The Journal of Physical Chemistry A最新文献

{"title":"Computational Study on the Dynamics of a Bis(benzoxazole)-Based Overcrowded Alkene.","authors":"Charlotte N Stindt, Taegeun Jo, Jorn D Steen, Ben L Feringa, Stefano Crespi","doi":"10.1021/acs.jpca.4c06773","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c06773","url":null,"abstract":"<p><p>Understanding and controlling molecular motions is of pivotal importance for designing molecular machinery and functional molecular systems, capable of performing complex tasks. Herein, we report a comprehensive theoretical study to elucidate the dynamic behavior of a bis(benzoxazole)-based overcrowded alkene displaying several coupled and uncoupled molecular motions. The benzoxazole moieties give rise to 4 different stable conformers that interconvert through single-bond rotations. By performing excited- and ground-state molecular dynamics simulations, DFT calculations, and NMR studies, we found that the photochemical <i>E-Z</i> isomerization of the central double bond of each stable conformer is directional and leads to a mixture of metastable isomers. This transformation is analogous to the classical Feringa-type molecular motors, with the notable difference that, during the photochemical isomerization and the subsequent thermal helix inversion (THI) steps, multiple possible pathways take place that involve single-bond rotations that can be both coupled and uncoupled to the rotation of the naphthyl half of the molecule.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143027473","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}

{"title":"A Tribute to Richard J. Saykally.","authors":"Ronald C Cohen, Kevin R Wilson, Martina Havenith, Lucy M Ziurys","doi":"10.1021/acs.jpca.4c08425","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c08425","url":null,"abstract":"","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 3","pages":"643-644"},"PeriodicalIF":2.7,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143021255","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}

{"title":"Determining the Recruiting Rate of Spontaneously Blinking Rhodamines by Density Functional Calculations.","authors":"Qinlin Yuan, Mingyue Ma, Mingyu Wang, Pingping Sun, Xingqing Xiao, Weijie Chi","doi":"10.1021/acs.jpca.4c06408","DOIUrl":"10.1021/acs.jpca.4c06408","url":null,"abstract":"<p><p>A recruiting rate (<i>k</i>_rc) of 0.1-5 s^-1 has been proposed as the criterion for super-resolution spontaneously blinking rhodamines. Accurate prediction of the recruiting rate (<i>k</i>_rc) of rhodamines is very important for developing spontaneously blinking rhodamines. However, as far as we know, there is no reliable theoretical method to predict the <i>k</i>_rc. Herein, we meticulously investigated the effect of intermolecular hydrogen bonds on the spirocyclization reactions of rhodamines. Moreover, a theoretical descriptor (Δ<i>E</i>_C-T) was proposed to reliably assess the <i>k</i>_rc. Δ<i>E</i>_C-T quantified the ring-opening energy barrier of spirocyclization reactions. A robust linear correlation was established between theoretical Δ<i>E</i>_C-T values and experimentally <i>k</i>_rc values. Based on this correlation, we designed and screened five spontaneously blinking sulfonamide rhodamine dyes with optimized <i>k</i>_rc values. We expected that these findings could enable the targeted design of spontaneously blinking rhodamines.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"667-676"},"PeriodicalIF":2.7,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142961988","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}

{"title":"Simulations of Attosecond Metallization in Quartz and Diamond Probed with Inner-Shell Transient Absorption Spectroscopy.","authors":"Lucas Kurkowski, Adonay Sissay, Mengqi Yang, Alexander Meyer, Kenneth Lopata","doi":"10.1021/acs.jpca.4c05137","DOIUrl":"10.1021/acs.jpca.4c05137","url":null,"abstract":"<p><p>When dielectrics are hit with intense infrared (IR) laser pulses, transient metalization can occur. The initial attosecond dynamics behind this metallization are not entirely understood. Therefore, simulations are needed to understand this process and to help interpret experimental observations of it, such as with attosecond transient absorption (ATA). In this paper, we present first-principles simulations of ATA based on bulk-mimicking clusters and real-time time-dependent density functional theory (RT-TDDFT), with Koopmans-tuned range-separated hybrid functionals and Gaussian basis sets. Our method gives good agreement with the experiment for the breakdown threshold in silica and diamond. This breakdown voltage corresponds to a Keldysh parameter of approximately one and thus involves a transition to a regime where the dynamics are driven by tunneling. Pumping at an amplitude just below this value causes a mixture of multiphoton and tunneling excitations across the band gap to occur. The computed extreme ultraviolet and X-ray attosecond transient spectra also agree well with the experiment and show a decrease in optical density due to the transient population of the conduction band from the IR field. First-principles approaches such as this are valuable for interpreting the complicated modulations in a spectrum and for guiding future attosecond experiments on solids.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"650-660"},"PeriodicalIF":2.7,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968743","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}

{"title":"Resonant Auger Decay in Benzene.","authors":"Nayanthara K Jayadev, Thomas-C Jagau, Anna I Krylov","doi":"10.1021/acs.jpca.4c07304","DOIUrl":"10.1021/acs.jpca.4c07304","url":null,"abstract":"<p><p>We present ab initio calculations of the resonant Auger spectrum of benzene. In the resonant process, Auger decay ensues following the excitation of a core-level electron to a virtual orbital. Hence, resonant Auger decay gives rise to higher-energy Auger electrons compared to nonresonant decay. We apply equation-of-motion coupled-cluster (EOM-CC) methods to compute the spectrum in order to explain the main features in the experimental spectrum and to assess the capability and limitations of the available theoretical approaches. The results indicate that participator decay can be well described with the Feshbach-Fano approach based on EOM-CC wave functions in the singles and doubles (SD) approximation, but spectator decay is more difficult to describe. This is because the target states of spectator decay are doubly excited, resulting in the need to include triple excitations in the EOM-CC wave function. Resonant Auger decay in benzene is thus a challenging test case for EOM-CC theory. We examine the performance of different noniterative triple corrections to EOM-IP-CCSD and our numerical results highlight the need to include triple excitations iteratively.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"733-743"},"PeriodicalIF":2.7,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142976752","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}

{"title":"Analysis of the NMR Parameters Shielding and Spin-Spin Coupling Constants of Glycine Conformers.","authors":"Danillo Valverde, Herbert C Georg, Gabriel I Pagola, Patricio F Provasi","doi":"10.1021/acs.jpca.4c06527","DOIUrl":"10.1021/acs.jpca.4c06527","url":null,"abstract":"<p><p>In this study, we worked at the CCSD/aug-cc-pVTZ level to obtain the conformers of glycine in its neutral and zwitterionic forms in the gas and water phases. We then computed the NMR properties (spin-spin coupling constants and nuclear magnetic shieldings) at the SOPPA/aug-cc-pVTZ-J level. We attempt to elucidate the apparent discrepancy arising from two previous works by Valverde et al. [<i>J. Chem. Phys.</i>, <b>2018</b>, <i>148</i>, 024305] and Caputo and Provasi [<i>Sci</i>, <b>2021</b>, <i>3</i>, 41]. Our optimized structures align with previous theoretical predictions, although some geometries were not found. Additionally, our results suggest that in the gas phase the Δ ¹<i>J</i>(O,C) = ¹<i>J</i>(O_cis,C_O) - ¹<i>J</i>(O_trans,C_O) is positive when the acid group is in the <i>trans</i> conformation and negative in the <i>cis</i> conformation; however, this trend is not well reproduced in water. From magnetic shielding calculations, we cannot distinguish between an O-H in the <i>cis</i> or <i>trans</i> conformation.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"686-694"},"PeriodicalIF":2.7,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142941467","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}

{"title":"Anisotropic Shock Response of 3,4-Dinitropyrazole Revealed by First-Principles Calculations.","authors":"Chaowen Yang, Yi Yang, Shuangfei Zhu, Shuhai Zhang, Yang Liu, Yahong Chen","doi":"10.1021/acs.jpca.4c06583","DOIUrl":"10.1021/acs.jpca.4c06583","url":null,"abstract":"<p><p>DNP (3,4-dinitropyrazole) has attracted much interest due to its promising melting characteristics and high detonation performances, such as low melting point, high density, high detonation velocity, and low sensitivity. In this work, first-principles molecular dynamics (MD) simulations were performed to investigate the anisotropic shock response of DNP in conjunction with the multiscale shock technique (MSST). The initial decomposition mechanism was revealed through the evolution of the chemical reaction and product analysis. Independent gradients based on the Hirshfeld partition (IGMH) method showed that van der Waals forces mainly exist between the layered structures. Chemical reaction analyses revealed four major initial decomposition reactions for the DNP molecule. At different shock velocities, the molecules in <math><mo>(</mo><mover><mn>1</mn><mo>¯</mo></mover><mn>01</mn><mo>)</mo></math> were more inclined to undergo H dissociation reactions, whereas the molecules in <math><mo>(</mo><mover><mn>1</mn><mo>¯</mo></mover><mn>0</mn><mover><mn>1</mn><mo>¯</mo></mover><mo>)</mo></math> were more inclined to undergo nitro-dissociation reactions. Product analysis showed that the faster the shock velocities, the earlier the DNP molecules completely disappeared. Furthermore, N₂ and CO₂ were mainly produced by the ring-opening reaction, and their numbers in <math><mo>(</mo><mover><mn>1</mn><mo>¯</mo></mover><mn>01</mn><mo>)</mo></math> were higher than in <math><mo>(</mo><mover><mn>1</mn><mo>¯</mo></mover><mn>0</mn><mover><mn>1</mn><mo>¯</mo></mover><mo>)</mo></math>, indicating that the ring-opening reaction was more easy to occur in <math><mo>(</mo><mover><mn>1</mn><mo>¯</mo></mover><mn>01</mn><mo>)</mo></math>. The ring-opening reaction mainly occurred in <math><mo>(</mo><mover><mn>1</mn><mo>¯</mo></mover><mn>01</mn><mo>)</mo></math>, suggesting that <math><mo>(</mo><mover><mn>1</mn><mo>¯</mo></mover><mn>01</mn><mo>)</mo></math> was more decomposable than <math><mo>(</mo><mover><mn>1</mn><mo>¯</mo></mover><mn>0</mn><mover><mn>1</mn><mo>¯</mo></mover><mo>)</mo></math>. The fitting results of the state equation showed that the theoretical detonation pressures for <math><mo>(</mo><mover><mn>1</mn><mo>¯</mo></mover><mn>01</mn><mo>)</mo></math> and <math><mo>(</mo><mover><mn>1</mn><mo>¯</mo></mover><mn>0</mn><mover><mn>1</mn><mo>¯</mo></mover><mo>)</mo></math> are close to the experimental value. These results could help to increase the understanding of shock-induced anisotropy in energetic materials.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"695-704"},"PeriodicalIF":2.7,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142976749","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}

{"title":"Accelerating Fock Build via Hybrid Analytical-Numerical Integration.","authors":"Yong Zhang, Rongding Lei, Bingbing Suo, Wenjian Liu","doi":"10.1021/acs.jpca.4c07454","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07454","url":null,"abstract":"&lt;p&gt;&lt;p&gt;A hybrid analytical-numerical integration scheme is introduced to accelerate the Fock build in self-consistent field (SCF) and time-dependent density functional theory (TDDFT) calculations. To evaluate the Coulomb matrix &lt;b&gt;J&lt;/b&gt;[&lt;b&gt;D&lt;/b&gt;], the density matrix &lt;b&gt;D&lt;/b&gt; is first decomposed into two parts, the superposition of atomic density matrices &lt;b&gt;D&lt;/b&gt;&lt;sub&gt;⊕&lt;/sub&gt;&lt;sup&gt;&lt;i&gt;A&lt;/i&gt;&lt;/sup&gt; and the rest &lt;b&gt;D&lt;/b&gt;&lt;sup&gt;&lt;i&gt;R&lt;/i&gt;&lt;/sup&gt; = &lt;b&gt;D&lt;/b&gt;-&lt;b&gt;D&lt;/b&gt;&lt;sub&gt;⊕&lt;/sub&gt;&lt;sup&gt;&lt;i&gt;A&lt;/i&gt;&lt;/sup&gt;. While &lt;b&gt;J&lt;/b&gt;[&lt;b&gt;D&lt;/b&gt;&lt;sub&gt;⊕&lt;/sub&gt;&lt;sup&gt;&lt;i&gt;A&lt;/i&gt;&lt;/sup&gt;] is evaluated analytically, &lt;b&gt;J&lt;/b&gt;[&lt;b&gt;D&lt;/b&gt;&lt;sup&gt;&lt;i&gt;R&lt;/i&gt;&lt;/sup&gt;] is evaluated fully numerically [with the multipole expansion of the Coulomb potential (MECP)] during the SCF iterations. Upon convergence, &lt;b&gt;D&lt;/b&gt;&lt;sup&gt;&lt;i&gt;R&lt;/i&gt;&lt;/sup&gt; is further split into those of near (&lt;b&gt;D&lt;/b&gt;&lt;sup&gt;&lt;i&gt;RC&lt;/i&gt;&lt;/sup&gt;) and distant (&lt;b&gt;D&lt;/b&gt;&lt;sup&gt;&lt;i&gt;RL&lt;/i&gt;&lt;/sup&gt;) atomic orbital (AO) pairs, such that &lt;b&gt;J&lt;/b&gt;[&lt;b&gt;D&lt;/b&gt;&lt;sup&gt;&lt;i&gt;RC&lt;/i&gt;&lt;/sup&gt;] and &lt;b&gt;J&lt;/b&gt;[&lt;b&gt;D&lt;/b&gt;&lt;sup&gt;&lt;i&gt;RL&lt;/i&gt;&lt;/sup&gt;] are evaluated seminumerically and fully numerically (with MECP). Such a hybrid &lt;b&gt;J&lt;/b&gt;-build is dubbed \"analytic-MECP\" (aMECP). Likewise, the analytic evaluation of &lt;b&gt;K&lt;/b&gt;[&lt;b&gt;D&lt;/b&gt;&lt;sub&gt;⊕&lt;/sub&gt;&lt;sup&gt;&lt;i&gt;A&lt;/i&gt;&lt;/sup&gt;] and seminumerical evaluation of &lt;b&gt;K&lt;/b&gt;[&lt;b&gt;D&lt;/b&gt;&lt;sup&gt;&lt;i&gt;R&lt;/i&gt;&lt;/sup&gt;] are also invoked for the construction of the exchange matrix &lt;b&gt;K&lt;/b&gt;[&lt;b&gt;D&lt;/b&gt;] during the SCF iterations. The chain-of-spheres (COSX) algorithm [Chem. Phys. 356, 98 (2009]) is employed for &lt;b&gt;K&lt;/b&gt;[&lt;b&gt;D&lt;/b&gt;&lt;sup&gt;&lt;i&gt;R&lt;/i&gt;&lt;/sup&gt;] but with a revised construction of the S-junctions for overlap AO pairs. To distinguish from the original COSX algorithm (which does not involve the partition of the density matrix &lt;b&gt;D&lt;/b&gt;), we denote the presently revised variant as COSx. Upon convergence, &lt;b&gt;D&lt;/b&gt;&lt;sup&gt;&lt;i&gt;R&lt;/i&gt;&lt;/sup&gt; is further split into those of near (&lt;b&gt;D&lt;/b&gt;&lt;sup&gt;&lt;i&gt;RC&lt;/i&gt;&lt;/sup&gt;) and distant (&lt;b&gt;D&lt;/b&gt;&lt;sup&gt;&lt;i&gt;RL&lt;/i&gt;&lt;/sup&gt;) AO pairs followed by a rescaling, leading to &lt;math&gt;&lt;msup&gt;&lt;mover&gt;&lt;mi&gt;D&lt;/mi&gt;&lt;mo&gt;~&lt;/mo&gt;&lt;/mover&gt;&lt;mrow&gt;&lt;mi&gt;R&lt;/mi&gt;&lt;mi&gt;C&lt;/mi&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;/math&gt; and &lt;math&gt;&lt;msup&gt;&lt;mover&gt;&lt;mi&gt;D&lt;/mi&gt;&lt;mo&gt;~&lt;/mo&gt;&lt;/mover&gt;&lt;mrow&gt;&lt;mi&gt;R&lt;/mi&gt;&lt;mi&gt;L&lt;/mi&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;/math&gt;, respectively. &lt;math&gt;&lt;mi&gt;K&lt;/mi&gt;&lt;mrow&gt;&lt;mo&gt;[&lt;/mo&gt;&lt;msup&gt;&lt;mover&gt;&lt;mi&gt;D&lt;/mi&gt;&lt;mo&gt;~&lt;/mo&gt;&lt;/mover&gt;&lt;mrow&gt;&lt;mi&gt;R&lt;/mi&gt;&lt;mi&gt;C&lt;/mi&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;mo&gt;]&lt;/mo&gt;&lt;/mrow&gt;&lt;/math&gt; and &lt;math&gt;&lt;mi&gt;K&lt;/mi&gt;&lt;mrow&gt;&lt;mo&gt;[&lt;/mo&gt;&lt;msup&gt;&lt;mover&gt;&lt;mi&gt;D&lt;/mi&gt;&lt;mo&gt;~&lt;/mo&gt;&lt;/mover&gt;&lt;mrow&gt;&lt;mi&gt;R&lt;/mi&gt;&lt;mi&gt;L&lt;/mi&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;mo&gt;]&lt;/mo&gt;&lt;/mrow&gt;&lt;/math&gt; are then evaluated analytically and seminumerically (with COSx), respectively. Such a hybrid &lt;b&gt;K&lt;/b&gt;-build is dubbed \"analytic-COSx\" (aCOSx). Extensive numerical experimentations reveal that the combination of aMECP and aCOSx is highly accurate for ground state SCF calculations (&lt;math&gt;&lt;mo&gt;&lt;&lt;/mo&gt;&lt;mi&gt;μ&lt;/mi&gt;&lt;msub&gt;&lt;mi&gt;E&lt;/mi&gt;&lt;mi&gt;h&lt;/mi&gt;&lt;/msub&gt;&lt;mo&gt;/&lt;/mo&gt;&lt;mtext&gt;atom&lt;/mtext&gt;&lt;/math&gt; error in energy) and is particularly efficient for calculations of large molecules with extended basis sets. As for TDDFT excitation energies, a medium grid for MECP and a ","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143021334","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}

{"title":"Enhanced Near-Infrared Fluorescence Emission near a Graphene-Metal Hybrid Structure.","authors":"Xiaowei Wang, Zhihui Chen, Guang Feng, Qiang Wang, Qinsong Yao, Yang Wang, Zhiyuan Wang, Yibiao Yang","doi":"10.1021/acs.jpca.4c06433","DOIUrl":"10.1021/acs.jpca.4c06433","url":null,"abstract":"<p><p>Plasmon resonance plays an important role in improving the detection of biomolecules, and it is one of the focuses of research to use metal plasmon resonance to achieve fluorescence enhancement and to improve detection sensitivity. However, the problems of nondynamic tuning and fluorescence quenching of metal plasmon resonance need to be solved. Graphene surface plasmon resonance can be dynamically controlled, and the graphene adsorption of fluorescent molecules can avoid fluorescence quenching and greatly improve the fluorescence emission intensity. The graphene-metal hybrid structure designed in this work can solve the above two problems well, and the plasmon resonance can improve the fluorescence emission efficiency of molecules on the surface of graphene and improve the sensitivity of biological detection. At the same time, graphene nanoribbons in our hybrid structure do not require patterning, which greatly lowers the threshold for graphene application in biosensing.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"677-685"},"PeriodicalIF":2.7,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142941471","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}

{"title":"Top-Down versus Bottom-Up Approaches for σ-Functionals Based on the Approximate Exchange Kernel.","authors":"Yannick Lemke, Christian Ochsenfeld","doi":"10.1021/acs.jpca.4c05289","DOIUrl":"10.1021/acs.jpca.4c05289","url":null,"abstract":"<p><p>Recently, we investigated a number of so-called σ- and τ-functionals based on the adiabatic-connection fluctuation-dissipation theorem (ACFDT); particularly, extensions of the random phase approximation (RPA) with inclusion of an exchange kernel in the form of an antisymmetrized Hartree kernel. One of these functionals, based upon the approximate exchange kernel (AXK) of Bates and Furche, leads to a nonlinear contribution of the spline function used within σ-functionals, which we previously avoided through the introduction of a simplified \"top-down\" approach in which the σ-functional modification is inserted a posteriori following the analytic coupling strength integration within the framework of the ACFDT and which was shown to provide excellent performance for the GMTKN55 database when using hybrid PBE0 reference orbitals. In this work, we examine the analytic \"bottom-up\" approach in which the spline function is inserted a priori, i.e., before evaluation of the analytic coupling strength integral. The new bottom-up functionals, denoted σ↑AXK, considerably improve upon their top-down counterparts for problems dominated by self-interaction and delocalization errors. Despite a small loss of accuracy for noncovalent interactions, the σ↑AXK@PBE0 functionals comprehensively outperform regular σ-functionals, scaled σ-functionals, and the previously derived σ+SOSEX- and τ-functionals in the WTMAD-1 and WTMAD-2 metrics of the GMTKN55 database.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"774-787"},"PeriodicalIF":2.7,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142941522","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}