""},"PeriodicalIF":2.6,"publicationDate":"2022-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43944538","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A unified secondary electron cut-off presentation and common mistakes in photoelectron spectroscopy 统一的二次电子截止表示及光电子能谱中的常见错误

IF 2.6

Electronic Structure Pub Date : 2022-11-03 DOI: 10.1088/2516-1075/ac9ffb

T. Schultz

引用次数: 7

Non-empirical double-hybrid density functionals as reliable tools for electronic structure calculations 非经验双混合密度泛函作为电子结构计算的可靠工具

IF 2.6

Electronic Structure Pub Date : 2022-10-11 DOI: 10.1088/2516-1075/ac9942

J. Sancho‐García, É. Brémond, Á. Pérez‐Jiménez, Ilaria Cioﬁni, C. Adamo

{"title":"Non-empirical double-hybrid density functionals as reliable tools for electronic structure calculations","authors":"J. Sancho‐García, É. Brémond, Á. Pérez‐Jiménez, Ilaria Cioﬁni, C. Adamo","doi":"10.1088/2516-1075/ac9942","DOIUrl":"https://doi.org/10.1088/2516-1075/ac9942","url":null,"abstract":"The development of universal and accurate approximations for electronic structure calculations lies at the central core of (past and modern) research in theoretical and computational chemistry. For that purpose, any reliable method needs to treat in a balanced way exchange and correlation effects arising from the intricate structure of matter at the nanoscopic level. Following this principle, we have developed a set of non-empirical (double-hybrid) density functional expressions, minimizing the parameterization and also widely applicable even for systems of considerable size, while being accurate enough to compete with wavefunction methods or even matching experimental information. The underlying expressions are now implemented in many available codes worldwide, then allowing the access to the whole set of key properties needed for addressing chemical structure, reactivity, and bonding, at all nanostructured levels and/or states of matter. Additionally, the recent extension to excited states through a time-dependent (linear-response) formalism also allows one to deal with photochemistry, photophysical, and related properties. Therefore, this family of methods can now be successfully applied to organic, inorganic, or biomolecular compounds, or any other complex system, within an affordable computational effort.","PeriodicalId":42419,"journal":{"name":"Electronic Structure","volume":" ","pages":""},"PeriodicalIF":2.6,"publicationDate":"2022-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43617399","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 2

A divide-and-conquer method to improve performance in quantum transport calculations: conductance in rotated graphene nanoribbons side-contact junctions 一种提高量子输运计算性能的分而治之的方法：旋转石墨烯纳米带侧面接触结中的电导

IF 2.6

Electronic Structure Pub Date : 2022-09-30 DOI: 10.1088/2516-1075/ac96b8

M. J. Rodríguez, Carlos Ramírez

引用次数: 0

Diabatic potential energy surfaces and semiclassical multi-state dynamics for fourteen coupled 3 A′ states of O3 O3 14个3A′态耦合的非绝热势能面和半经典多态动力学

IF 2.6

Electronic Structure Pub Date : 2022-09-23 DOI: 10.1088/2516-1075/ac94ac

Z. Varga, Yinan Shu, Jiaxin Ning, D. Truhlar

{"title":"Diabatic potential energy surfaces and semiclassical multi-state dynamics for fourteen coupled 3 A′ states of O3","authors":"Z. Varga, Yinan Shu, Jiaxin Ning, D. Truhlar","doi":"10.1088/2516-1075/ac94ac","DOIUrl":"https://doi.org/10.1088/2516-1075/ac94ac","url":null,"abstract":"Dissociation and energy transfer in high-energy collisions of O2 play important roles in simulating thermal energy content and heat flux in flows around hypersonic vehicles. Furthermore, atomic oxygen reactions on the vehicle surface are an important contributor to heat shield erosion. Molecular dynamics modeling is needed to better understand the relevant rate processes. Because it is necessary to model the gas flows in high-temperature shock waves, electronically excited states of O2 and O can be populated, and molecular dynamics simulations should include collisions of electronically excited species and electronically nonadiabatic collisions. This requires potential energy surfaces and state couplings for many energetically accessible electronic states. Here we report a systematic strategy to calculate such surfaces and couplings. We have applied this method to the fourteen lowest-energy potential energy surfaces in the 3 A′ manifold of O3, and we report a neural-network fit to diabatic potential energy matrix (DPEM). We illustrate the use of the resulting DPEM by carrying out semiclassical dynamics calculations of cross sections for excitation of O2 in 3 A′ collisions with O at two collision energies; these dynamics calculations are carried out by the curvature-driven coherent switching with decay of mixing method.","PeriodicalId":42419,"journal":{"name":"Electronic Structure","volume":" ","pages":""},"PeriodicalIF":2.6,"publicationDate":"2022-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41999778","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 5

Modified HSE06 functional applied to anatase TiO2: influence of exchange fraction on the quasiparticle electronic structure and optical response 改性HSE06官能团在锐钛矿TiO2上的应用:交换分数对准粒子电子结构和光学响应的影响

IF 2.6

Electronic Structure Pub Date : 2022-09-02 DOI: 10.1088/2516-1075/ac8f03

Sruthil lal S B, Murali D, M. Posselt, A. A. Sasikala Devi, A. Sharan

{"title":"Modified HSE06 functional applied to anatase TiO2: influence of exchange fraction on the quasiparticle electronic structure and optical response","authors":"Sruthil lal S B, Murali D, M. Posselt, A. A. Sasikala Devi, A. Sharan","doi":"10.1088/2516-1075/ac8f03","DOIUrl":"https://doi.org/10.1088/2516-1075/ac8f03","url":null,"abstract":"The influence of non-interacting Kohn–Sham Hamiltonian on the non-self consistent GW(G 0 W 0) quasiparticle gap and Bethe–Salpeter-equation (BSE) optical spectra of anatase TiO2 is systematically evaluated. G 0 W 0 and BSE calculations are carried out starting with HSE06 (Heyd–Scuseria–Ernzerhof) type functionals containing 20%, 25% and 30% exact Hartree–Fock exchange. The results are also compared against G 0 W 0 + BSE calculations starting from semi-local (PBE) functionals. Our results indicate that the G 0 W 0 and BSE calculations of anatase TiO2 depend critically on the mean-field starting point, wherein its dependence is mainly introduced through the dielectric screening evaluated at the intermediate G 0 W 0. We find that the band dispersion, density of states, and consequently the oscillator strengths of optical excitation and spatial localization of excitons are insensitive to the starting points while the quasiparticle gap, optical gap and exciton binding energies are strongly affected. G 0 W 0 quasiparticle gap of anatase TiO2 computed over hybrid functional starting points is typically overestimated compared to measured values. However, by varying the amount of exact exchange, the dielectric screening can be tuned, and thus the quasiparticle gap. Exciton binding energy is shown to increase in proportion to the increase of the amount of exact exchange. A simple extrapolation of the calculated data leads to the exact match with the recently measured value with 13% of the exact exchange. Systematic analysis of G 0 W 0 + BSE calculation starting from screened hybrid functionals provided in this study forms a reference for all such future calculations of pristine anatase TiO2 and its derivatives.","PeriodicalId":42419,"journal":{"name":"Electronic Structure","volume":" ","pages":""},"PeriodicalIF":2.6,"publicationDate":"2022-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41920611","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 4

Insights into the stability of engineered mini-proteins from their dynamic electronic properties 从动态电子特性深入了解工程微型蛋白的稳定性

IF 2.6

Electronic Structure Pub Date : 2022-08-24 DOI: 10.1088/2516-1075/ac8c73

A. Steeves, H. Kulik

引用次数: 1