Journal of Chemical Physics最新文献_第6页

Electron-driven processes in enantiomeric forms of glutamic acid initiated by low-energy resonance electron attachment. 由低能共振电子附着引发的谷氨酸对映体中的电子驱动过程。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-09-21 DOI: 10.1063/5.0232036

Stanislav A Pshenichnyuk, Nail L Asfandiarov, Rustam G Rakhmeyev, Alexei S Komolov, Oleg E Tereshchenko

{"title":"Electron-driven processes in enantiomeric forms of glutamic acid initiated by low-energy resonance electron attachment.","authors":"Stanislav A Pshenichnyuk, Nail L Asfandiarov, Rustam G Rakhmeyev, Alexei S Komolov, Oleg E Tereshchenko","doi":"10.1063/5.0232036","DOIUrl":"https://doi.org/10.1063/5.0232036","url":null,"abstract":"Low-energy (0-14 eV) resonance electron interaction and fragment species produced by dissociative electron attachment (DEA) for enantiomeric forms of glutamic acid (Glu) are studied under gas-phase conditions by means of DEA spectroscopy and density functional theory calculations. Contrary to a series of amino acids studied earlier employing the DEA technique, the most abundant species are not associated with the elimination of a hydrogen atom from the parent molecular negative ion. Besides this less intense closed-shell [Glu - H]- fragment, only two mass-selected negative ions, [Glu - 19]- and [Glu - 76]-, are detected within the same electron energy region, with the yield maximum observed at around 0.9 eV. This value matches well the energy of vertical electron attachment into the lowest normally empty π* COOH molecular orbital of Glu located at 0.88 eV according to the present B3LYP/6-31G(d) calculations. Although the detection of asymmetric DEA properties a priori is not accessible under the present experimental conditions, \"chirality non-conservation\" can be associated with some decay channels. Evidently, the measured spectra for the L- and D-forms are found to be identical, the results, nevertheless, being of interest for the forthcoming experiments utilizing spin-polarized electron beam as a chiral factor in the framework of conventional DEA technique.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142288164","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

Equation-of-motion regularized orbital-optimized second-order perturbation theory with the density-fitting approximation. 运动方程正则化轨道优化二阶扰动理论与密度拟合近似。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-09-21 DOI: 10.1063/5.0223132

Aslı Ünal, Uğur Bozkaya

{"title":"Equation-of-motion regularized orbital-optimized second-order perturbation theory with the density-fitting approximation.","authors":"Aslı Ünal, Uğur Bozkaya","doi":"10.1063/5.0223132","DOIUrl":"https://doi.org/10.1063/5.0223132","url":null,"abstract":"The density-fitted equation-of-motion (EOM) orbital-optimized second-order perturbation theory (DF-EOM-OMP2) method is presented for the first time. In addition, κ-DF-EOM-MP2 and κ-DF-EOM-OMP2 methods are implemented with the addition of κ-regularization. The accuracy of the DF-EOM-OMP2, κ-DF-EOM-MP2, and κ-DF-EOM-OMP2 methods are compared to the density-fitted EOM-MP2 (DF-EOM-MP2), EOM coupled-cluster (CC) singles and doubles (DF-EOM-CCSD), and EOM-CCSD with the triples excitation correction model [EOM-CCSD(fT)] for excitation energies of many closed- and open-shell chemical systems. The excitation energies computed using different test cases and methods were compared to the EOM-CCSD(fT) method and mean absolute errors (MAEs) are presented. The MAE values of closed- and open-shell cases (closed-shell organic chromophores set, open-shell set, peptide radicals set, and radical set) according to the EOM-CCSD(fT) method show that the κ-regularization technique yields highly accurate results for the first excited states. Our results indicate that the κ-DF-EOM-MP2 and κ-DF-EOM-OMP2 methods perform noticeably better than the DF-EOM-MP2 and DF-EOM-OMP2 methods. They approach the EOM-CCSD quality, at a significantly reduced cost, for the computation of excitation energies. Especially, the κ-DF-EOM-MP2 method provides outstanding results for most test cases considered. Overall, we conclude that the κ-versions of DF-EOM-MP2 and DF-EOM-OMP2 emerge as a useful computational tool for the study of excited-state molecular properties.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142288165","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

Theory of high-temperature superfluorescence in hybrid perovskite thin films. 混合包晶体薄膜的高温超荧光理论。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-09-21 DOI: 10.1063/5.0226221

B D Fainberg, V Al Osipov

{"title":"Theory of high-temperature superfluorescence in hybrid perovskite thin films.","authors":"B D Fainberg, V Al Osipov","doi":"10.1063/5.0226221","DOIUrl":"https://doi.org/10.1063/5.0226221","url":null,"abstract":"The recent discovery of high-temperature superfluorescence in hybrid perovskite thin films has opened new possibilities for harnessing macroscopic quantum phenomena in nanotechnology. This study aimed to elucidate the mechanism that enables high-temperature superfluorescence in these systems. The proposed model describes a quasi-2D Wannier exciton in a thin film that interacts with phonons via the longitudinal optical phonon-exciton Fröhlich interaction. We show that the super-radiant properties of the coherent state in hybrid perovskites are stable against perturbations caused by the longitudinal optical phonon-exciton Fröhlich interaction. Using the multiconfiguration Hartree approach, we derive semiclassical equations of motion for a single-exciton wavefunction, where the vibrational degrees of freedom interact with the Wannier exciton through a mean-field Hartree term. Super-radiance is effectively described by a non-Hermitian term in the Hamiltonian. The analysis was then extended to multiple excited states using the semiclassical Hamiltonian as the basic model. We demonstrate that the ground state of the model exciton Hamiltonian with long-range interactions is a symmetric Dicke super-radiant state, where the Fröhlich interaction is nullified. The additional density matrix-based consideration draws an analogy between this system and stable systems, where the conservation laws determine the nullification of the constant (momentum-independent) decay rate part. In the exciton-phonon system, nullification is associated with the absence of a momentum-independent component in the Wannier exciton-phonon interaction coupling function.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142288181","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

A configuration sampling study of reaction intermediates constituting catalytic cycles for CO oxidation with Pt1/TiO2. 构成 Pt1/TiO2 氧化 CO 催化循环的反应中间产物的构型取样研究。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-09-21 DOI: 10.1063/5.0225962

Nicholas Humphrey, Selin Bac, Shaama Mallikarjun Sharada

{"title":"A configuration sampling study of reaction intermediates constituting catalytic cycles for CO oxidation with Pt1/TiO2.","authors":"Nicholas Humphrey, Selin Bac, Shaama Mallikarjun Sharada","doi":"10.1063/5.0225962","DOIUrl":"https://doi.org/10.1063/5.0225962","url":null,"abstract":"We combine ab initio molecular dynamics (AIMD) simulations with an unsupervised machine learning approach to automate the search for possible configurations of CO oxidation reaction intermediates catalyzed by the atomically dispersed Pt1/TiO2 catalyst. Following the example of Roncoroni and co-workers [Phys. Chem. Chem. Phys. 25, 13741 (2023)], we employ t-distributed stochastic neighbor embedding and hierarchical density-based spatial clustering of applications with noise to reduce the dimensionality and cluster AIMD snapshots based on the local coordination environment of Pt. We identify new local minima, particularly in cases where CO2 is bound to the active site, because it can coordinate in various ways with both the metal and support. The new minima constitute additional elementary steps in some proposed pathways for CO oxidation, resulting in turnover frequencies that differ from prior estimates by several orders of magnitude. This work, therefore, demonstrates that configuration sampling is a necessary component of computational studies of catalytic cycles for atomically dispersed catalysts.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142288145","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

Single vibronic level fluorescence spectra from Hagedorn wavepacket dynamics. 来自哈格多恩波包动力学的单振子级荧光光谱。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-09-21 DOI: 10.1063/5.0219005

Zhan Tong Zhang, Jiří J L Vaníček

{"title":"Single vibronic level fluorescence spectra from Hagedorn wavepacket dynamics.","authors":"Zhan Tong Zhang, Jiří J L Vaníček","doi":"10.1063/5.0219005","DOIUrl":"https://doi.org/10.1063/5.0219005","url":null,"abstract":"In single vibronic level (SVL) fluorescence experiments, the electronically excited initial state is also excited in one or several vibrational modes. Because computing such spectra by evaluating all contributing Franck-Condon factors becomes impractical (and unnecessary) in large systems, here we propose a time-dependent approach based on Hagedorn wavepacket dynamics. We use Hagedorn functions-products of a Gaussian and carefully generated polynomials-to represent SVL initial states because in systems whose potential is at most quadratic, Hagedorn functions are exact solutions to the time-dependent Schrödinger equation and can be propagated with the same equations of motion as a simple Gaussian wavepacket. Having developed an efficient recursive algorithm to compute the overlaps between two Hagedorn wavepackets, we can now evaluate emission spectra from arbitrary vibronic levels using a single trajectory. We validate the method in two-dimensional global harmonic models by comparing it with quantum split-operator calculations. In addition, we study the effects of displacement, distortion (squeezing), and Duschinsky rotation on SVL fluorescence spectra. Finally, we demonstrate the applicability of the Hagedorn approach to high-dimensional systems on a displaced, distorted, and Duschinsky-rotated harmonic model with 100 degrees of freedom.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142288175","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

Efficient random phase approximation for diradicals. 高效随机相位逼近二元化合物。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-09-21 DOI: 10.1063/5.0227556

Reza G Shirazi, Vladimir V Rybkin, Michael Marthaler, Dmitry S Golubev

引用次数: 0

Photoelectron spectroscopy of deprotonated benzonitrile. 去质子化苯腈的光电子能谱。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-09-21 DOI: 10.1063/5.0231206

Eleanor K Ashworth, James N Bull

{"title":"Photoelectron spectroscopy of deprotonated benzonitrile.","authors":"Eleanor K Ashworth, James N Bull","doi":"10.1063/5.0231206","DOIUrl":"https://doi.org/10.1063/5.0231206","url":null,"abstract":"The recent discovery of cyano-substituted aromatic and two-ring polycyclic aromatic hydrocarbon molecules in Taurus Molecular Cloud-1 has prompted questions on how the electronic structure and excited-state dynamics of these molecules are linked with their existence and abundance. Here, we report a photodetachment and frequency- and angle-resolved photoelectron spectroscopy study of jet-cooled para-deprotonated benzonitrile (p-[Bzn-H]-). The adiabatic detachment energy was determined as 1.70 ± 0.01 eV, in good agreement with CCSD(T)/aug-cc-pVTZ calculations. The spectra across the first few electron-volts above threshold are dominated by prompt autodetachment processes associated with excitation of at least five short-lived (tens of femtoseconds) temporary anion shaped resonances since excitation cross sections are several orders of magnitude larger than direct photodetachment cross sections. The photoexcitation vibronic profile is dominated by a ≈640 cm-1 ring deformation mode. [Bzn-H]- lacks a valence-localized excited state situated below the detachment threshold and does not exhibit thermionic emission following excitation of the temporary anion resonances. Thus, [Bzn-H]- is unlikely to be stable in many interstellar environments.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142288171","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

Polarization-dependent photoemission electron microscopy for domain imaging of inorganic and molecular materials. 用于无机和分子材料畴成像的偏振相关光发射电子显微镜。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-09-21 DOI: 10.1063/5.0225765

Atreyie Ghosh, Joseph L Spellberg, Sarah B King

引用次数: 0

MOSP: A user-interface package for simulating metal nanoparticle's structure and reactivity under operando conditions. MOSP：在操作条件下模拟金属纳米粒子结构和反应性的用户界面软件包。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-09-21 DOI: 10.1063/5.0226023

Lei Ying, Beien Zhu, Yi Gao

引用次数: 0

A DFT/MRCI Hamiltonian parameterized using only ab initio data. II. Core-excited states. 仅使用 ab initio 数据参数化的 DFT/MRCI 哈密顿参数。II.核心激发态。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-09-21 DOI: 10.1063/5.0227385

Teagan Shane Costain, Jibrael B Rolston, Simon P Neville, Michael S Schuurman

{"title":"A DFT/MRCI Hamiltonian parameterized using only ab initio data. II. Core-excited states.","authors":"Teagan Shane Costain, Jibrael B Rolston, Simon P Neville, Michael S Schuurman","doi":"10.1063/5.0227385","DOIUrl":"https://doi.org/10.1063/5.0227385","url":null,"abstract":"A newly parameterized combined density functional theory and multi-reference configuration interaction (DFT/MRCI) Hamiltonian, termed core-valence separation (CVS)-QE12, is defined for the computation of K-shell core-excitation and core-ionization energies. This CVS counterpart to the recently reported QE8 Hamiltonian [Costain et al., J. Chem. Phys, 160, 224106 (2024)] is parameterized by fitting to benchmark quality ab initio data. The definition of the CVS-QE12 and QE8 Hamiltonians differ from previous CVS-DFT/MRCI parameterizations in three primary ways: (i) the replacement of the BHLYP exchange-correlation functional with QTP17 to yield a balanced description of both core and valence excitation energies, (ii) the adoption of a new, three-parameter damping function, and (iii) the introduction of separate scaling of the core-valence and valence-valence Coulombic interactions. Crucially, the parameters of the CVS-QE12 Hamiltonian are obtained via fitting exclusively to highly accurate ab initio vertical core-excitation and ionization energies computed at the CVS-EOM-CCSDT level of theory. The CVS-QE12 Hamiltonian is validated against further benchmark computations and is found to furnish K-edge core vertical excitation and ionization energies exhibiting absolute errors ≤0.5 eV at low computational cost.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142288146","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